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Sample records for thermal decomposition mechanisms

  1. Resolving Some Paradoxes in the Thermal Decomposition Mechanism of Acetaldehyde

    Energy Technology Data Exchange (ETDEWEB)

    Sivaramakrishnan, Raghu; Michael, Joe V.; Harding, Lawrence B.; Klippenstein, Stephen J.

    2015-07-16

    The mechanism for the thermal decomposition of acetaldehyde has been revisited with an analysis of literature kinetics experiments using theoretical kinetics. The present modeling study was motivated by recent observations, with very sensitive diagnostics, of some unexpected products in high temperature micro-tubular reactor experiments on the thermal decomposition of CH3CHO and its deuterated analogs, CH3CDO, CD3CHO, and CD3CDO. The observations of these products prompted the authors of these studies to suggest that the enol tautomer, CH2CHOH (vinyl alcohol), is a primary intermediate in the thermal decomposition of acetaldehyde. The present modeling efforts on acetaldehyde decomposition incorporate a master equation re-analysis of the CH3CHO potential energy surface (PES). The lowest energy process on this PES is an isomerization of CH3CHO to CH2CHOH. However, the subsequent product channels for CH2CHOH are substantially higher in energy, and the only unimolecular process that can be thermally accessed is a re-isomerization to CH3CHO. The incorporation of these new theoretical kinetics predictions into models for selected literature experiments on CH3CHO thermal decomposition confirms our earlier experiment and theory based conclusions that the dominant decomposition process in CH3CHO at high temperatures is C-C bond fission with a minor contribution (~10-20%) from the roaming mechanism to form CH4 and CO. The present modeling efforts also incorporate a master-equation analysis of the H + CH2CHOH potential energy surface. This bimolecular reaction is the primary mechanism for removal of CH2CHOH, which can accumulate to minor amounts at high temperatures, T > 1000 K, in most lab-scale experiments that use large initial concentrations of CH3CHO. Our modeling efforts indicate that the observation of ketene, water and acetylene in the recent micro-tubular experiments are primarily due to bimolecular reactions of CH3CHO and CH2CHOH with H-atoms, and have no bearing on

  2. Mechanism of the Thermal Decomposition of Ethanethiol and Dimethylsulfide

    Science.gov (United States)

    Melhado, William Francis; Whitman, Jared Connor; Kong, Jessica; Anderson, Daniel Easton; Vasiliou, AnGayle (AJ)

    2016-06-01

    Combustion of organosulfur contaminants in petroleum-based fuels and biofuels produces sulfur oxides (SO_x). These pollutants are highly regulated by the EPA because they have been linked to poor respiratory health and negative environmental impacts. Therefore much effort has been made to remove sulfur compounds in petroleum-based fuels and biofuels. Currently desulfurization methods used in the fuel industry are costly and inefficient. Research of the thermal decomposition mechanisms of organosulfur species can be implemented via engineering simulations to modify existing refining technologies to design more efficient sulfur removal processes. We have used a resistively-heated SiC tubular reactor to study the thermal decomposition of ethanethiol (CH_3CH_2SH) and dimethylsulfide (CH_3SCH_3). The decomposition products are identified by two independent techniques: 118.2 nm VUV photoionization mass spectroscopy and infrared spectroscopy. The thermal cracking products for CH_3CH_2SH are CH_2CH_2, SH, and H_2S and the thermal cracking products from CH_3SCH_3 are CH_3S, CH_2S, and CH_3.

  3. The kinetics and mechanism of induced thermal decomposition of ...

    Indian Academy of Sciences (India)

    The kinetics of induced decomposition of potassium peroxomonosulphate (PMS) by the phase transfer catalysts (PTC), viz. tetrabutylammonium chloride [TBAC] and tetrabutylphosphonium chloride [TBPC] have been investigated. The effect of [PMS], [PTC], ionic strength of the medium and temperature on the rate of ...

  4. The kinetics and mechanism of induced thermal decomposition of ...

    Indian Academy of Sciences (India)

    Unknown

    only in organic chemistry 1 but also in inorganic chemistry 2, analytical application 3, in electrochemistry 4–7, photochemistry 8,9 and in polymer chemistry 10–15. The spontaneous decomposition of potassium peroxomonosulphate (PMS) in aqueous solution suggests that free radicals are not formed. The kinetics and ...

  5. Ab initio kinetics and thermal decomposition mechanism of mononitrobiuret and 1,5-dinitrobiuret

    Science.gov (United States)

    Sun, Hongyan; Vaghjiani, Ghanshyam L.

    2015-05-01

    Mononitrobiuret (MNB) and 1,5-dinitrobiuret (DNB) are tetrazole-free, nitrogen-rich, energetic compounds. For the first time, a comprehensive ab initio kinetics study on the thermal decomposition mechanisms of MNB and DNB is reported here. In particular, the intramolecular interactions of amine H-atom with electronegative nitro O-atom and carbonyl O-atom have been analyzed for biuret, MNB, and DNB at the M06-2X/aug-cc-pVTZ level of theory. The results show that the MNB and DNB molecules are stabilized through six-member-ring moieties via intramolecular H-bonding with interatomic distances between 1.8 and 2.0 Å, due to electrostatic as well as polarization and dispersion interactions. Furthermore, it was found that the stable molecules in the solid state have the smallest dipole moment amongst all the conformers in the nitrobiuret series of compounds, thus revealing a simple way for evaluating reactivity of fuel conformers. The potential energy surface for thermal decomposition of MNB was characterized by spin restricted coupled cluster theory at the RCCSD(T)/cc-pV∞ Z//M06-2X/aug-cc-pVTZ level. It was found that the thermal decomposition of MNB is initiated by the elimination of HNCO and HNN(O)OH intermediates. Intramolecular transfer of a H-atom, respectively, from the terminal NH2 group to the adjacent carbonyl O-atom via a six-member-ring transition state eliminates HNCO with an energy barrier of 35 kcal/mol and from the central NH group to the adjacent nitro O-atom eliminates HNN(O)OH with an energy barrier of 34 kcal/mol. Elimination of HNN(O)OH is also the primary process involved in the thermal decomposition of DNB, which processes C2v symmetry. The rate coefficients for the primary decomposition channels for MNB and DNB were quantified as functions of temperature and pressure. In addition, the thermal decomposition of HNN(O)OH was analyzed via Rice-Ramsperger-Kassel-Marcus/multi-well master equation simulations, the results of which reveal the formation

  6. Ab Initio Kinetics and Thermal Decomposition Mechanism of Mononitrobiuret and 1,5- Dinitrobiuret

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Hongyan; Vaghjiani, Ghanshyam G.

    2015-05-26

    Mononitrobiuret (MNB) and 1,5-dinitrobiuret (DNB) are tetrazole-free, nitrogen-rich, energetic compounds. For the first time, a comprehensive ab initio kinetics study on the thermal decomposition mechanisms of MNB and DNB is reported here. In particular, the intramolecular interactions of amine H-atom with electronegative nitro O-atom and carbonyl O-atom have been analyzed for biuret, MNB, and DNB at the M06-2X/aug-cc-pVTZ level of theory. The results show that the MNB and DNB molecules are stabilized through six-member-ring moieties via intramolecular H-bonding with interatomic distances between 1.8 and 2.0 Å, due to electrostatic as well as polarization and dispersion interactions. Furthermore, it was found that the stable molecules in the solid state have the smallest dipole moment amongst all the conformers in the nitrobiuret series of compounds, thus revealing a simple way for evaluating reactivity of fuel conformers. The potential energy surface for thermal decomposition of MNB was characterized by spin restricted coupled cluster theory at the RCCSD(T)/cc-pV∞ Z//M06-2X/aug-cc-pVTZ level. It was found that the thermal decomposition of MNB is initiated by the elimination of HNCO and HNN(O)OH intermediates. Intramolecular transfer of a H-atom, respectively, from the terminal NH2 group to the adjacent carbonyl O-atom via a six-member-ring transition state eliminates HNCO with an energy barrier of 35 kcal/mol and from the central NH group to the adjacent nitro O-atom eliminates HNN(O)OH with an energy barrier of 34 kcal/mol. Elimination of HNN(O)OH is also the primary process involved in the thermal decomposition of DNB, which processes C2v symmetry. The rate coefficients for the primary decomposition channels for MNB and DNB were quantified as functions of temperature and pressure. In addition, the thermal decomposition of HNN(O)OH was analyzed via Rice–Ramsperger–Kassel–Marcus/multi-well master equation simulations, the results of which reveal the

  7. Study on the kinetics and mechanism of grain growth during the thermal decomposition of magnesite

    Energy Technology Data Exchange (ETDEWEB)

    Fu, Daxue; Feng, Naixiang; Wang, Yaowu [Northeastern Univ., Shenyang (China)

    2012-04-15

    The X-ray line broadening technique was used to calculate the grain size of MgO at 1023, 1123, 1223 K respectively either in CO{sub 2} or during the thermal decomposition of magnesites in air as well as in vacuum. By referring to the conventional grain growth equation, D{sup n} = kt, the activation energy and pre-exponential factor for the process in air are gained as 125.8 kJ/mol and 1.56 X 10{sup 8} nm{sup 4}/s, respectively. Raman spectroscopy was employed to study the surface structure of MgO obtained during calcination of magnesite, by which the mechanism of grain growth was analyzed and discussed. It is suggested that a kind of highly reactive MgO is produced during the thermal decomposition of magnesites, which is exactly the reason why the activation energy of the grain growth during the thermal decomposition of magnesite is lower than that of bulk diffusion or surface diffusion.

  8. Study on the kinetics and mechanism of grain growth during the thermal decomposition of magnesite

    Energy Technology Data Exchange (ETDEWEB)

    Fu, Daxue; Feng, Naixiang; Wang, Yaowu [Northeastern Univ., Shenyang (China)

    2012-04-15

    The X-ray line broadening technique was used to calculate the grain size of MgO at 1023, 1123, 1223 K respectively either in CO{sub 2} or during the thermal decomposition of magnesites in air as well as in vacuum. By referring to the conventional grain growth equation, D{sup n} = kt, the activation energy and pre-exponential factor for the process in air are gained as 125.8 kJ/mol and 1.56 X 10{sup 8} nm{sup 4}/s, respectively. Ran man spectroscopy was employed to study the surface structure of MgO obtained during calcination of magnesite, by which the mechanism of grain growth was analyzed and discussed. It is suggested that a kind of highly reactive MgO is produced during the thermal decomposition of magnesites, which is exactly the reason why the activation energy of the grain growth during the thermal decomposition of magnesite is lower than that of bulk diffusion or surface diffusion.

  9. Ab initio kinetics and thermal decomposition mechanism of mononitrobiuret and 1,5-dinitrobiuret

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Hongyan, E-mail: hongyan.sun1@gmail.com, E-mail: ghanshyam.vaghjiani@us.af.mil; Vaghjiani, Ghanshyam L., E-mail: hongyan.sun1@gmail.com, E-mail: ghanshyam.vaghjiani@us.af.mil [Propellants Branch, Rocket Propulsion Division, Aerospace Systems Directorate, Air Force Research Laboratory, AFRL/RQRP, 10 E. Saturn Blvd., Edwards AFB, California 93524 (United States)

    2015-05-28

    Mononitrobiuret (MNB) and 1,5-dinitrobiuret (DNB) are tetrazole-free, nitrogen-rich, energetic compounds. For the first time, a comprehensive ab initio kinetics study on the thermal decomposition mechanisms of MNB and DNB is reported here. In particular, the intramolecular interactions of amine H-atom with electronegative nitro O-atom and carbonyl O-atom have been analyzed for biuret, MNB, and DNB at the M06-2X/aug-cc-pVTZ level of theory. The results show that the MNB and DNB molecules are stabilized through six-member-ring moieties via intramolecular H-bonding with interatomic distances between 1.8 and 2.0 Å, due to electrostatic as well as polarization and dispersion interactions. Furthermore, it was found that the stable molecules in the solid state have the smallest dipole moment amongst all the conformers in the nitrobiuret series of compounds, thus revealing a simple way for evaluating reactivity of fuel conformers. The potential energy surface for thermal decomposition of MNB was characterized by spin restricted coupled cluster theory at the RCCSD(T)/cc-pV∞ Z//M06-2X/aug-cc-pVTZ level. It was found that the thermal decomposition of MNB is initiated by the elimination of HNCO and HNN(O)OH intermediates. Intramolecular transfer of a H-atom, respectively, from the terminal NH{sub 2} group to the adjacent carbonyl O-atom via a six-member-ring transition state eliminates HNCO with an energy barrier of 35 kcal/mol and from the central NH group to the adjacent nitro O-atom eliminates HNN(O)OH with an energy barrier of 34 kcal/mol. Elimination of HNN(O)OH is also the primary process involved in the thermal decomposition of DNB, which processes C{sub 2v} symmetry. The rate coefficients for the primary decomposition channels for MNB and DNB were quantified as functions of temperature and pressure. In addition, the thermal decomposition of HNN(O)OH was analyzed via Rice–Ramsperger–Kassel–Marcus/multi-well master equation simulations, the results of which

  10. Thermal decomposition of hemicelluloses

    OpenAIRE

    Werner, Kajsa; Pommer, Linda; Broström, Markus

    2014-01-01

    Decomposition modeling of biomass often uses commercially available xylan as model compound representing hemicelluloses, not taking in account the heterogeneous nature of that group of carbohydrates. In this study, the thermal decomposition behavior of seven different hemicelluloses (beta-glucan, arabinogalactan, arabinoxylan, galactomannan, glucomannan, xyloglucan, and xylan) were investigated in inert atmosphere using (i) thermogravimetric analysis coupled to Fourier transform infrared spec...

  11. Research on the Thermal Decomposition Reaction Kinetics and Mechanism of Pyridinol-Blocked Isophorone Diisocyanate

    Directory of Open Access Journals (Sweden)

    Sen Guo

    2016-02-01

    Full Text Available A series of pyridinol-blocked isophorone isocyanates, based on pyridinol including 2-hydroxypyridine, 3-hydroxypyridine, and 4-hydroxypyridine, was synthesized and characterized by 1H-NMR, 13C-NMR, and FTIR spectra. The deblocking temperature of blocked isocyanates was established by thermo-gravimetric analysis (TGA, differential scanning calorimetry (DSC, and the CO2 evaluation method. The deblocking studies revealed that the deblocking temperature was increased with pyridinol nucleophilicity in this order: 3-hydroxypyridine > 4-hydroxypyridine > 2-hydroxypyridine. The thermal decomposition reaction of 4-hydroxypyridine blocked isophorone diisocyanate was studied by thermo-gravimetric analysis. The Friedman–Reich–Levi (FRL equation, Flynn–Wall–Ozawa (FWO equation, and Crane equation were utilized to analyze the thermal decomposition reaction kinetics. The activation energy calculated by FRL method and FWO method was 134.6 kJ·mol−1 and 126.2 kJ·mol−1, respectively. The most probable mechanism function calculated by the FWO method was the Jander equation. The reaction order was not an integer because of the complicated reactions of isocyanate.

  12. Thermal Decomposition Mechanisms of Lignin Model Compounds: From Phenol to Vanillin

    Science.gov (United States)

    Scheer, Adam Michael

    Lignin is a complex, aromatic polymer abundant in cellulosic biomass (trees, switchgrass etc.). Thermochemical breakdown of lignin for liquid fuel production results in undesirable polycyclic aromatic hydrocarbons that lead to tar and soot byproducts. The fundamental chemistry governing these processes is not well understood. We have studied the unimolecular thermal decomposition mechanisms of aromatic lignin model compounds using a miniature SiC tubular reactor. Products are detected and characterized using time-of-flight mass spectrometry with both single photon (118.2 nm; 10.487 eV) and 1 + 1 resonance-enhanced multiphoton ionization (REMPI) as well as matrix isolation infrared spectroscopy. Gas exiting the heated reactor (300 K--1600 K) is subject to a free expansion after a residence time of approximately 100 micros. The expansion into vacuum rapidly cools the gas mixture and allows the detection of radicals and other highly reactive intermediates. By understanding the unimolecular fragmentation patterns of phenol (C6H5OH), anisole (C6H 5OCH3) and benzaldehyde (C6H5CHO), the more complicated thermocracking processes of the catechols (HO-C 6H4-OH), methoxyphenols (HO-C6H4-OCH 3) and hydroxybenzaldehydes (HO-C6H4-CHO) can be interpreted. These studies have resulted in a predictive model that allows the interpretation of vanillin, a complex phenolic ether containing methoxy, hydroxy and aldehyde functional groups. This model will serve as a guide for the pyrolyses of larger systems including lignin monomers such as coniferyl alcohol. The pyrolysis mechanisms of the dimethoxybenzenes (H3C-C 6H4-OCH3) and syringol, a hydroxydimethoxybenzene have also been studied. These results will aid in the understanding of the thermal fragmentation of sinapyl alcohol, the most complex lignin monomer. In addition to the model compound work, pyrolyisis of biomass has been studied via the pulsed laser ablation of poplar wood. With the REMPI scheme, aromatic lignin decomposition

  13. Thermal decomposition of illite

    Directory of Open Access Journals (Sweden)

    Araújo José Humberto de

    2004-01-01

    Full Text Available The effect of heat treatment on illite in air at temperatures ranging from 750 to 1150 °C was studied using the Mössbauer effect in 57Fe. The dependence of the Mössbauer parameters and relative percentage of the radiation absorption area was measured as a function of the firing temperature. The onset of thermal structural decomposition occurred at 800 °C. With rising temperature, the formation of hematite (Fe2O3 increased at the expense of the silicate mineral.

  14. Structure-Activity Relationship Analysis of the Thermal Stabilities of Nitroaromatic Compounds Following Different Decomposition Mechanisms.

    Science.gov (United States)

    Li, Jiazhong; Liu, Huanxiang; Huo, Xing; Gramatica, Paola

    2013-02-01

    The decomposition behavior of energetic materials is very important for the safety problems concerning their production, transportation, use and storage, because molecular decomposition is intimately connected to their explosive properties. Nitroaromatic compounds, particularly nitrobenzene derivatives, are often considered as prototypical energetic molecules, and some of them are commonly used as high explosives. Quantitative structure-activity relationship (QSAR) represents a potential tool for predicting the thermal stability properties of energetic materials. But it is reported that constructing general reliable models to predict their stability and their potential explosive properties is a very difficult task. In this work, we make our efforts to investigate the relationship between the molecular structures and corresponding thermal stabilities of 77 nitrobenzene derivatives with various substituent functional groups (in ortho, meta and/or para positions). The proposed best MLR model, developed by the new software QSARINS, based on Genetic Algorithm for variable selection and with various validation tools, is robust, stable and predictive with R(2) of 0.86, QLOO (2) of 0.79 and CCC of 0.90. The results indicated that, though difficult, it is possible to build predictive, externally validated QSAR models to estimate the thermal stability of nitroaromatic compounds. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Ab initio Kinetics and Thermal Decomposition Mechanism of Mononitrobiuret and 1,5-Dinitrobiuret

    Science.gov (United States)

    2016-03-14

    energy barrier of 35 kcal/mol, and from the central NH group to the adjacent nitro O-atom eliminates HNN(O)OH with an energy barrier of 34 kcal/mol...Elimination of HNN(O)OH is also the primary channel involved in the thermal decomposition of DNB, which processes C2v symmetry . The rate coefficients... central NH group to the adjacent nitro O-atom eliminates HNN(O)OH with an energy barrier of 34 kcal/mol. Elimination of HNN(O)OH is also the primary

  16. Thermal stability and mechanism of decomposition of emulsion explosives in the presence of pyrite.

    Science.gov (United States)

    Xu, Zhi-Xiang; Wang, Qian; Fu, Xiao-Qi

    2015-12-30

    The reaction of emulsion explosives (ammonium nitrate) with pyrite was studied using techniques of TG-DTG-DTA. TG-DSC-MS was also used to analyze samples thermal decomposition process. When a mixture of pyrite and emulsion explosives was heated at a constant heating rate of 10K/min from room temperature to 350°C, exothermic reactions occurred at about 200°C. The essence of reaction between emulsion explosives and pyrite is the reaction between ammonium nitrate and pyrite. Emulsion explosives have excellent thermal stability but it does not mean it showed the same excellent thermal stability when pyrite was added. Package emulsion explosives were more suitable to use in pyrite shale than bulk emulsion explosives. The exothermic reaction was considered to take place between ammonium nitrate and pyrite where NO, NO2, NH3, SO2 and N2O gases were produced. Based on the analysis of the gaseous, a new overall reaction was proposed, which was thermodynamically favorable. The results have significant implication in the understanding of stability of emulsion explosives in reactive mining grounds containing pyrite minerals. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. Thermal Decomposition of Methyl Esters in Biodiesel Fuel: Kinetics, Mechanisms and Products

    Science.gov (United States)

    Chai, Ming

    Biodiesel continues to enjoy increasing popularity. However, recent studies on carbonyl compounds emissions from biodiesel fuel are inconclusive. Emissions of carbonyl compounds from petroleum diesel fuels were compared to emissions from pure biodiesel fuels and petroleum-biodiesel blends used in a non-road diesel generator. The concentration of total carbonyl compounds was the highest when the engine was idling. The carbonyl emissions, as well as ozone formation potential, from biodiesel fuel blends were higher than those emitted from petroleum diesel fuel. The sulfur content of diesel fuel and the source of biodiesel fuel were not found to have a significant impact on emissions of carbonyl compounds. Mechanism parameters of the thermal decomposition of biodiesel-range methyl esters were obtained from the results of thermal gravimetric analysis (TGA). The overall reaction orders are between 0.49 and 0.71 and the energies of activation are between 59.9 and 101.3 kJ/mole. Methyl esters in air have lower activation energies than those in nitrogen. Methyl linoleate has the lowest activation energy, followed by methyl oleate, and methyl stearate. The pyrolysis and oxidation of the three methyl esters were investigated using a semi-isothermal tubular flow reactor. The profiles of major products versus reaction temperature are presented. In the pyrolysis of methyl stearate, the primary reaction pathway is the decarboxylic reaction at the methyl ester functional group. Methyl oleate's products indicate more reactions on its carbon-carbon double bond. Methyl linoleate shows highest reactivity among the three methyl esters, and 87 products were detected. The oxidation of three methyl esters resulted in more products in all compound classes, and 55, 114, and 127 products were detected, respectively. The oxidation of methyl esters includes decarboxylation on ester group. The methyl ester's carbon chain could be oxidized as a hydrocarbon compound and form oxidized esters and

  18. Thermal stability and mechanism of decomposition of emulsion explosives in the presence of pyrite

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Zhi-Xiang; Wang, Qian [School of Energy and Power Engineering, Jiangsu University, Zhenjiang 212013 (China); Fu, Xiao-Qi, E-mail: xzx19820708@163.com [School of Chemistry and Chemical Engineering, Jiangsu University Zhenjiang 212013 (China)

    2015-12-30

    Highlights: • An exothermic reaction occurs at about 200 °C between pyrite and ammonium nitrate (emulsion explosives). • The essence of reaction between emulsion explosives and pyrite is reaction between ammonium nitrate and pyrite. • The excellent thermal stability of emulsion explosives does not mean it was also showed when pyrite was added. • A new overall reaction has been proposed as: • 14FeS{sub 2}(s) + 91NH{sub 4}NO{sub 3}(s) → 52NO(g) + 26SO{sub 2}(g) + 6Fe{sub 2}O{sub 3}(s) + 78NH{sub 3}(g) + 26N{sub 2}O(g) + 2FeSO{sub 4}(s) + 65H{sub 2}O(g). - Abstract: The reaction of emulsion explosives (ammonium nitrate) with pyrite was studied using techniques of TG-DTG-DTA. TG–DSC–MS was also used to analyze samples thermal decomposition process. When a mixture of pyrite and emulsion explosives was heated at a constant heating rate of 10 K/min from room temperature to 350 °C, exothermic reactions occurred at about 200 °C. The essence of reaction between emulsion explosives and pyrite is the reaction between ammonium nitrate and pyrite. Emulsion explosives have excellent thermal stability but it does not mean it showed the same excellent thermal stability when pyrite was added. Package emulsion explosives were more suitable to use in pyrite shale than bulk emulsion explosives. The exothermic reaction was considered to take place between ammonium nitrate and pyrite where NO, NO{sub 2}, NH{sub 3}, SO{sub 2} and N{sub 2}O gases were produced. Based on the analysis of the gaseous, a new overall reaction was proposed, which was thermodynamically favorable. The results have significant implication in the understanding of stability of emulsion explosives in reactive mining grounds containing pyrite minerals.

  19. Self-healing slip pulses driven by thermal decomposition: Towards identifying dynamic weakening mechanisms in seismic observations

    Science.gov (United States)

    Platt, J. D.; Viesca, R. C.; Garagash, D.

    2012-12-01

    Seismological observations indicate that earthquake ruptures commonly propagate as self-healing slip pulses, with slip duration at any location on the fault being much shorter than the total event duration [Heaton 1990]. Theoretical work has linked these slip pulses to low values of the background driving stress on the fault [Zheng and Rice 1998]. Recent experiments [Han et al. 2007;Brantut et al. 2008] have shown that fault materials may thermally decompose during shear. These endothermic reactions release pore fluid, leading to an increase in pore pressure and a decrease in temperature [Sulem and Famin 2009]. An Arrhenius kinetic controls the reaction rate, and dynamic weakening only occurs when the temperature reaches a critical temperature triggering the reaction. This abrupt change is in sharp contrast with thermal pressurization where the pore pressure increases smoothly with slip. Previous theoretical studies of thermal decomposition have focused on simple mechanical systems with imposed slip rates [Sulem and Famin 2009], or coupling to a spring-slider model [Brantut et al. 2011]. We present the first solutions to couple thermal decomposition with dynamic rupture, extending the model in Garagash [2012] to solve for self-healing slip pulses. For a range of driving stresses there are two possible slip pulses, compared with a single solution for thermal pressurization alone. One solution corresponds to small slip and a low temperature rise that precludes the reaction; the other is a larger slip solution with weakening due to thermal pressurization at the rupture tip, and weakening due to thermal decomposition in the middle of the pulse. A dramatic drop in fault strength accompanies the onset of the reaction, leading to peak slip rates coinciding with the onset of the reaction. For thermal pressurization alone the maximum strain rate always occurs at the rupture tip, and depends sensitively on the driving stress. Thermal decomposition is identified by slower

  20. Thermal decomposition of natural dolomite

    Indian Academy of Sciences (India)

    Keywords. TGA–DTA; FTIR; X-ray diffraction; dolomite. Abstract. Thermal decomposition behaviour of dolomite sample has been studied by thermogravimetric (TG) measurements. Differential thermal analysis (DTA) curve of dolomite shows two peaks at 777.8°C and 834°C. The two endothermic peaks observed in dolomite ...

  1. Thermal decomposition of ammonium hexachloroosmate

    DEFF Research Database (Denmark)

    Asanova, T I; Kantor, Innokenty; Asanov, I. P.

    2016-01-01

    polymeric structure. Being revealed for the first time the intermediate was subjected to determine the local atomic structure around osmium. The thermal decomposition of hexachloroosmate is much more complex and occurs within a minimum two-step process, which has never been observed before....

  2. Thermal decomposition and non-isothermal decomposition kinetics of carbamazepine

    Science.gov (United States)

    Qi, Zhen-li; Zhang, Duan-feng; Chen, Fei-xiong; Miao, Jun-yan; Ren, Bao-zeng

    2014-12-01

    The thermal stability and kinetics of isothermal decomposition of carbamazepine were studied under isothermal conditions by thermogravimetry (TGA) and differential scanning calorimetry (DSC) at three heating rates. Particularly, transformation of crystal forms occurs at 153.75°C. The activation energy of this thermal decomposition process was calculated from the analysis of TG curves by Flynn-Wall-Ozawa, Doyle, distributed activation energy model, Šatava-Šesták and Kissinger methods. There were two different stages of thermal decomposition process. For the first stage, E and log A [s-1] were determined to be 42.51 kJ mol-1 and 3.45, respectively. In the second stage, E and log A [s-1] were 47.75 kJ mol-1 and 3.80. The mechanism of thermal decomposition was Avrami-Erofeev (the reaction order, n = 1/3), with integral form G(α) = [-ln(1 - α)]1/3 (α = ˜0.1-0.8) in the first stage and Avrami-Erofeev (the reaction order, n = 1) with integral form G(α) = -ln(1 - α) (α = ˜0.9-0.99) in the second stage. Moreover, Δ H ≠, Δ S ≠, Δ G ≠ values were 37.84 kJ mol-1, -192.41 J mol-1 K-1, 146.32 kJ mol-1 and 42.68 kJ mol-1, -186.41 J mol-1 K-1, 156.26 kJ mol-1 for the first and second stage, respectively.

  3. Quantum mechanical studies of the kinetics, mechanisms and thermodynamics of gas-phase thermal decomposition of ethyl dithiocarbonate (xanthate

    Directory of Open Access Journals (Sweden)

    I.A. Adejoro

    2017-09-01

    Full Text Available Theoretical studies were carried out to investigate the thermal decomposition of ethyl dithiocarbonates (xanthate using Hartree–Fock at the HF/321-G* level and the density functional method with Becke 3 Lee Yang pair DFT/(B3LYP, 6-31G*, 6-31G**, 6-31+G*, MP2 and CCSD in the ab initio method of calculation using Spartan 10. Geometric parameters, such as the bond length, bond angles, dihedral angles, heat of formation, atomic charges and vibrational frequencies, were obtained. The data were used to calculate the thermodynamics parameters, change in entropy ΔS, enthalpy change ΔH, free energy G, pre-exponential factor A, rate k at 623 K, and variation of rate k with temperatures from 498–623 K at temperature intervals of 25 K. It was observed that the values obtained are in good agreement with the experimental values for the ab initio methods, and according to Arrhenius theory, the calculated rate k increases with increasing temperature.

  4. Development of a QSPR model for predicting thermal stabilities of nitroaromatic compounds taking into account their decomposition mechanisms.

    Science.gov (United States)

    Fayet, Guillaume; Rotureau, Patricia; Joubert, Laurent; Adamo, Carlo

    2011-10-01

    The molecular structures of 77 nitroaromatic compounds have been correlated to their thermal stabilities by combining the quantitative structure-property relationship (QSPR) method with density functional theory (DFT). More than 300 descriptors (constitutional, topological, geometrical and quantum chemical) have been calculated, and multilinear regressions have been performed to find accurate quantitative relationships with experimental heats of decomposition (-ΔH). In particular, this work demonstrates the importance of accounting for chemical mechanisms during the selection of an adequate experimental data set. A reliable QSPR model that presents a strong correlation with experimental data for both the training and the validation molecular sets (R (2) = 0.90 and 0.84, respectively) was developed for non-ortho-substituted nitroaromatic compounds. Moreover, its applicability domain was determined, and the model's predictivity reached 0.86 within this applicability domain. To our knowledge, this work has produced the first QSPR model, developed according to the OECD principles of regulatory acceptability, for predicting the thermal stabilities of energetic compounds.

  5. Thermal decomposition mechanisms of the methoxyphenols: formation of phenol, cyclopentadienone, vinylacetylene, and acetylene.

    Science.gov (United States)

    Scheer, Adam M; Mukarakate, Calvin; Robichaud, David J; Nimlos, Mark R; Ellison, G Barney

    2011-11-24

    The pyrolyses of the guaiacols or methoxyphenols (o-, m-, and p-HOC(6)H(4)OCH(3)) have been studied using a heated SiC microtubular (μ-tubular) reactor. The decomposition products are detected by both photoionization time-of-flight mass spectroscopy (PIMS) and matrix isolation infrared spectroscopy (IR). Gas exiting the heated SiC μ-tubular reactor is subject to a free expansion after a residence time of approximately 50-100 μs. The PIMS reveals that, for all three guaiacols, the initial decomposition step is loss of methyl radical: HOC(6)H(4)OCH(3) → HOC(6)H(4)O + CH(3). Decarbonylation of the HOC(6)H(4)O radical produces the hydroxycyclopentadienyl radical, C(5)H(4)OH. As the temperature of the μ-tubular reactor is raised to 1275 K, the C(5)H(4)OH radical loses a H atom to produce cyclopentadienone, C(5)H(4)═O. Loss of CO from cyclopentadienone leads to the final products, acetylene and vinylacetylene: C(5)H(4)═O → [CO + 2 HC≡CH] or [CO + HC≡C-CH═CH(2)]. The formation of C(5)H(4)═O, HCCH, and CH(2)CHCCH is confirmed with IR spectroscopy. In separate studies of the (1 + 1) resonance-enhanced multiphoton ionization (REMPI) spectra, we observe the presence of C(6)H(5)OH in the molecular beam: C(6)H(5)OH + λ(275.1 nm) → [C(6)H(5)OH Ã] + λ(275.1nm) → C(6)H(5)OH(+). From the REMPI and PIMS signals and previous work on methoxybenzene, we suggest that phenol results from a radical/radical reaction: CH(3) + C(5)H(4)OH → [CH(3)-C(5)H(4)OH]* → C(6)H(5)OH + 2H.

  6. Doped tricalcium phosphate scaffolds by thermal decomposition of naphthalene: Mechanical properties and in vivo osteogenesis in a rabbit femur model.

    Science.gov (United States)

    Ke, Dongxu; Dernell, William; Bandyopadhyay, Amit; Bose, Susmita

    2015-11-01

    Tricalcium phosphate (TCP) is a bioceramic that is widely used in orthopedic and dental applications. TCP structures show excellent biocompatibility as well as biodegradability. In this study, porous β-TCP scaffolds were prepared by thermal decomposition of naphthalene. Scaffolds with 57.64% ± 3.54% density and a maximum pore size around 100 μm were fabricated via removing 30% naphthalene at 1150°C. The compressive strength for these scaffolds was 32.85 ± 1.41 MPa. Furthermore, by mixing 1 wt % SrO and 0.5 wt % SiO2 , pore interconnectivity improved, but the compressive strength decreased to 22.40 ± 2.70 MPa. However, after addition of polycaprolactone coating layers, the compressive strength of doped scaffolds increased to 29.57 ± 3.77 MPa. Porous scaffolds were implanted in rabbit femur defects to evaluate their biological property. The addition of dopants triggered osteoinduction by enhancing osteoid formation, osteocalcin expression, and bone regeneration, especially at the interface of the scaffold and host bone. This study showed processing flexibility to make interconnected porous scaffolds with different pore size and volume fraction porosity, while maintaining high compressive mechanical strength and excellent bioactivity. Results show that SrO/SiO2 -doped porous TCP scaffolds have excellent potential to be used in bone tissue engineering applications. © 2014 Wiley Periodicals, Inc.

  7. Studies on thermal decomposition mechanism of CL-20 by pyrolysis gas chromatography-mass spectrometry (Py-GC/MS)

    Energy Technology Data Exchange (ETDEWEB)

    Naik, N.H.; Gore, G.M. [High Energy Materials Research Laboratory, Sutarwadi, Pune 411021 (India); Gandhe, B.R. [Directorate of Armament, DRDO Bhavan, New Delhi 110011 (India); Sikder, A.K. [High Energy Materials Research Laboratory, Sutarwadi, Pune 411021 (India)], E-mail: ak_sikder@yahoo.com

    2008-11-30

    The thermal decomposition study of CL-20 (hexanitrohexaazaisowurtzitane) using pyrolysis GC/MS was carried out mainly by electron impact (EI) mode. Chemical ionization (CI) mode was used for further confirmation of identified species. Mass spectrum of CL-20 decomposition products predominantly revealed fragments with m/z 81 and 96 corresponding to C{sub 4}H{sub 5}N{sub 2}{sup +} and C{sub 4}H{sub 4}N{sub 2}O{sup +} ions, respectively. The total ion chromatogram (TIC) of CL-20 pyrolysis shows peak within first 2 min due to the presence of low molecular weight gases. Peaks corresponding to several other products were also observed including the atmospheric gases. Cyanogen formation (C{sub 2}N{sub 2}, m/z 52) observed to be enriched at the scan number 300-500. The low molecular mass range decomposition products formed by cleavage of C-N ring structure were found in majority. Additional structural information was sought by employing chemical ionization mode. The data generated during this study was instrumented in determining decomposition pathways of CL-20.

  8. Modeling yields insight into thermal decomposition

    Energy Technology Data Exchange (ETDEWEB)

    Case, J.L.; Carr, R.V.; Simpson, M.S. [Air Products and Chemicals, Inc., Allentown, PA (United States)

    1995-12-01

    A fundamental understanding of the thermal decomposition of nitrotoluenes is critical in evaluating the hazards associated with transporting and storing commercial volumes of these chemicals. Detailed modeling of an adiabatic, low PHI and semi-open (vented to a larger pressure vessel) calorimeter provides insight into a multiple reaction mechanism. The reaction rates developed, along with the significant effect of reactant or intermediates vaporization were confirmed with additional experimental results. Such an interpretation of nitrotoluene decomposition is consistent with recent isothermal experiments as well as with the body of data reported in the open literature. The low temperature or induction reactions are accurately represented with a first order Arrhenius model having typical values for kinetic and thermodynamic parameters. These reactions generate minimal amounts of non condensable gas. If the material is maintained at an elevated temperature, but prevented from self-heating (by external cooling), the intermediate products form thermally unstable and nonvolatile oligomers. At higher temperatures the remaining materials undergo explosive reactions characterized by high heats of reaction, large activation energies and massive releases of non condensable gas. Quantifying the rates of nitrotoluene and/or intermediate vaporization versus oligomerization is essential in evaluating the hazard of a thermal explosion involving a commercial quantity of nitrotoluene.

  9. Mechanical, thermal and decomposition behavior of poly(epsilon-caprolactone) nanocomposites with clay-supported carbon nanotube hybrids

    NARCIS (Netherlands)

    Terzopoulou, Zoe; Bikiaris, Dimitrios N.; Triantafyllidis, Konstantinos S.; Potsi, Georgia; Gournis, Dimitrios; Papageorgiou, George Z.; Rudolf, Petra

    2016-01-01

    Poly(epsilon-caprolactone) (PCL) nanocomposites with hybrid clay-supported carbon nanotubes (Clay-CNT) in concentrations 0.5, 1.0 and 2.5 wt% were prepared by melt mixing. Mechanical, structural and thermal properties of the nanocomposites were studied. All nanocomposites exhibited similar

  10. Preparation, Structure Characterization and Thermal Decomposition ...

    African Journals Online (AJOL)

    NJD

    thermal decomposition process of [Dy(m-MBA)3phen]2·H2O has been followed by thermal analysis. KEYWORDS ... X-ray diffraction, elemental analysis, UV and IR spectroscopy, .... diffractometer with graphite-monochromated Mo Kα radiation.

  11. Thermal decomposition of barium valerate in argon

    DEFF Research Database (Denmark)

    Torres, P.; Norby, Poul; Grivel, Jean-Claude

    2015-01-01

    The thermal decomposition of barium valerate (Ba(C4H9CO2)(2)/Ba-pentanoate) was studied in argon by means of thermogravimetry, differential thermal analysis, IR-spectroscopy, X-ray diffraction and hot-stage optical microscopy. Melting takes place in two different steps, at 200 degrees C and 280...

  12. Thermal decomposition of natural dolomite

    Indian Academy of Sciences (India)

    TECS

    the effects of experimental variables i.e. sample weight, particle size, purge gas velocity and crystalline structure, ... effect of chlorine ions on the decomposition kinetics of dolomite at various temperatures studied by ... to 1000°C at a heating rate of 10 K/min, (ii) N2-gas dyna- mic atmosphere (90 cm. 3 min. –1. ), (iii) alumina ...

  13. Thermal stability of the 'cave' mineral brushite CaHPO{sub 4}.2H{sub 2}O - Mechanism of formation and decomposition

    Energy Technology Data Exchange (ETDEWEB)

    Frost, Ray L., E-mail: r.frost@qut.edu.au [Chemistry Discipline, Faculty of Science and Technology, Queensland University of Technology, 2 George St., GPO Box 2434, Brisbane, Queensland 4001 (Australia); Palmer, Sara J. [Chemistry Discipline, Faculty of Science and Technology, Queensland University of Technology, 2 George St., GPO Box 2434, Brisbane, Queensland 4001 (Australia)

    2011-07-10

    Highlights: {yields} In this study the thermal stability of brushite is reported. {yields} Such a study is relevant to the elimination of renal canal stones. {yields} A mechanism for the formation of brushite is proposed. {yields} A mechanism for the decomposition of brushite is discussed. {yields} This research has implications for the control and removal of kidney stones. - Abstract: Thermogravimetry combined with evolved gas mass spectrometry has been used to ascertain the stability of the 'cave' mineral brushite. X-ray diffraction shows that brushite from the Jenolan Caves is very pure. Thermogravimetric analysis coupled with ion current mass spectrometry shows a mass loss at 111 {sup o}C due to loss of water of hydration. A further decomposition step occurs at 190 {sup o}C with the conversion of hydrogen phosphate to a mixture of calcium ortho-phosphate and calcium pyrophosphate. TG-DTG shows the mineral is not stable above 111 {sup o}C. A mechanism for the formation of brushite on calcite surfaces is proposed, and this mechanism has relevance to the formation of brushite in urinary tracts.

  14. On formation mechanism of Pd-Ir bimetallic nanoparticles through thermal decomposition of [Pd(NH{sub 3}){sub 4}][IrCl{sub 6}

    Energy Technology Data Exchange (ETDEWEB)

    Asanova, Tatyana I., E-mail: nti@niic.nsc.ru; Asanov, Igor P. [Nikolaev Institute of Inorganic Chemistry SB RAS (Russian Federation); Kim, Min-Gyu [Pohang University of Science and Technology, Beamline Research Division (Korea, Republic of); Gerasimov, Evgeny Yu. [Boreskov Institute of Catalysis SB RAS (Russian Federation); Zadesenets, Andrey V.; Plyusnin, Pavel E.; Korenev, Sergey V. [Nikolaev Institute of Inorganic Chemistry SB RAS (Russian Federation)

    2013-10-15

    The formation mechanism of Pd-Ir nanoparticles during thermal decomposition of double complex salt [Pd(NH{sub 3}){sub 4}][IrCl{sub 6}] has been studied by in situ X-ray absorption (XAFS) and photoelectron (XPS) spectroscopies. The changes in the structure of the Pd and Ir closest to the surroundings and chemical states of Pd, Ir, Cl, and N atoms were traced in the range from room temperature to 420 Degree-Sign C in inert atmosphere. It was established that the thermal decomposition process is carried out in 5 steps. The Pd-Ir nanoparticles are formed in pyramidal/rounded Pd-rich (10-200 nm) and dendrite Ir-rich (10-50 nm) solid solutions. A d charge depletion at Ir site and a gain at Pd, as well as the intra-atomic charge redistribution between the outer d and s and p electrons of both Ir and Pd in Pd-Ir nanoparticles, were found to occur.Graphical Abstract.

  15. Dissociative Ionization and Thermal Decomposition of Cyclopentanone.

    Science.gov (United States)

    Pastoors, Johan I M; Bodi, Andras; Hemberger, Patrick; Bouwman, Jordy

    2017-09-21

    Despite the growing use of renewable and sustainable biofuels in transportation, their combustion chemistry is poorly understood, limiting our efforts to reduce harmful emissions. Here we report on the (dissociative) ionization and the thermal decomposition mechanism of cyclopentanone, studied using imaging photoelectron photoion coincidence spectroscopy. The fragmentation of the ions is dominated by loss of CO, C 2 H 4 , and C 2 H 5 , leading to daughter ions at m/z 56 and 55. Exploring the C 5 H 8 O . + potential energy surface reveals hydrogen tunneling to play an important role in low-energy decarbonylation and probably also in the ethene-loss processes, yielding 1-butene and methylketene cations, respectively. At higher energies, pathways without a reverse barrier open up to oxopropenyl and cyclopropanone cations by ethyl-radical loss and a second ethene-loss channel, respectively. A statistical Rice-Ramsperger-Kassel-Marcus model is employed to test the viability of this mechanism. The pyrolysis of cyclopentanone is studied at temperatures ranging from about 800 to 1100 K. Closed-shell pyrolysis products, namely 1,3-butadiene, ketene, propyne, allene, and ethene, are identified based on their photoion mass-selected threshold photoelectron spectrum. Furthermore, reactive radical species such as allyl, propargyl, and methyl are found. A reaction mechanism is derived incorporating both stable and reactive species, which were not predicted in prior computational studies. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  16. Lignin Derivatives Formation In Catalysed Thermal Decomposition ...

    African Journals Online (AJOL)

    denise

    in the heat of gasification and mass fraction of non-combustible volatiles in solid. NaOH-catalysed thermal decomposition of pure and fire-retardant- cellulose. Kuroda and co-workers14 studied the Curie-point pyrolysis of Japanese softwood species of the red pine, cedar and cypress in the presence of inorganic substances ...

  17. Thermal decomposition of lead titanyl oxalate tetrahydrate

    NARCIS (Netherlands)

    van de Velde, G.M.H.; Oranje, P.J.D.

    1976-01-01

    The thermal behaviour of PbTiO(C2O4)2·4H2O (PTO) has been investigated, employing TG, quantitative DTA, infrared spectroscopy and (high temperature) X-ray powder diffraction. The decomposition involves four main steps. The first is the dehydration of the tetrahydrate (30–180°C), followed by a small

  18. An investigation of the decomposition mechanism of calcium carbonate

    Directory of Open Access Journals (Sweden)

    D. Wang

    2017-01-01

    Full Text Available This paper focuses on investigating the decomposition mechanism of ca lcium carbonate. The non-isothermal thermal decompositions of calcium carbonate under vacuum and flowing nitrogen atmosphere have been studied by thermogravimetric analysis. With the application of the advanced nonlinear isoconversional method, the determined activation energy for each condition is dependent on the extent of reaction. Based on the dependences, a process involving two consecutive decomposition steps has been simulated. The simulation results match the experimental results of flowing nitrogen atmosphere. Results indicate that the decomposition of calcium carbonate undergoes the process of the formation of the intermediate and metastable product.

  19. Thermal decompositions of light lanthanide aconitates

    Energy Technology Data Exchange (ETDEWEB)

    Brzyska, W.; Ozga, W. (Uniwersytet Marii Curie-Sklodowskiej, Lublin (Poland))

    The conditions of thermal decomposition of Y, La, Ce(III), Pr, Nd, Sm, and Gd aconitates have been studied. On heating, the aconitate of Ce(III) loses crystallization water to yield anhydrous salt, which then is transformed to oxide CeO/sub 2/. The aconitates of Y, Pr, Nd, Sm, Eu and Gd decompose in three stages. First, aconitates undergo dehydration to form the anhydrous salts, which next decompose to Ln/sub 2/O/sub 2/CO/sub 3/. In the last stage the thermal decomposition of Ln/sub 2/O/sub 2/CO/sub 3/ is accompanied by endothermic effect. Dehydration of aconitate of La undergoes in two stages. The anhydrous complex decomposes to La/sub 2/O/sub 2/CO/sub 3/; this subsequently decomposes to La/sub 2/O/sub 3/.

  20. Thermal Decomposition of IMX-104: Ingredient Interactions Govern Thermal Insensitivity

    Energy Technology Data Exchange (ETDEWEB)

    Maharrey, Sean [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Wiese-Smith, Deneille [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Highley, Aaron M. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Steill, Jeffrey D. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Behrens, Richard [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Kay, Jeffrey J. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2015-04-01

    This report summarizes initial studies into the chemical basis of the thermal insensitivity of INMX-104. The work follows upon similar efforts investigating this behavior for another DNAN-based insensitive explosive, IMX-101. The experiments described demonstrate a clear similarity between the ingredient interactions that were shown to lead to the thermal insensitivity observed in IMX-101 and those that are active in IMX-104 at elevated temperatures. Specifically, the onset of decomposition of RDX is shifted to a lower temperature based on the interaction of the RDX with liquid DNAN. This early onset of decomposition dissipates some stored energy that is then unavailable for a delayed, more violent release.

  1. Thermal decomposition of meat and bone meal

    Energy Technology Data Exchange (ETDEWEB)

    Conesa, J.A.; Fullana, A.; Font, R. [Department of Chemical Engineering, University of Alicante, P.O. Box 99, E-03080 Alicante (Spain)

    2003-12-01

    A series of runs has been performed to study the thermal behavior of meat and bone meal (MBM) both in inert and reactive atmosphere. Although they are actually burned, the thermal decomposition of such MBM wastes has not been studied from a scientific point of view until now. The aim of this work is to present and discuss the thermogravimetric behavior of MBM both in nitrogen and air atmospheres. A thermobalance has been used to carry out the study at three different heating rates. A kinetic scheme able to correlate simultaneously (with no variation of the kinetic constants) the runs performed at different heating rates and different atmospheres of reaction is presented.

  2. Thermal decomposition as route for silver nanoparticles

    Directory of Open Access Journals (Sweden)

    Navaladian S

    2006-01-01

    Full Text Available AbstractSingle crystalline silver nanoparticles have been synthesized by thermal decomposition of silver oxalate in water and in ethylene glycol. Polyvinyl alcohol (PVA was employed as a capping agent. The particles were spherical in shape with size below 10 nm. The chemical reduction of silver oxalate by PVA was also observed. Increase of the polymer concentration led to a decrease in the size of Ag particles. Ag nanoparticle was not formed in the absence of PVA. Antibacterial activity of the Ag colloid was studied by disc diffusion method.

  3. Synthesis of a novel volatile platinum complex for use in CVD and a study of the mechanism of its thermal decomposition in solution

    Energy Technology Data Exchange (ETDEWEB)

    Tagge, C.D.; Simpson, R.D.; Bergman, R.G. [Univ. of California, Berkeley, CA (United States); Hostetler, M.S.; Girolami, G.S.; Nuzzo, R.G. [Univ. of Illinois, Urbana, IL (United States)

    1996-03-20

    The synthesis, characterization, chemical vapor deposition, and mechanistic investigation of the thermal decomposition in aromatic solvents of cis-bis({eta}{sup 2},{eta}{sup 1}-pent-4-en-1-yl)platinum (1) are described. Complex 1 has a unique chelated structure, giving rise to enhanced volatility, and has proved useful for the chemical vapor deposition of thin platinum films under mild conditions. Films deposited on a glass slide in a hot walled glass tube at 175{degree}C have an elemental composition of 82% Pt and 18% C. Kinetic, deuterium labeling and chemical trapping experiments indicate that the decomposition of 1 in aromatic solvents proceeds by reversible {beta}-hydride elimination followed by reversible dissociation of 1,4-pentadiene to give a 3-coordinate platinum hydride intermediate (9). Reductive elimination of 1-pentene from 9 deposits metallic platinum. The rate of decomposition exhibits a significant {beta}-deuterium isotope effect of k{sub H}/k{sub D}=3.8{+-}0.3. Added olefins are rapidly isomerized during the decomposition of 1; trapping experiments with diphenylacetylene indicate that intermediate 9 is the highly active catalyst that is responsible for the alkene isomerization. 47 refs., 5 figs.

  4. Catalysis mechanism of Pd-promoted γ-alumina in the thermal decomposition of methane to hydrogen: A density functional theory study

    Energy Technology Data Exchange (ETDEWEB)

    Salam, M. Abdus; Abdullah, Bawadi, E-mail: bawadi_abdullah@utp.edu.my

    2017-02-15

    Thermo-catalytic methane decomposition to elemental hydrogen mechanism in transitional metals (Pd, Ni & Mo) promoted Al{sub 2}O{sub 3} (001) catalyst have been studied using the density functional theory (DFT). Decomposition reactions are spontaneous and favourable above 775 K for all promoter. Pd-promoted Al{sub 2}O{sub 3} (001) catalyst demonstrates a breakthrough decomposition activity in hydrogen production as compared to Ni− and Mo-promoted Al{sub 2}O{sub 3} (001) catalysts. The activation energy (E{sub a}) range of the catalysis for Pd promoted Al{sub 2}O{sub 3} (001) catalysts is 0.003–0.34 eV. Whereas, Ni and Mo promoted Al{sub 2}O{sub 3} (001) catalysts display activation energy E{sub a} in the range of 0.63–1.15 eV and 0.04–5.98 eV, respectively. Pd-promoted catalyst also shows a higher adsorption energy (−0.68 eV) and reactivity than that of Ni and Mo promoted Al{sub 2}O{sub 3} (001) catalysts. The rates of successive decomposition of methane are found to be 16.15 × 10{sup 12}, 15.95 × 10{sup 12} and 16.09 × 10{sup 12} s{sup −1} for the promoter of Pd, Ni and Mo, respectively. Pd promoted Al{sub 2}O{sub 3} (001) catalyst reduces the methane decomposition temperature (775 K) and deactivation rate significantly. The catalytic conditions and catalyst is promising in producing hydrogen to support hydrogen economy. - Highlights: • Transition metals (Pd, Ni & Mo) promoted γ-alumina catalysts are designed successfully. • Pd-promoted catalyst showed breakthrough activity in methane decomposition to hydrogen. • DFT study explored the catalysis mechanism of methane decomposition at atomic level. • Pd-promoted catalyst reduced temperature and activation barrier of methane decomposition reaction significantly.

  5. Thermal decompositions of heavy lanthanide aconitates

    Energy Technology Data Exchange (ETDEWEB)

    Brzyska, W.; Ozga, W. (Uniwersytet Marii Curie-Sklodowskiej, Lublin (Poland))

    The conditions of thermal decomposition of Tb(III), Dy, Ho, Er, Tm, Yb and Lu aconitates have been studied. On heating, the aconitates of heavy lanthanides lose crystallization water to yield anhydrous salts, which are then transformed into oxides. The aconitate of Tb(III) decomposes in two stages. First, the complex undergoes dehydration to form the anhydrous salt, which next decomposes directly to Tb/sub 4/O/sub 7/. The aconitates of Dy, Ho, Er, Tm, Yb and Lu decompose in three stages. On heating, the hydrated complexes lose crystallization water, yielding the anhydrous complexes; these subsequently decompose to Ln/sub 2/O/sub 3/ with intermediate formation of Ln/sub 2/O/sub 2/CO/sub 3/.

  6. Thermal Decomposition of Radiation-Damaged Polystyrene

    Energy Technology Data Exchange (ETDEWEB)

    J Abrefah GS Klinger

    2000-09-26

    The radiation-damaged polystyrene material (''polycube'') used in this study was synthesized by mixing a high-density polystyrene (''Dylene Fines No. 100'') with plutonium and uranium oxides. The polycubes were used on the Hanford Site in the 1960s for criticality studies to determine the hydrogen-to-fissile atom ratios for neutron moderation during processing of spent nuclear fuel. Upon completion of the studies, two methods were developed to reclaim the transuranic (TRU) oxides from the polymer matrix: (1) burning the polycubes in air at 873 K; and (2) heating the polycubes in the absence of oxygen and scrubbing the released monomer and other volatile organics using carbon tetrachloride. Neither of these methods was satisfactory in separating the TRU oxides from the polystyrene. Consequently, the remaining polycubes were sent to the Hanford Plutonium Finishing Plant (PFP) for storage. Over time, the high dose of alpha and gamma radiation has resulted in a polystyrene matrix that is highly cross-linked and hydrogen deficient and a stabilization process is being developed in support of Defense Nuclear Facility Safety Board Recommendation 94-1. Baseline processes involve thermal treatment to pyrolyze the polycubes in a furnace to decompose the polystyrene and separate out the TRU oxides. Thermal decomposition products from this degraded polystyrene matrix were characterized by Pacific Northwest National Laboratory to provide information for determining the environmental impact of the process and for optimizing the process parameters. A gas chromatography/mass spectrometry (GC/MS) system coupled to a horizontal tube furnace was used for the characterization studies. The decomposition studies were performed both in air and helium atmospheres at 773 K, the planned processing temperature. The volatile and semi-volatile organic products identified for the radiation-damaged polystyrene were different from those observed for virgin

  7. Thermal Decomposition of Radiation-Damaged Polystyrene

    Energy Technology Data Exchange (ETDEWEB)

    Abrefah, John; Klinger, George S.

    2000-09-26

    The radiation-damaged polystyrene (given the identification name of 'polycube') was fabricated by mixing high-density polystyrene material ("Dylene Fines # 100") with plutonium and uranium oxides. The polycubes were used in the 1960s for criticality studies during processing of spent nuclear fuel. The polycubes have since been stored for almost 40 years at the Hanford Plutonium Finishing Plant (PFP) after failure of two processes to reclaim the plutonium and uranium oxides from the polystyrene matrix. Thermal decomposition products from this highly cross-linked polystyrene matrix were characterized using Gas Chromatograph/Mass Spectroscopy (GC/MS) system coupled to a horizontal furnace. The decomposition studies were performed in air and helium atmospheres at about 773 K. The volatile and semi-volatile organic products for the radiation-damaged polystyrene were different compared to virgin polystyrene. The differences were in the number of organic species generated and their concentrations. In the inert (i.e., helium) atmosphere, the major volatile organic products identified (in order of decreasing concentrations) were styrene, benzene, toluene, ethylbenzene, xylene, nathphalene, propane, .alpha.-methylbenzene, indene and 1,2,3-trimethylbenzene. But in air, the major volatile organic species identified changed slightly. Concentrations of the organic species in the inert atmosphere were significantly higher than those for the air atmosphere processing. Overall, 38 volatile organic species were identified in the inert atmosphere compared to 49 species in air. Twenty of the 38 species in the inert conditions were also products in the air atmosphere. Twenty-two oxidized organic products were identified during thermal processing in air.

  8. Thermal decomposition of dolomite under CO2-air atmosphere

    Science.gov (United States)

    Subagjo, Wulandari, Winny; Adinata, Pratitis Mega; Fajrin, Anita

    2017-01-01

    This paper reports a study on thermal decomposition of dolomite under CO2-air. Calcination was carried out non-isothermally by using thermogravimetry analysis-differential scanning calorimetry (TGA-DSC) with a heating rate of 10°C/minute in an air atmosphere as well as 10 vol% CO2 and 90 vol% air atmosphere from 25 to 950°C. In addition, a thermodynamic modeling was also carried out to simulate dolomite calcination in different level of CO2-air atmosphere by using FactSage® 7.0. The the main constituents of typical dolomite from Gresik, East Java include MgCO3 (magnesite), CaCO3 (calcite), Ca(OH)2, CaO, MgO, and less than 1% of metal impurities. Based on the kinetics analysis from TGA results, it is found that non-isothermal dolomite calcination in 10 vol% CO2 atmosphere is occurred in a two-stage reaction; the first stage is the decomposition of magnesite at 650-740 °C with activation energy of 161.23 kJ/mol, and the second stage is the decomposition of calcite at 775-820 °C with activation energy of 162.46 kJ/mol. The magnesite decomposition is found to follow nucleation reaction mechanism of Avrami Eroveyef (A3), while calcite decomposition follows second order chemical reaction equation. Thermodynamic modeling supports these kinetic analyses. The results of this research give insight to the kinetics of dolomite decomposition in CO2-air atmosphere.

  9. Preparation and formation mechanism of porous carbon nanosheets by thermal decomposition of polyvinyl alcohol films impregnated with zinc (II) and nitrate ions

    Science.gov (United States)

    Hattori, Yoshiyuki; Kojima, Rikio; Sagisaka, Kento; Umeda, Motoki; Tanaka, Toshihisa; Kondo, Atsushi; Iiyama, Taku; Kimura, Mutsumi; Fujimoto, Hiroyuki; Touhara, Hidekazu

    2017-03-01

    Porous carbon nanosheets (PCNS) with high surface areas were prepared by thermal decomposition of polyvinyl alcohol (PVA) films impregnated with Zn2+ and NO3-. Through this simple preparation method that required no additional activation processes, curved carbon nanosheets (1600 m2 g-1) and bimodal pore structure consisting of micropores and mesopores. Because of their unique structural properties, the PCNS are attractive for use as electrode materials. The electrode performance of the PCNS was investigated in 1-M tetraethylammonium tetrafluoroborate ((C2H5)4NBF4) in propylene carbonate. The PCNS electrodes displayed high specific capacitance (86 F g-1 for cations and 115 F g-1 for anions). They also showed exceptionally high rate performance with ∼90% capacitance retention at current densities up to 2 A g-1 because their nanosheet structure allowed the rapid diffusion of ions inside the electrode.

  10. Thermal-decomposition studies of HMX

    Energy Technology Data Exchange (ETDEWEB)

    Kolb, J.R.; Garza, R.G.

    1981-10-20

    We have investigated the rates of decomposition as functions of time and temperature on a combined thermogravimetric analyzer-residual gas analyzer (TGA-RGA). This technique also allows us to identify decomposition products generated as the original HMX begins to decompose. The temperature range studied was 50 to 200/sup 0/C. The decomposition process and the nature of decomposition products as functions of HMX polymorphs and conformations of the organic ring systems and possible reactive intermediates are discussed. 7 figures, 3 tables.

  11. Numerical analysis of thermal decomposition for RDX, TNT, and Composition B

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Shin Hyuk; Nyande, Baggie W. [Department of Chemical Engineering, Hanbat National University, 125 Dongseo-daero, Yuseong-gu, Daejeon 305-719 (Korea, Republic of); Kim, Hyoun Soo; Park, Jung Su [Agency for Defence Development, 462 Jochiwon-gil, Yuseong-gu, Daejeon 305-150 (Korea, Republic of); Lee, Woo Jin [Hanwha corporation, 117 Yeosusandan 3-ro, Yeosu-si, Jeollanam-do (Korea, Republic of); Oh, Min, E-mail: minoh@hanbat.ac.kr [Department of Chemical Engineering, Hanbat National University, 125 Dongseo-daero, Yuseong-gu, Daejeon 305-719 (Korea, Republic of)

    2016-05-05

    Highlights: • Reaction mechanism of thermal decomposition of military explosives is investigated. • Mathematical modeling of thermal decomposition are executed. • Commercial scale reactor is employed for demilitarization of waste explosives. • Dynamic response of thermal decomposition is examined in a reactor. - Abstract: Demilitarization of waste explosives on a commercial scale has become an important issue in many countries, and this has created a need for research in this area. TNT, RDX and Composition B have been used as military explosives, and they are very sensitive to thermal shock. For the safe waste treatment of these high-energy and highly sensitive explosives, the most plausible candidate suggested has been thermal decomposition in a rotary kiln. This research examines the safe treatment of waste TNT, RDX and Composition B in a rotary kiln type incinerator with regard to suitable operating conditions. Thermal decomposition in this study includes melting, 3 condensed phase reactions in the liquid phase and 263 gas phase reactions. Rigorous mathematical modeling and dynamic simulation for thermal decomposition were carried out for analysis of dynamic behavior in the reactor. The results showed time transient changes of the temperature, components and mass of the explosives and comparisons were made for the 3 explosives. It was concluded that waste explosives subject to heat supplied by hot air at 523.15 K were incinerated safely without any thermal detonation.

  12. Kinetics of the thermal decomposition of tetramethylsilane behind ...

    Indian Academy of Sciences (India)

    Thermal decomposition of tetramethylsilane (TMS) diluted in argon was studied behind the reflected shock waves in a single pulse shock tube (SPST) in the temperature range of 1058–1194 K. The major products formed in the decomposition are methane (CH4) and ethylene (C2H4); whereas ethane and propylene were ...

  13. Thermal decomposition of ethylenediaminetetraacetic acid in the presence of 1,2-phenylenediamine and hydrochloric acid

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Jingwen [Yancheng Institute of Technology, Yancheng (China); Gao, Jinhao [Nanjing Univ., Nanjing (China). Coordination Chemistry Institute. State Key Lab. of Coordination Chemistry; Wang, Xiaoyong [Nanjing Univ., Nanjing (China). School of Life Science. State Key Lab. of Pharmaceutical Biotechnology]. E-mail: boxwxy@nju.edu.cn

    2006-09-15

    Based on the reaction products of ethylenediaminetetraacetic acid (EDTA) with 1,2- phenylenediamine (o-PDA), a novel thermal decomposition pathway of EDTA is proposed. The strong acidic medium and the presence of o-PDA facilitate the decomposition of EDTA as evidenced by the relatively lower reaction temperature. In addition to the steps described in literatures, rearrangement process is involved in the decomposition reaction. The rearranged intermediates condense with o-PDA, forming an unexpected biologically active compound 2,2,4- trimethyl-3H-5-hydro-1,5-benzodiazepine, thus provides the possibility to explore an alternative decomposition mechanism for this widely used chelator. (author)

  14. The correlation between elongation at break and thermal decomposition of aged EPDM cable polymer

    Science.gov (United States)

    Šarac, T.; Devaux, J.; Quiévy, N.; Gusarov, A.; Konstantinović, M. J.

    2017-03-01

    The effect of simultaneous thermal and gamma irradiation ageing on the mechanical and physicochemical properties of industrial EPDM was investigated. Accelerated ageing, covering a wide range of dose rates, doses and temperatures, was preformed in stagnant air on EPDM polymer samples extracted from the cables in use in the Belgian nuclear power plants. The mechanical properties, ultimate tensile stress and elongation at break, are found to exhibit the strong dependence on the dose, ageing temperature and dose rate. The thermal decomposition of aged polymer is observed to be the dose dependent when thermogravimetry test is performed under air atmosphere. No dose dependence is observed when thermal decomposition is performed under nitrogen atmosphere. The thermal decomposition rates are found to fully mimic the reduction of elongation at break for all dose rates and ageing temperatures. This effect is argued to be the result of thermal and radiation mediated oxidation degradation process.

  15. Thermal decomposition of potassium bis-oxalatodiaqua-indate (III ...

    Indian Academy of Sciences (India)

    2] 3H2O. Thermal decomposition studies show that the compound decomposes first to the anhydrous potassium indium oxalate ... Bio-inorganic Chemistry Laboratories, School of Chemistry, Andhra University, Visakhapatnam 530 003, India ...

  16. Decomposition of Amino Diazeniumdiolates (NONOates): Molecular Mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Shaikh, Nizamuddin; Valiev, Marat; Lymar, Sergei V.

    2014-08-23

    Although diazeniumdiolates (X[N(O)NO]-) are extensively used in biochemical, physiological, and pharmacological studies due to their ability to slowly release NO and/or its congeneric nitroxyl, the mechanisms of these processes remain obscure. In this work, we used a combination of spectroscopic, kinetic, and computational techniques to arrive at a qualitatively consistent molecular mechanism for decomposition of amino diazeniumdiolates (amino NONOates: R2N[N(O)NO]-, where R = -N(C2H5)2 (1), -N(C3H4NH2)2 (2), or -N(C2H4NH2)2 (3)). Decomposition of these NONOates is triggered by protonation of their [NN(O)NO]- group with apparent pKa and decomposition rate constants of 4.6 and 1 s-1 for 1-H, 3.5 and 83 x 10-3 s-1 for 2-H, and 3.8 and 3.3 x 10-3 s-1 for 3-H. Although protonation occurs mainly on the O atoms of the functional group, only the minor R2N(H)N(O)NO tautomer (population ~0.01%, for 1) undergoes the N-N heterolytic bond cleavage (k ~102 s-1 for 1) leading to amine and NO. Decompositions of protonated amino NONOates are strongly temperature-dependent; activation enthalpies are 20.4 and 19.4 kcal/mol for 1 and 2, respectively, which includes contributions from both the tautomerization and bond cleavage. The bond cleavage rates exhibit exceptional sensitivity to the nature of R substituents which strongly modulate activation entropy. At pH < 2, decompositions of all these NONOates are subject to additional acid catalysis that occurs through di-protonation of the [NN(O)NO]- group.

  17. Decomposition Mechanism and Decomposition Promoting Factors of Waste Hard Metal for Zinc Decomposition Process (ZDP)

    Energy Technology Data Exchange (ETDEWEB)

    Pee, J H; Kim, Y J; Kim, J Y; Cho, W S; Kim, K J [Whiteware Ceramic Center, KICET (Korea, Republic of); Seong, N E, E-mail: pee@kicet.re.kr [Recytech Korea Co., Ltd. (Korea, Republic of)

    2011-10-29

    Decomposition promoting factors and decomposition mechanism in the zinc decomposition process of waste hard metals which are composed mostly of tungsten carbide and cobalt were evaluated. Zinc volatility amount was suppressed and zinc steam pressure was produced in the reaction graphite crucible inside an electric furnace for ZDP. Reaction was done for 2 hrs at 650 deg. C, which 100% decomposed the waste hard metals that were over 30 mm thick. As for the separation-decomposition of waste hard metals, zinc melted alloy formed a liquid composed of a mixture of {gamma}-{beta}1 phase from the cobalt binder layer (reaction interface). The volume of reacted zone was expanded and the waste hard metal layer was decomposed-separated horizontally from the hard metal. Zinc used in the ZDP process was almost completely removed-collected by decantation and volatilization-collection process at 1000 deg. C. The small amount of zinc remaining in the tungsten carbide-cobalt powder which was completely decomposed was fully removed by using phosphate solution which had a slow cobalt dissolution speed.

  18. Thermal decomposition of yttrium(III) hexanoate in argon

    DEFF Research Database (Denmark)

    Grivel, Jean-Claude; Suarez Guevara, Maria Josefina; Attique, Fahmida

    2015-01-01

    The thermal decomposition of yttrium(III) hexanoate (Y(C5H11CO2)3)·xH2O in argon was studied by means of thermogravimetry, differential thermal analysis, IR-spectroscopy, X-ray diffraction at a laboratory Cu-tube source and in-situ experiments at a synchrotron radiation source as well as hot...

  19. Thermal decomposition of lanthanum(III) butyrate in argon atmosphere

    DEFF Research Database (Denmark)

    Grivel, Jean-Claude; Yue, Zhao; Xiao, Tang

    2013-01-01

    The thermal decomposition of La(C3H7CO2)3·xH2O (x≈0.82) was studied in argon during heating at 5K/min. After the loss of bound H2O, the anhydrous butyrate presents at 135°C a phase transition to a mesophase, which turns to an isotropic liquid at 180°C. The decomposition of the anhydrous butyrate ...

  20. The Products of the Thermal Decomposition of CH3CHO

    Energy Technology Data Exchange (ETDEWEB)

    Vasiliou, AnGayle; Piech, Krzysztof M.; Zhang, Xu; Nimlos, Mark R.; Ahmed, Musahid; Golan, Amir; Kostko, Oleg; Osborn, David L.; Daily, John W.; Stanton, John F.; Ellison, G. Barney

    2011-04-06

    We have used a heated 2 cm x 1 mm SiC microtubular (mu tubular) reactor to decompose acetaldehyde: CH3CHO + DELTA --> products. Thermal decomposition is followed at pressures of 75 - 150 Torr and at temperatures up to 1700 K, conditions that correspond to residence times of roughly 50 - 100 mu sec in the mu tubular reactor. The acetaldehyde decomposition products are identified by two independent techniques: VUV photoionization mass spectroscopy (PIMS) and infrared (IR) absorption spectroscopy after isolation in a cryogenic matrix. Besides CH3CHO, we have studied three isotopologues, CH3CDO, CD3CHO, and CD3CDO. We have identified the thermal decomposition products CH3(PIMS), CO (IR, PIMS), H (PIMS), H2 (PIMS), CH2CO (IR, PIMS), CH2=CHOH (IR, PIMS), H2O (IR, PIMS), and HC=CH (IR, PIMS). Plausible evidence has been found to support the idea that there are at least three different thermal decomposition pathways for CH3CHO: Radical decomposition: CH3CHO + DELTA --> CH3 + [HCO] --> CH3 + H + CO Elimination: CH3CHO + DELTA --> H2 + CH2=C=O. Isomerization/elimination: CH3CHO + DELTA --> [CH2=CH-OH] --> HC=CH + H2O. Both PIMS and IR spectroscopy show compelling evidence for the participation of vinylidene, CH2=C:, as an intermediate in the decomposition of vinyl alchohol: CH2=CH-OH + DELTA --> [CH2=C:] + H2O --> HC=CH + H2O.

  1. The thermal decomposition behavior of ammonium perchlorate and of an ammonium-perchlorate-based composite propellant

    Energy Technology Data Exchange (ETDEWEB)

    Behrens, R.; Minier, L.

    1998-03-24

    The thermal decomposition of ammonium perchlorate (AP) and ammonium-perchlorate-based composite propellants is studied using the simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS) technique. The main objective of the present work is to evaluate whether the STMBMS can provide new data on these materials that will have sufficient detail on the reaction mechanisms and associated reaction kinetics to permit creation of a detailed model of the thermal decomposition process. Such a model is a necessary ingredient to engineering models of ignition and slow-cookoff for these AP-based composite propellants. Results show that the decomposition of pure AP is controlled by two processes. One occurs at lower temperatures (240 to 270 C), produces mainly H{sub 2}O, O{sub 2}, Cl{sub 2}, N{sub 2}O and HCl, and is shown to occur in the solid phase within the AP particles. 200{micro} diameter AP particles undergo 25% decomposition in the solid phase, whereas 20{micro} diameter AP particles undergo only 13% decomposition. The second process is dissociative sublimation of AP to NH{sub 3} + HClO{sub 4} followed by the decomposition of, and reaction between, these two products in the gas phase. The dissociative sublimation process occurs over the entire temperature range of AP decomposition, but only becomes dominant at temperatures above those for the solid-phase decomposition. AP-based composite propellants are used extensively in both small tactical rocket motors and large strategic rocket systems.

  2. Kinetics of lithium peroxide monohydrate thermal decomposition

    Science.gov (United States)

    Nefedov, Roman; Posternak, Nikolay; Ferapontov, Yuriy

    2017-11-01

    Topochemical dehydration of lithium peroxide was studied to determine kinetic parameters at the range of temperatures from 90°C to 147°C in non-isothermal conditions by derivatographic method. The study was conducted to select optimal conditions of lithium peroxide synthesis in dehydration reaction of triple LiOH-H2O2-H2O system in ultra-high frequency radiation field. Conditions of dehydration reaction were caused by the thermal conductivity of LiOH -H2O2-H2O system. It is determined that dehydration process runs close to the first order reaction (n=0.85±0.03). The activation energy and pre-exponential factor values were found as Eak = 86.0 ± 0.8 kJ/mol, k0 = (2.19 ± 0.16) .1011 min-1, correspondingly. It is supposed that there is a similarity between the dehydration mechanism of lithium peroxide monohydrate and peroxide hydrates of alkaline-earth metals (calcium, barium and strontium).

  3. Thermal decomposition and kinetics of 2,4-dinitroimidazole: An insensitive high explosive

    Energy Technology Data Exchange (ETDEWEB)

    Anniyappan, M., E-mail: anniorganic@rediffmail.com; Sonawane, S.H.; Pawar, S.J.; Sikder, A.K.

    2015-08-20

    Highlights: • Pure 2,4-dinitroimidazole was prepared by re-crystallization from hot methanol. • A detailed thermal analysis of 2,4-DNI by DSC, TGA, GC–MS and ignition temperature. • Activation energy was calculated for thermal decomposition of 2,4-DNI • Effect of polymeric binder on thermal decomposition of 2,4-DNI were also studied. • Decomposition mechanisms of 2,4-DNI based on EI mass spectra were also described. - Abstract: 2,4-Dinitroimidazole (2,4-DNI) is a novel energetic material with much less sensitive and potential for use as a propellant/insensitive munition (IM) formulations. 2,4-DNI possess high thermal stability and less sensitivity as compared to RDX and HMX which are high explosives extensively used at present. This paper reports a detailed thermal study of 2,4-DNI using various instrumental techniques. The activation energy (E = 205 ± 15 kJ/mol) was calculated from thermal decomposition of 2,4-DNI using DSC at different heating rate. The ignition temperature of pure 2,4-DNI was measured and showed at 285 °C. The TGA experiments demonstrate that 2,4-DNI decomposes in three steps with 92% total weight lose. Moreover, the effect of thermal energy on decomposition of 2,4-DNI in presence of polymeric binders like GAP and HTPB were investigated. Further, decomposition mechanisms of 2,4-DNI based on Electron Impact mass spectra analysis were also reported along with its explosive properties.

  4. SIMULATION OF THERMAL DECOMPOSITION OF MINERAL INSULATING OIL

    Directory of Open Access Journals (Sweden)

    V. G. M. Cruz

    2015-09-01

    Full Text Available AbstractDissolved gas analysis (DGA has been applied for decades as the main predictive maintenance technique for diagnosing incipient faults in power transformers since the decomposition of the mineral insulating oil (MIO produces gases that remain dissolved in the liquid phase. Nevertheless, the most known diagnostic methods are based on findings of simplified thermodynamic and compositional models for the thermal decomposition of MIO, in addition to empirical data. The simulation results obtained from these models do not satisfactorily reproduce the empirical data. This paper proposes a flexible thermodynamic model enhanced with a kinetic approach and selects, among four compositional models, the one offering the best performance for the simulation of thermal decomposition of MIO. The simulation results obtained from the proposed model showed better adequacy to reported data than the results obtained from the classical models. The proposed models may be applied in the development of a phenomenologically-based diagnostic method.

  5. Thermal decomposition of fullerene nanowhiskers protected by amorphous carbon mask

    Science.gov (United States)

    Guo, Hongxuan; Wang, Chengxiang; Miyazawa, Kun'Ichi; Wang, Hongxin; Masuda, Hideki; Fujita, Daisuke

    2016-12-01

    Fullerene nanostructures are well known for their unique morphology, physical and mechanical properties. The thermal stability of fullerene nanostructures, such as their sublimation at high temperature is also very important for studying their structures and applications. In this work, We observed fullerene nanowhiskers (FNWs) in situ with scanning helium ion microscopy (HIM) at elevated temperatures. The FNWs exhibited different stabilities with different thermal histories during the observation. The pristine FNWs were decomposed at the temperatures higher than 300 °C in a vacuum environment. Other FNWs were protected from decomposition with an amorphous carbon (aC) film deposited on the surface. Based on high spacial resolution, aC film with periodic structure was deposited by helium ion beam induced deposition (IBID) on the surface of FNWs. Annealed at the high temperature, the fullerene molecules were selectively sublimated from the FNWs. The periodic structure was formed on the surface of FNWs and observed by HIM. Monte Carlo simulation and Raman characterization proved that the morphology of the FNWs was changed by helium IBID at high temperature. This work provides a new method of fabricating artificial structure on the surface of FNWs with periodic aC film as a mask.

  6. Thermal Decomposition Chemistry of Amine Borane (U)

    Energy Technology Data Exchange (ETDEWEB)

    Stowe, A. C.; Feigerle, J.; Smyrl, N. R.; Morrell, J. S.

    2010-01-29

    The conclusions of this presentation are: (1) Amine boranes potentially can be used as a vehicular hydrogen storage material. (2) Purity of the hydrogen stream is critical for use with a fuel cell. Pure H{sub 2} can be provided by carefully conditioning the fuel (encapsulation, drying, heating rate, impurities). (3) Thermodynamics and kinetics can be controlled by conditioning as well. (4) Regeneration of the spent amine borane fuel is still the greatest challenge to its potential use. (5) Addition of hydrocarbon-substituted amine boranes alter the chemistry dramatically. (6) Decomposition of the substituted amine borane mixed system favors reaction products that are more potentially easier to regenerate the hydrogenated fuel. (7) t-butylamine borane is not the best substituted amine borane to use since it releases isobutane; however, formation of CNBH{sub x} products does occur.

  7. A convenient thermal decomposition-co-reduction synthesis of ...

    Indian Academy of Sciences (India)

    ... Workshops · Refresher Courses · Symposia · Live Streaming. Home; Journals; Bulletin of Materials Science; Volume 28; Issue 5. A convenient thermal decomposition-co-reduction synthesis of nanocrystalline tungsten disilicide. Jianhua Ma Yihong Du Yitai Qian. Nanomaterials Volume 28 Issue 5 August 2005 pp 511-513 ...

  8. Effect of high heating rate on thermal decomposition behaviour of ...

    Indian Academy of Sciences (India)

    but rely on the concentration of hydrogen. The model ... first-order rate law. Lehmhus and Rausch (2004) have annealed TiH2 pow- der in air and argon. In argon, the powder does not develop a surface layer and as a result, a small amount of hydro- gen is lost ... rate effect on the thermal decomposition behaviour of TiH2.

  9. alumina phase transformation from thermal decomposition

    African Journals Online (AJOL)

    HOD

    . It was found to be stable at higher ... thermal stability of the gamma alumina phase gives it good advantage to be used for high temperature applications, such as support for catalyst ..... owing to the low intensity counts as well as broad peaks.

  10. Thermal decomposition of hydroxylamine: Isoperibolic calorimetric measurements at different conditions

    Energy Technology Data Exchange (ETDEWEB)

    Adamopoulou, Theodora [Department of Environmental and Natural Resources Management, University of Western Greece (formerly of University of Ioannina), Seferi 2, Agrinio GR30100 (Greece); Papadaki, Maria I., E-mail: mpapadak@cc.uoi.gr [Department of Environmental and Natural Resources Management, University of Western Greece (formerly of University of Ioannina), Seferi 2, Agrinio GR30100 (Greece); Kounalakis, Manolis [Department of Environmental and Natural Resources Management, University of Western Greece (formerly of University of Ioannina), Seferi 2, Agrinio GR30100 (Greece); Vazquez-Carreto, Victor; Pineda-Solano, Alba [Mary Kay O’Connor Process Safety Center, Artie McFerrin Department of Chemical Engineering, Texas A and M University, College Station, TX 77843 (United States); Wang, Qingsheng [Department of Fire Protection and Safety and Department of Chemical Engineering, Oklahoma State University, 494 Cordell South, Stillwater, OK 74078 (United States); Mannan, M.Sam [Mary Kay O’Connor Process Safety Center, Artie McFerrin Department of Chemical Engineering, Texas A and M University, College Station, TX 77843 (United States)

    2013-06-15

    Highlights: • Hydroxylamine thermal decomposition enthalpy was measured using larger quantities. • The rate at which heat is evolved depends on hydroxylamine concentration. • Decomposition heat is strongly affected by the conditions and the selected baseline. • The need for enthalpy measurements using a larger reactant mass is pinpointed. • Hydroxylamine decomposition in the presence of argon is much faster than in air. -- Abstract: Thermal decomposition of hydroxylamine, NH{sub 2}OH, was responsible for two serious accidents. However, its reactive behavior and the synergy of factors affecting its decomposition are not being understood. In this work, the global enthalpy of hydroxylamine decomposition has been measured in the temperature range of 130–150 °C employing isoperibolic calorimetry. Measurements were performed in a metal reactor, employing 30–80 ml solutions containing 1.4–20 g of pure hydroxylamine (2.8–40 g of the supplied reagent). The measurements showed that increased concentration or temperature, results in higher global enthalpies of reaction per unit mass of reactant. At 150 °C, specific enthalpies as high as 8 kJ per gram of hydroxylamine were measured, although in general they were in the range of 3−5 kJ g{sup −1}. The accurate measurement of the generated heat was proven to be a cumbersome task as (a) it is difficult to identify the end of decomposition, which after a fast initial stage, proceeds very slowly, especially at lower temperatures and (b) the environment of gases affects the reaction rate.

  11. The products of the thermal decomposition of CH3CHO.

    Science.gov (United States)

    Vasiliou, AnGayle; Piech, Krzysztof M; Zhang, Xu; Nimlos, Mark R; Ahmed, Musahid; Golan, Amir; Kostko, Oleg; Osborn, David L; Daily, John W; Stanton, John F; Ellison, G Barney

    2011-07-07

    We have used a heated 2 cm × 1 mm SiC microtubular (μtubular) reactor to decompose acetaldehyde: CH(3)CHO + Δ → products. Thermal decomposition is followed at pressures of 75-150 Torr and at temperatures up to 1675 K, conditions that correspond to residence times of roughly 50-100 μs in the μtubular reactor. The acetaldehyde decomposition products are identified by two independent techniques: vacuum ultraviolet photoionization mass spectroscopy (PIMS) and infrared (IR) absorption spectroscopy after isolation in a cryogenic matrix. Besides CH(3)CHO, we have studied three isotopologues, CH(3)CDO, CD(3)CHO, and CD(3)CDO. We have identified the thermal decomposition products CH(3) (PIMS), CO (IR, PIMS), H (PIMS), H(2) (PIMS), CH(2)CO (IR, PIMS), CH(2)=CHOH (IR, PIMS), H(2)O (IR, PIMS), and HC≡CH (IR, PIMS). Plausible evidence has been found to support the idea that there are at least three different thermal decomposition pathways for CH(3)CHO; namely, radical decomposition: CH(3)CHO + Δ → CH(3) + [HCO] → CH(3) + H + CO; elimination: CH(3)CHO + Δ → H(2) + CH(2)=C=O; isomerization∕elimination: CH(3)CHO + Δ → [CH(2)=CH-OH] → HC≡CH + H(2)O. An interesting result is that both PIMS and IR spectroscopy show compelling evidence for the participation of vinylidene, CH(2)=C:, as an intermediate in the decomposition of vinyl alcohol: CH(2)=CH-OH + Δ → [CH(2)=C:] + H(2)O → HC≡CH + H(2)O.

  12. The Effect of Water Vapor on the Thermal Decomposition of Pyrite in N2 Atmosphere

    Directory of Open Access Journals (Sweden)

    Nesrin BOYABAT

    2009-03-01

    Full Text Available In this study, the effect of water vapor on the thermal decomposition of pyrite mineral in nitrogen atmosphere has been investigated in a horizontal tube furnace. Temperature, time and water vapor concentration were used as experimental parameters. According to the data obtained at nitrogen/ water vapor environment, it was observed that the water vapor on the decomposition of pyrite increased the decomposition rate. The decomposition reaction is well represented by the "shrinking core" model and can be divided into two regions with different rate controlling step. The rate controlling steps were determined from the heat transfer through the gas film for the low conversions, while it was determined from the mass transfer through product ash layer for the high conversions. The activation energies of this gas and ash film mechanisms were found to be 77 and 81 kJ/mol-1, respectively.

  13. Effect of particle size on thermal decomposition of alkali metal picrates

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Rui; Zhang, Tonglai, E-mail: ztlbit@bit.edu.cn; Yang, Li; Zhou, Zunning

    2014-05-01

    Graphical abstract: The smaller-sized picrate has greater gas emission than do its larger counterpart. The small size effect reduces the thermal decomposition activation energy, accelerates the reaction rate, and promotes the reaction activity. - Highlights: • Picrates were prepared into three micron sizes by microemulsion synthesis. • Thermal decomposition kinetics and thermodynamics were studied by DPTA and DSC. • Smaller-sized picrate has higher activity and faster reaction rate. • Particle size effect on thermal decomposition kinetics and thermodynamics was revealed. - Abstract: Three alkali metal picrates, KPA, RbPA and CsPA, were prepared into three micron sizes by microemulsion synthesis, and their thermal decomposition behaviors were investigated by DPTA at different temperatures and by DSC at different heating rates. The smaller-sized picrate has greater gas emission and smaller kinetic and thermodynamic parameters than do its larger counterpart. It can be attributed to the decreasing particle size which leads to the high surface energy, the fast mass and heat transfer, and the increasing active sites on the reaction interface. The small size effect and surface effect cause the autocatalysis which reduces the activation energy and promotes the reaction activity. The particle size does not affect the reaction mechanism. However, the picrates with different central alkali metals exhibit different reaction mechanisms even though they are of the same size. This is because the central metal determines the bond energy and consequently affects the stability of picrate.

  14. Pollutant content in marine debris and characterization by thermal decomposition.

    Science.gov (United States)

    Iñiguez, M E; Conesa, J A; Fullana, A

    2017-04-15

    Marine debris (MDs) produces a wide variety of negative environmental, economic, safety, health and cultural impacts. Most marine litter has a very low decomposition rate (plastics), leading to a gradual accumulation in the coastal and marine environment. Characterization of the MDs has been done in terms of their pollutant content: PAHs, ClBzs, ClPhs, BrPhs, PCDD/Fs and PCBs. The results show that MDs is not a very contaminated waste. Also, thermal decomposition of MDs materials has been studied in a thermobalance at different atmospheres and heating rates. Below 400-500K, the atmosphere does not affect the thermal degradation of the mentioned waste. However, at temperatures between 500 and 800K the presence of oxygen accelerates the decomposition. Also, a kinetic model is proposed for the combustion of the MDs, and the decomposition is compared with that of their main constituents, i.e., polyethylene (PE), polystyrene (PS), polypropylene (PP), nylon and polyethylene-terephthalate (PET). Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Plant identity influences decomposition through more than one mechanism.

    Directory of Open Access Journals (Sweden)

    Jennie R McLaren

    Full Text Available Plant litter decomposition is a critical ecosystem process representing a major pathway for carbon flux, but little is known about how it is affected by changes in plant composition and diversity. Single plant functional groups (graminoids, legumes, non-leguminous forbs were removed from a grassland in northern Canada to examine the impacts of functional group identity on decomposition. Removals were conducted within two different environmental contexts (fertilization and fungicide application to examine the context-dependency of these identity effects. We examined two different mechanisms by which the loss of plant functional groups may impact decomposition: effects of the living plant community on the decomposition microenvironment, and changes in the species composition of the decomposing litter, as well as the interaction between these mechanisms. We show that the identity of the plant functional group removed affects decomposition through both mechanisms. Removal of both graminoids and forbs slowed decomposition through changes in the decomposition microenvironment. We found non-additive effects of litter mixing, with both the direction and identity of the functional group responsible depending on year; in 2004 graminoids positively influenced decomposition whereas in 2006 forbs negatively influenced decomposition rate. Although these two mechanisms act independently, their effects may be additive if both mechanisms are considered simultaneously. It is essential to understand the variety of mechanisms through which even a single ecosystem property is affected if we are to predict the future consequences of biodiversity loss.

  16. Kinetics of the thermal decomposition of pine needles

    Directory of Open Access Journals (Sweden)

    Dhaundiyal Alok

    2015-12-01

    Full Text Available A kinetic study of the pyrolysis process of pine needles was examined using a thermogravimetric analyser. The weight loss was measured in nitrogen atmosphere at a purge flow rate of 100 ml/min. The samples were heated over a range of temperature of 19°C–600°C with a heating rate of 10°C/min. The results obtained from the thermal decomposition process indicate that there are three main stages: dehydration, active and passive pyrolysis. The kinetic parameters for the different samples, such as activation energy and pre-exponential factor, are obtained by the shrinking core model (reaction-controlled regime, the model-free, and the first-order model. Experimental results showed that the shrinking model is in good agreement and can be successfully used to understand degradation mechanism of loose biomass. The result obtained from the reaction-controlled regime represented actual values of kinetic parameters which are the same for the whole pyrolysis process; whereas the model-free method presented apparent values of kinetic parameters, as they are dependent on the unknown function ϕ(C, on the sum of the parameters of the physical processes, and on the chemical reactions that happen simultaneously during pyrolysis. Experimental results showed that values of kinetic constant from the first-order model and the SCM are in good agreement and can be successfully used to understand the behaviour of loose biomass (pine needles in the presence of inert atmosphere. Using TGA results, the simulating pyrolysis can be done, with the help of computer software, to achieve a comprehensive detail of the devolatilization process of different types of biomasses.

  17. Mechanistic and kinetic studies of the thermal decomposition of TNAZ and NDNAZ

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, K.; Homsy, J.; Behrens, R. [Sandia National Labs., Livermore, CA (United States). Combustion Research Facility; Bulusu, S. [Army Armament Research, Development and Engineering Center, Dover, NJ (United States). Energetic Materials Div.

    1998-12-31

    The authors have studied the mechanism and detailed reaction kinetics of the thermal decomposition of 1,3,3-trinitroazetidine (TNAZ), and separately, its key decomposition intermediate, 1-nitroso-3,3-dinitroacetidine (NDNAZ), using a simultaneous thermogravimetric modulated beam mass spectrometer (STMBMS). These decompositions were conducted in a sealed alumina cell with a 2.5 {micro}m orifice, at varying temperatures and at a range of isothermal temperatures (at 10 C intervals from 120--160 C for NDNAZ and 160--210 C for TNAZ). The gaseous products have been identified and their rates of formation have been measured as a function of time, temperature, and pressure. This system is complex, with TNAZ decomposing by four separate routes, one of which leads to NDNAZ, which itself decomposes by at least two distinct routes.

  18. Structural effects and thermal decomposition kinetics of chalcones under non-isothermal conditions

    Directory of Open Access Journals (Sweden)

    G. Manikandan

    2016-09-01

    Full Text Available Two chalcones namely, 1,5-bis(4-hydroxy-3-methoxyphenylpentan-1,4-dien-3-one (BHMPD and 2,5-bis(4-hydroxy-3-methoxybenzylidenecyclopentanone (BHMBC have been synthesised and characterized by microanalysis, FT-IR, mass spectra and NMR (1H and 13C techniques. The thermal decomposition of these compounds was studied by TGA and DTA under dynamic nitrogen atmosphere at different heating rates of 10, 15 and 20 K min−1. The kinetic parameters were calculated using model-fitting (Coats–Redfern, CR and model-free methods (Friedman, Kissinger–Akahira–Sunose, KAS and Flynn–Wall–Ozawa, FWO. The decomposition process of BHMPD and BHMBC followed a single step mechanism as evidenced from the data. Existence of compensation effect was noticed for the decomposition of these compounds. Invariant kinetic parameters are consistent with the average values obtained by Friedman and KAS isoconversional method in both compounds.

  19. Isoconversional Kinetic Study Of The Thermal Decomposition Of Sugarcane Straw For Thermal Conversion Processes.

    OpenAIRE

    Rueda-Ordóñez, Yesid Javier; Tannous, Katia

    2016-01-01

    The aim of this work was investigate the kinetics of the thermal decomposition reaction of sugarcane straw. The thermal decomposition experiments were conducted at four heating rates (1.25, 2.5, 5 and 10 degrees C/min) in a thermogravimetric analyzer using nitrogen as inert atmosphere. The kinetic analysis was carried out applying the isoconversional method of Friedman, and the activation energies obtained varied from 154.1 kJ/mol to 177.8 kJ/mol. The reaction model was determined through mas...

  20. Programming Enhancements for Low Temperature Thermal Decomposition Workstation

    Energy Technology Data Exchange (ETDEWEB)

    Igou, R.E.

    1998-10-01

    This report describes a new control-and-measurement system design for the Oak Ridge Y-12 Plant's Low Temperature Thermal Decomposition (LTTD) process. The new design addresses problems with system reliability stemming from equipment obsolescence and addresses specific functional improvements that plant production personnel have identified, as required. The new design will also support new measurement techniques, which the Y-12 Development Division has identified for future operations. The new techniques will function in concert with the original technique so that process data consistency is maintained.

  1. Thermal Plasma Decomposition Of Nickel And Cobalt Compounds

    Directory of Open Access Journals (Sweden)

    Woch M.

    2015-06-01

    Full Text Available The paper presents the study on manufacturing of nickel and cobalt powders by thermal plasma decomposition of the carbonates of these metals. It was shown the dependence of process parameters and grain size of initial powder on the composition of final product which was ether metal powder, collected in the container as well as the nanopowder with crystallite size of 70 - 90 nm, collected on the inner wall of the reaction chamber. The occurrence of metal oxides in the final products was confirmed and discussed.

  2. Decomposition kinetics study of zirconium hydride by interrupted thermal desorption spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Mingwang; Liang, Li; Tang, Binghua; Xiang, Wei; Wang, Yuan; Cheng, Yanlin; Tan, Xiaohua, E-mail: caepiee@163.com

    2015-10-05

    Highlights: • Interrupted TDS was applied to investigate the mechanism of ZrH{sub 2} decomposition. • The activation energies for the five desorption peaks were determined. • The origins of the five desorption peaks were identified. • The γZrH phase was observed at ambient conditions. - Abstract: Thermal desorption kinetics of zirconium hydride powder were studied using thermogravimetry and simultaneous thermal desorption spectroscopy. The activation energies for observed desorption peaks were estimated according to Kissinger relation. The intermediate phase composition was studied using X-ray diffraction by rapid cooling on different stages of heating. The origins of the peaks were described as the equilibrium hydrogen pressure of a number of consecutive phase regions that decomposition reaction passed through. The zirconium monohydride γZrH was observed for extended periods of time at ambient conditions, which has been supposed to be metastable for a long time.

  3. Dynamics in the Decompositions Approach to Quantum Mechanics

    Science.gov (United States)

    Harding, John

    2017-12-01

    In Harding (Trans. Amer. Math. Soc. 348(5), 1839-1862 1996) it was shown that the direct product decompositions of any non-empty set, group, vector space, and topological space X form an orthomodular poset Fact X. This is the basis for a line of study in foundational quantum mechanics replacing Hilbert spaces with other types of structures. Here we develop dynamics and an abstract version of a time independent Schrödinger's equation in the setting of decompositions by considering representations of the group of real numbers in the automorphism group of the orthomodular poset Fact X of decompositions.

  4. Thermal decomposition behavior of amino groups modified bimodal mesoporous silicas as aspirin carrier.

    Science.gov (United States)

    Gao, Lin; Sun, Jihong; Zhang, Li; Li, Yuzhen; Ren, Bo

    2011-12-01

    Two kinds of amino groups were employed to functionalize bimodal mesoporous silicas and related drug carriers were prepared. The characterization results of XRD, N2 adsorption and desorption, FT-IR and TG all confirmed the structural integrity of the bimodal mesopore architecture after introduction treatment of functional groups and the successful adsorption of aspirin. In order to investigate the interaction among the mesoporous structure, the functional groups grafted onto the mesoporous surface and the existential microenvironment of the drug molecules inside the mesoporous channels, the thermal decomposition behaviors of amino groups modified and aspirin loaded carriers were studied based on the thermogravimetric analysis in details. According to the thermogravimetry and derivative thermogravimetry results, the apparent activation energies E(a) of thermal decomposition for all related samples have been evaluated by Kissinger and Flynn-Wall-Ozawa methods. Meanwhile, their thermal decomposition mechanisms have been suggested by using Coats and Redfern methods. All these featured consequence could provide a deeper understanding for large loading capacity and controlled release of drug-carriers in the pharmaceutical application.

  5. Prediction of the thermal decomposition of organic peroxides by validated QSPR models

    Energy Technology Data Exchange (ETDEWEB)

    Prana, Vinca [Institut de Recherche de Chimie Paris, Chimie ParisTech CNRS, 11 rue P. et M. Curie, Paris 75005 (France); Institut National de l’Environnement Industriel et des Risques (INERIS), Parc Technologique Alata, BP2, Verneuil-en-Halatte 60550 (France); Rotureau, Patricia, E-mail: patricia.rotureau@ineris.fr [Institut National de l’Environnement Industriel et des Risques (INERIS), Parc Technologique Alata, BP2, Verneuil-en-Halatte 60550 (France); Fayet, Guillaume [Institut National de l’Environnement Industriel et des Risques (INERIS), Parc Technologique Alata, BP2, Verneuil-en-Halatte 60550 (France); André, David; Hub, Serge [ARKEMA, rue Henri Moissan, BP63, Pierre Benite 69493 (France); Vicot, Patricia [Institut National de l’Environnement Industriel et des Risques (INERIS), Parc Technologique Alata, BP2, Verneuil-en-Halatte 60550 (France); Rao, Li [Institut de Recherche de Chimie Paris, Chimie ParisTech CNRS, 11 rue P. et M. Curie, Paris 75005 (France); Adamo, Carlo [Institut de Recherche de Chimie Paris, Chimie ParisTech CNRS, 11 rue P. et M. Curie, Paris 75005 (France); Institut Universitaire de France, 103 Boulevard Saint Michel, Paris F-75005 (France)

    2014-07-15

    Highlights: • QSPR models were developed for thermal stability of organic peroxides. • Two accurate MLR models were exhibited based on quantum chemical descriptors. • Performances were evaluated by a series of internal and external validations. • The new QSPR models satisfied all OCDE principles of validation for regulatory use. - Abstract: Organic peroxides are unstable chemicals which can easily decompose and may lead to explosion. Such a process can be characterized by physico-chemical parameters such as heat and temperature of decomposition, whose determination is crucial to manage related hazards. These thermal stability properties are also required within many regulatory frameworks related to chemicals in order to assess their hazardous properties. In this work, new quantitative structure–property relationships (QSPR) models were developed to predict accurately the thermal stability of organic peroxides from their molecular structure respecting the OECD guidelines for regulatory acceptability of QSPRs. Based on the acquisition of 38 reference experimental data using DSC (differential scanning calorimetry) apparatus in homogenous experimental conditions, multi-linear models were derived for the prediction of the decomposition heat and the onset temperature using different types of molecular descriptors. Models were tested by internal and external validation tests and their applicability domains were defined and analyzed. Being rigorously validated, they presented the best performances in terms of fitting, robustness and predictive power and the descriptors used in these models were linked to the peroxide bond whose breaking represents the main decomposition mechanism of organic peroxides.

  6. Thermal wet decomposition of Prussian Blue: implications for prebiotic chemistry.

    Science.gov (United States)

    Ruiz-Bermejo, Marta; Rogero, Celia; Menor-Salván, César; Osuna-Esteban, Susana; Martín-Gago, José Angel; Veintemillas-Verdaguer, Sabino

    2009-09-01

    The complex salt named Prussian Blue, Fe4[Fe(CN)6]3 x 15 H2O, can release cyanide at pH > 10. From the point of view of the origin of life, this fact is of interest, since the oligomers of HCN, formed in the presence of ammonium or amines, leads to a variety of biomolecules. In this work, for the first time, the thermal wet decomposition of Prussian Blue was studied. To establish the influence of temperature and reaction time on the ability of Prussian Blue to release cyanide and to subsequently generate other compounds, suspensions of Prussian Blue were heated at temperatures from room temperature to 150 degrees at pH 12 in NH3 environment for several days. The NH3 wet decomposition of Prussian Blue generated hematite, alpha-Fe2O3, the soluble complex salt (NH4)4[Fe(CN6)] x 1.5 H2O, and several organic compounds, the nature and yield of which depend on the experimental conditions. Urea, lactic acid, 5,5-dimethylhydantoin, and several amino acids and carboxylic acids were identified by their trimethylsilyl (TMS) derivatives. HCN, cyanogen (C2N2), and formamide (HCONH2) were detected in the gas phase by GC/MS analysis.

  7. Physicochemical Characterization and Thermal Decomposition of Garin Maiganga Coal

    Directory of Open Access Journals (Sweden)

    Nyakuma Bemgba Bevan

    2016-12-01

    Full Text Available The paper examined physicochemical and thermal characteristics of the newly discovered Garin Maiganga (GMG coal from Nigeria. The physicochemical characterization comprised of elemental, proximate, calorific value, and classification (rank analyses. Thermal analysis was examined using combined Thermogravimetric (TG and Derivative Thermogravimetric analyses (DTG. Hence, the coal was heated from 30°C to 1000°C at 20°C/min under inert conditions to examine its thermal degradation behaviour and temperature profile characteristics (TPC. The results indicated that the GMG coal fuel properties consist of low Ash, Nitrogen, and Sulphur content. Moisture content was > 5%, Volatile Matter > 50%, Fixed Carbon > 22%, and Heating Value (HHV 23.74 MJ/kg. Based on its fuel properties, the GMG coal can be classified as a Sub-Bituminous B, non-agglomerating low rank coal (LRC. The GMG coal TPCs – onset, peak, and offset temperatures – were 382.70°C, 454.60°C, and 527.80°C, respectively. The DTG profile revealed four (4 endothermic peaks corresponding to loss of moisture (drying, volatile matter (devolatization, and coke formation. The residual mass Rm was 50.16%, which indicates that higher temperatures above 1000°C are required for the complete pyrolytic decomposition of the GMG coal. In conclusion, the results indicate that the GMG coal is potentially suitable for future utilization in electric power generation and the manufacture of cement and steel.

  8. A High Temperature Kinetic Study for the Thermal Unimolecular Decomposition of Diethyl Carbonate

    KAUST Repository

    Alabbad, Mohammed

    2017-07-08

    Thermal unimolecular decomposition of diethyl carbonate (DEC) was investigated in a shock tube by measuring ethylene concentration with a CO2 gas laser over 900 - 1200 K and 1.2 – 2.8 bar. Rate coefficients were extracted using a simple kinetic scheme comprising of thermal decomposition of DEC as initial step followed by rapid thermal decomposition of the intermediate ethyl-hydrogen-carbonate. Our results were further analysed using ab initio and master equation calculations to obtain pressure- and temperature- dependence of rate coefficients. Similar to alkyl esters, unimolecular decomposition of DEC is found to undergo six-center retro-ene elimination of ethylene in a concerted manner.

  9. Effect of urea additive on the thermal decomposition kinetics of flame retardant greige cotton nonwoven fabric

    Science.gov (United States)

    Sunghyun Nam; Brian D. Condon; Robert H. White; Qi Zhao; Fei Yao; Michael Santiago Cintrón

    2012-01-01

    Urea is well known to have a synergistic action with phosphorus-based flame retardants (FRs) in enhancing the FR performance of cellulosic materials, but the effect of urea on the thermal decomposition kinetics has not been thoroughly studied. In this study, the activation energy (Ea) for the thermal decomposition of greige...

  10. A quasimechanism of melt acceleration in the thermal decomposition of crystalline organic solids

    Energy Technology Data Exchange (ETDEWEB)

    Henson, Bryan F [Los Alamos National Laboratory

    2009-01-01

    It has been know for half a century that many crystalline organic solids undergo an acceleration in the rate of thermal decomposition as the melting temperature is approached. This acceleration terminates at the melting point, exhibiting an Arrhenius-like temperature dependence in the faster decomposition rate from the liquid phase. This observation has been modeled previously using various premelting behaviors based on e.g. freezing point depression induced by decomposition products or solvent impurities. These models do not, however, indicate a mechanism for liquid formation and acceleration which is an inherent function of the bulk thermodynamics of the molecule. Here we show that such an inherent thermodynamic mechanism for liquid formation exists in the form of the so-called quasi-liquid layer at the solid surface. We explore a kinetic mechanism which describes the acceleration of rate and is a function of the free energies of sublimation and vaporization. We construct a differential rate law from these thermodynamic free energies and a normalized progress variable. We further construct a reduced variable formulation of the model which is a simple function of the metastable liquid activity below the melting point, and show that it is applicable to the observed melt acceleration in several common organic crystalline solids. A component of the differential rate law, zero order in the progress variable, is shown to be proportional to the thickness of the quasiliquid layer predicted by a recent thermodynamic theory for this phenomenon. This work therefore serves not only to provide new insight into thermal decomposition in a broad class or organic crystalline solids, but also further validates the underlying thermodynamic nature of the phenomenon of liquid formation on the molecular surface at temperatures below the melting point.

  11. The response of the HMX-based material PBXN-9 to thermal insults: thermal decomposition kinetics and morphological changes

    Energy Technology Data Exchange (ETDEWEB)

    Glascoe, E A; Hsu, P C; Springer, H K; DeHaven, M R; Tan, N; Turner, H C

    2010-12-10

    PBXN-9, an HMX-formulation, is thermally damaged and thermally decomposed in order to determine the morphological changes and decomposition kinetics that occur in the material after mild to moderate heating. The material and its constituents were decomposed using standard thermal analysis techniques (DSC and TGA) and the decomposition kinetics are reported using different kinetic models. Pressed parts and prill were thermally damaged, i.e. heated to temperatures that resulted in material changes but did not result in significant decomposition or explosion, and analyzed. In general, the thermally damaged samples showed a significant increase in porosity and decrease in density and a small amount of weight loss. These PBXN-9 samples appear to sustain more thermal damage than similar HMX-Viton A formulations and the most likely reasons are the decomposition/evaporation of a volatile plasticizer and a polymorphic transition of the HMX from {beta} to {delta} phase.

  12. Prediction of the thermal decomposition of organic peroxides by validated QSPR models.

    Science.gov (United States)

    Prana, Vinca; Rotureau, Patricia; Fayet, Guillaume; André, David; Hub, Serge; Vicot, Patricia; Rao, Li; Adamo, Carlo

    2014-07-15

    Organic peroxides are unstable chemicals which can easily decompose and may lead to explosion. Such a process can be characterized by physico-chemical parameters such as heat and temperature of decomposition, whose determination is crucial to manage related hazards. These thermal stability properties are also required within many regulatory frameworks related to chemicals in order to assess their hazardous properties. In this work, new quantitative structure-property relationships (QSPR) models were developed to predict accurately the thermal stability of organic peroxides from their molecular structure respecting the OECD guidelines for regulatory acceptability of QSPRs. Based on the acquisition of 38 reference experimental data using DSC (differential scanning calorimetry) apparatus in homogenous experimental conditions, multi-linear models were derived for the prediction of the decomposition heat and the onset temperature using different types of molecular descriptors. Models were tested by internal and external validation tests and their applicability domains were defined and analyzed. Being rigorously validated, they presented the best performances in terms of fitting, robustness and predictive power and the descriptors used in these models were linked to the peroxide bond whose breaking represents the main decomposition mechanism of organic peroxides. Copyright © 2014 Elsevier B.V. All rights reserved.

  13. Synthesis, characterization and thermal decomposition of poly(decamethylene 2,6-naphthalamide

    Directory of Open Access Journals (Sweden)

    2010-06-01

    Full Text Available A novel engineering plastic, poly(decamethylene 2,6-naphthalamide (PA10N was prepared via a reaction of 2,6-naphthalene dicarboxylic acid and 1,10-decanediamine. The structure of synthesized PA10N was characterized by elemental analysis, Fourier transform infrared (FT-IR spectroscopy and proton nuclear magnetic resonance (1H-NMR. The thermal behavior was determined by differential scanning calorimetry (DSC, thermo-gravimetric analysis (TGA and dynamic mechanical analysis (DMA. Melting temperature (Tm, glass transition temperature (Tg and decomposition temperature (Td of PA10N are 320, 144 and 495°C, respectively. The solubility, water-absorbing capacity, and mechanical properties of PA10N have also been investigated. Pyrolysis products and thermal decomposition mechanism of PA10N were analyzed by flash pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS. The results show that the heat resistance and mechanical properties of PA10N are near to those of poly(nonamethylene terephthalamide (PA9T, and PA10N is a promising heat-resistant and processable engineering plastic.

  14. An investigation on the modelling of kinetics of thermal decomposition of hazardous mercury wastes.

    Science.gov (United States)

    Busto, Yailen; M G Tack, Filip; Peralta, Luis M; Cabrera, Xiomara; Arteaga-Pérez, Luis E

    2013-09-15

    The kinetics of mercury removal from solid wastes generated by chlor-alkali plants were studied. The reaction order and model-free method with an isoconversional approach were used to estimate the kinetic parameters and reaction mechanism that apply to the thermal decomposition of hazardous mercury wastes. As a first approach to the understanding of thermal decomposition for this type of systems (poly-disperse and multi-component), a novel scheme of six reactions was proposed to represent the behaviour of mercury compounds in the solid matrix during the treatment. An integration-optimization algorithm was used in the screening of nine mechanistic models to develop kinetic expressions that best describe the process. The kinetic parameters were calculated by fitting each of these models to the experimental data. It was demonstrated that the D₁-diffusion mechanism appeared to govern the process at 250°C and high residence times, whereas at 450°C a combination of the diffusion mechanism (D₁) and the third order reaction mechanism (F3) fitted the kinetics of the conversions. The developed models can be applied in engineering calculations to dimension the installations and determine the optimal conditions to treat a mercury containing sludge. Copyright © 2013 Elsevier B.V. All rights reserved.

  15. Effect of Nano-Magnesium Hydride on the Thermal Decomposition Behaviors of RDX

    Directory of Open Access Journals (Sweden)

    Miao Yao

    2013-01-01

    Full Text Available In order to improve the detonation performance of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX explosive, addictives with high heat values were used, and magnesium hydride (MgH2 is one of the candidates. However, it is important to see whether MgH2 is a safe addictive. In this paper, the thermal and kinetic properties of RDX and mixture of RDX/MgH2 were investigated by differential scanning calorimeter (DSC and accelerating rate calorimeter (ARC, respectively. The apparent activation energy (E and frequency factor (A of thermal explosion were calculated based on the data of DSC experiments using the Kissinger and Ozawa approaches. The results show that the addition of MgH2 decreases both E and A of RDX, which means that the mixture of RDX/MgH2 has a lower thermal stability than RDX, and the calculation results obtained from the ARC experiments data support this too. Besides, the most probable mechanism functions about the decomposition of RDX and RDX/MgH2 were given in this paper which confirmed the change of the decomposition mechanism.

  16. Radiolysis of lignin: Prospective mechanism of high-temperature decomposition

    Science.gov (United States)

    Ponomarev, A. V.

    2017-12-01

    The range of the radiation-thermal processes resulting in conversion of lignin into monomeric phenols is considered. Statistically the most probable places of macromolecule ionization are aromatic units. Release of phenolic products from a lignin macromolecule is the multistage process beginning via fragmentation of primary cation-radicals. Reactions of electrons and small radicals with macromolecules, also as degradation of cation-radicals, result in formation of phenoxyl radicals. Macroradicals possess lower heat stability in comparison with macromolecules. Thermal decomposition of macroradicals leads to release of monohydric and dihydric phenols. The probability of benzenediols formation increases in the presence of alkanes. As noted, partial transformation of lignin into charcoal is inevitable.

  17. Effect of Copper Oxide, Titanium Dioxide, and Lithium Fluoride on the Thermal Behavior and Decomposition Kinetics of Ammonium Nitrate

    Science.gov (United States)

    Vargeese, Anuj A.; Mija, S. J.; Muralidharan, Krishnamurthi

    2014-07-01

    Ammonium nitrate (AN) is crystallized along with copper oxide, titanium dioxide, and lithium fluoride. Thermal kinetic constants for the decomposition reaction of the samples were calculated by model-free (Friedman's differential and Vyzovkins nonlinear integral) and model-fitting (Coats-Redfern) methods. To determine the decomposition mechanisms, 12 solid-state mechanisms were tested using the Coats-Redfern method. The results of the Coats-Redfern method show that the decomposition mechanism for all samples is the contracting cylinder mechanism. The phase behavior of the obtained samples was evaluated by differential scanning calorimetry (DSC), and structural properties were determined by X-ray powder diffraction (XRPD). The results indicate that copper oxide modifies the phase transition behavior and can catalyze AN decomposition, whereas LiF inhibits AN decomposition, and TiO2 shows no influence on the rate of decomposition. Possible explanations for these results are discussed. Supplementary materials are available for this article. Go to the publisher's online edition of the Journal of Energetic Materials to view the free supplemental file.

  18. Validation of Heat Transfer Thermal Decomposition and Container Pressurization of Polyurethane Foam.

    Energy Technology Data Exchange (ETDEWEB)

    Scott, Sarah Nicole; Dodd, Amanda B.; Larsen, Marvin E.; Suo-Anttila, Jill M.; Erickson, Kenneth L

    2014-09-01

    Polymer foam encapsulants provide mechanical, electrical, and thermal isolation in engineered systems. In fire environments, gas pressure from thermal decomposition of polymers can cause mechanical failure of sealed systems. In this work, a detailed uncertainty quantification study of PMDI-based polyurethane foam is presented to assess the validity of the computational model. Both experimental measurement uncertainty and model prediction uncertainty are examined and compared. Both the mean value method and Latin hypercube sampling approach are used to propagate the uncertainty through the model. In addition to comparing computational and experimental results, the importance of each input parameter on the simulation result is also investigated. These results show that further development in the physics model of the foam and appropriate associated material testing are necessary to improve model accuracy.

  19. Room temperature and thermal decomposition of magnesium hydride/deuteride thin films

    Energy Technology Data Exchange (ETDEWEB)

    Ares, J.R.; Leardini, F.; Bodega, J.; Macia, M.D.; Diaz-Chao, P.; Ferrer, I.J.; Fernandez, J.F.; Sanchez, C. [Universidad Autonoma de Madrid (Spain). Lab. de Materiales de Interes en Energias Renovables

    2010-07-01

    Magnesium hydride (MgH{sub 2}) can be considered an interesting material to store hydrogen as long as two main drawbacks were solved: (i) its high stability and (ii) slow (de)hydriding kinetics. In that context, magnesium hydride films are an excellent model system to investigate the influence of structure, morphology and dimensionality on kinetic and thermodynamic properties. In the present work, we show that desorption mechanism of Pd-capped MgH{sub 2} at room temperature is controlled by a bidimensional interphase mechanism and a similar rate step limiting mechanism is observed during thermal decomposition of MgH{sub 2}. This mechanism is different to that occurring in bulk MgH{sub 2} (nucleation and growth) and obtained activation energies are lower than those reported in bulk MgH{sub 2}. We also investigated the Pd-capping properties upon H-absorption/desorption by means of RBS and isotope experiments. (orig.)

  20. Synthesis, Optical Characterization, and Thermal Decomposition of Complexes Based on Biuret Ligand

    National Research Council Canada - National Science Library

    Wang, Mei-Ling; Zhong, Guo-Qing; Chen, Ling

    2016-01-01

    .... The nickel and manganese ions were all hexacoordinated. The thermal decomposition processes of the complexes under air included the loss of water molecule, the pyrolysis of ligands, and the decomposition of inorganic salts, and the final residues were nickel oxide and manganese oxide, respectively.

  1. Nanomechanical properties and thermal decomposition of Cu-Al2O3 composites for FGM applications

    Directory of Open Access Journals (Sweden)

    Koumoulos Elias P.

    2016-01-01

    Full Text Available It is widely reported that copper-alumina (Cu-Al2O3 nanocomposite materials exhibit high potential for use in structural applications in which enhanced mechanical characteristics are required. The investigation of Cu-Al2O3 nanocomposites which are to form a functionally graded material (FGM structure in terms of nanomechanical/structural integrity and thermal stability is still scarce. In this work, fully characterized nanosized Al2O3 powder has been incorporated in Cu matrix in various compositions (2, 5 and 10 wt.% of Al2O3 content. The produced composites were evaluated in terms of their morphology, structural analysis, thermal behavior, nanomechanical properties and their extent of viscoplasticity. The results reveal that all nanocomposites degrade at elevated temperatures; increased surface mass gain with decreasing Al2O3 content was observed, while no such difference of % mass gain in 5 and 10 wt.% of Al and Al2O3 content in Cu was observed. The increase of Al2O3 wt.% content results in thermal stability enhancement of the nanocomposites. The thermal decomposition process of the material is reduced in the presence of 10 wt.% of Al2O3 content. This result for the matrix decomposition can be explained by a decrease in the diffusion of oxygen and volatile degradation products throughout the composite material due to the incorporation of Al and Al2O3. The Al2O3 powder enhances the overall thermal stability of the system. All samples exhibited significant pile-up of the materials after nanoindentation testing. Increasing the wt.% of Al2O3 content was found to increase the creep deformation of the samples as well as the hardness and elastic modulus values.

  2. SYNTHESIS AND CHARACTERIZATION OF METALLIC COPPER NANOPARTICLES VIA THERMAL DECOMPOSITION METHOD

    OpenAIRE

    A. Dinesh Karthik; Dr. K. Geetha

    2017-01-01

    Copper (II) fumarate was used as a precursor to prepare metallic copper nanoparticles by thermal decomposition. Synthesis of inorganic nanoparticles by thermal decomposition is one of the methods to produce stable nanodisperse suspensions with the ability of self assembly. Copper (II) fumarate precursor was treated with oleylamine which is used as both the medium and the Stabilizing reagent. The precursor and copper nanoparticles were characterized by UV-Vis Spectroscopy, FT - IR, XRD, CV, AF...

  3. In Situ Thermal Decomposition of Exfoliated Two-Dimensional Black Phosphorus.

    Science.gov (United States)

    Liu, Xiaolong; Wood, Joshua D; Chen, Kan-Sheng; Cho, EunKyung; Hersam, Mark C

    2015-03-05

    With a semiconducting band gap and high charge carrier mobility, two-dimensional (2D) black phosphorus (BP)—often referred to as phosphorene—holds significant promise for next generation electronics and optoelectronics. However, as a 2D material, it possesses a higher surface area to volume ratio than bulk BP, suggesting that its chemical and thermal stability will be modified. Herein, an atomic-scale microscopic and spectroscopic study is performed to characterize the thermal degradation of mechanically exfoliated 2D BP. From in situ scanning/transmission electron microscopy, decomposition of 2D BP is observed to occur at ∼400 °C in vacuum, in contrast to the 550 °C bulk BP sublimation temperature. This decomposition initiates via eye-shaped cracks along the [001] direction and then continues until only a thin, amorphous red phosphorus like skeleton remains. In situ electron energy loss spectroscopy, energy-dispersive X-ray spectroscopy, and energy-loss near-edge structure changes provide quantitative insight into this chemical transformation process.

  4. CFD SIMULATION FOR DEMILITARIZATION OF RDX IN A ROTARY KILN BY THERMAL DECOMPOSITION

    Directory of Open Access Journals (Sweden)

    SI H. LEE

    2017-06-01

    Full Text Available Demilitarization requires the recovery and disposal of obsolete ammunition and explosives. Since open burning/detonation of hazardous waste has caused serious environmental and safety problems, thermal decomposition has emerged as one of the most feasible methods. RDX is widely used as a military explosive due to its high melting temperature and detonation power. In this work, the feasible conditions under which explosives can be safely incinerated have been investigated via a rotary kiln simulation. To solve this problem, phase change along with the reactions of RDX has been incisively analyzed. A global reaction mechanism consisting of condensed phase and gas phase reactions are used in Computational Fluid Dynamics simulation. User Defined Functions in FLUENT is utilized in this study to inculcate the reactions and phase change into the simulation. The results divulge the effect of temperature and the varying amounts of gas produced in the rotary kiln during the thermal decomposition of RDX. The result leads to the prospect of demilitarizing waste explosives to avoid the possibility of detonation.

  5. Thermal Decomposition of RDX from Reactive Molecular Dynamics

    National Research Council Canada - National Science Library

    Strachan, Alejandro; Kober, Edward M; van Duin, Adri C; Oxgaard, Jonas; Goddard, III, William A

    2005-01-01

    ...] at various temperatures and densities. We find that the time evolution of the potential energy can be described reasonably well with a single exponential function from which we obtain an overall characteristic time of decomposition...

  6. The surface quasiliquid melt acceleration and the role of thermodynamic phase in the thermal decomposition of crystalline organic explosives

    Energy Technology Data Exchange (ETDEWEB)

    Henson, Bryan F [Los Alamos National Laboratory

    2010-01-01

    We show that melt acceleration in the thermal decomposition of crystalline organic solids is a manifestation of the surface quasiliquid phase. We derive a single universal rate law for melt acceleration that is a simple function of the metastable liquid activity below the melting point, and has a zero order term proportional to the quasiliquid thickness. We argue that the underlying mechanisms of this model will provide a molecular definition for the stability of the class of secondary explosives.

  7. Thermal Decomposition Model Development of EN-7 and EN-8 Polyurethane Elastomers.

    Energy Technology Data Exchange (ETDEWEB)

    Keedy, Ryan Michael [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Harrison, Kale Warren [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Cordaro, Joseph Gabriel [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2017-10-01

    Thermogravimetric analysis - gas chromatography/mass spectrometry (TGA- GC/MS) experiments were performed on EN-7 and EN-8, analyzed, and reported in [1] . This SAND report derives and describes pyrolytic thermal decomposition models for use in predicting the responses of EN-7 and EN-8 in an abnormal thermal environment.

  8. Thermal decomposition of AP/HTPB propellants in presence of Zn nanoalloys

    Science.gov (United States)

    Chaturvedi, Shalini; Dave, Pragnesh N.; Patel, Nikul N.

    2015-01-01

    Composite solid propellants were prepared with and without nanoalloys (Zn-Cu, Zn-Ni, Zn-Fe), where nanoalloys are used as catalyst. Catalytic properties of these nanomaterials measured on ammonium perchlorate/hydroxyl-terminated polybutadiene propellant by thermogravimetric analysis and differential thermal analysis. Both experimental results show enhancement in the thermal decomposition of propellants in presence of nanoalloys. In differential thermal analysis method, experiments had done at three heating rates, β1 = 5°, β2 = 10°, β3 = 15° per minute. Calculation of activation energy of high temperature decomposition step was done by using following Kissinger equation. Zn-Cu was found to be the best.

  9. Thermal decomposition of nano-enabled thermoplastics: Possible environmental health and safety implications

    Energy Technology Data Exchange (ETDEWEB)

    Sotiriou, Georgios A.; Singh, Dilpreet; Zhang, Fang [Center for Nanotechnology and Nanotoxicology, Department of Environmental Health, T.H. Chan School of Public Health, Harvard University, 665 Huntington Ave., Boston, MA 02115 (United States); Chalbot, Marie-Cecile G. [Department of Environmental and Occupational Health, College of Public Health, University of Arkansas for Medical Sciences, Little Rock, AR 72205 (United States); Spielman-Sun, Eleanor [Department of Civil and Environmental Engineering, Carnegie Mellon University, Pittsburgh, PA 15213 (United States); Hoering, Lutz [BASF SE, Material Physics, 67056 Ludwigshafen (Germany); Kavouras, Ilias G. [Department of Environmental and Occupational Health, College of Public Health, University of Arkansas for Medical Sciences, Little Rock, AR 72205 (United States); Lowry, Gregory V. [Department of Civil and Environmental Engineering, Carnegie Mellon University, Pittsburgh, PA 15213 (United States); Wohlleben, Wendel [Center for Nanotechnology and Nanotoxicology, Department of Environmental Health, T.H. Chan School of Public Health, Harvard University, 665 Huntington Ave., Boston, MA 02115 (United States); BASF SE, Material Physics, 67056 Ludwigshafen (Germany); Demokritou, Philip, E-mail: pdemokri@hsph.harvard.edu [Center for Nanotechnology and Nanotoxicology, Department of Environmental Health, T.H. Chan School of Public Health, Harvard University, 665 Huntington Ave., Boston, MA 02115 (United States)

    2016-03-15

    Highlights: • Nano-enabled products might reach their end-of-life by thermal decomposition. • Thermal decomposition provides two by-products: released aerosol and residual ash. • Is there any nanofiller release in byproducts? • Risk assessment of potential environmental health implications. - Abstract: Nano-enabled products (NEPs) are currently part of our life prompting for detailed investigation of potential nano-release across their life-cycle. Particularly interesting is their end-of-life thermal decomposition scenario. Here, we examine the thermal decomposition of widely used NEPs, namely thermoplastic nanocomposites, and assess the properties of the byproducts (released aerosol and residual ash) and possible environmental health and safety implications. We focus on establishing a fundamental understanding on the effect of thermal decomposition parameters, such as polymer matrix, nanofiller properties, decomposition temperature, on the properties of byproducts using a recently-developed lab-based experimental integrated platform. Our results indicate that thermoplastic polymer matrix strongly influences size and morphology of released aerosol, while there was minimal but detectable nano-release, especially when inorganic nanofillers were used. The chemical composition of the released aerosol was found not to be strongly influenced by the presence of nanofiller at least for the low, industry-relevant loadings assessed here. Furthermore, the morphology and composition of residual ash was found to be strongly influenced by the presence of nanofiller. The findings presented here on thermal decomposition/incineration of NEPs raise important questions and concerns regarding the potential fate and transport of released engineered nanomaterials in environmental media and potential environmental health and safety implications.

  10. Kinetics of the thermal decomposition of tetramethylsilane behind ...

    Indian Academy of Sciences (India)

    equal concentrations via reaction 1. It was further con- firmed that, 1,3-butadiene does not decompose in the investigated range of the temperatures, by carrying out its decomposition independently. Skinner et al.,37 and. Hidaka et al.,38 also have reported that 1,3-butadiene does not decompose in this temperature range.

  11. Lignin derivatives formation in catalysed thermal decomposition of ...

    African Journals Online (AJOL)

    Decomposition of elephant grass (Panicum maxima) lignocellulose was carried out with Pd and Ni/Pt-doped alumina as catalysts; chromic oxide was also used in some cases. For systems that contained no chromic oxide, formation of gaseous and volatile liquid products was highest for Ni/Pt, intermediate for Pd/λ- and least ...

  12. Thermal decomposition of natural polysaccharides: Chitin and chitosan

    Directory of Open Access Journals (Sweden)

    Kuchina Yu.A.

    2015-03-01

    Full Text Available The results of the thermal analysis of shrimp’s chitin and chitosan have been presented (samples of polysaccharide differed by the deacetylation degree have been studied. The thermal analysis has been carried out by differential thermogravimetry and differential scanning calorimetry. Activation energy of process of chitin and chitosan thermal destruction has been calculated

  13. Effect of aging temperature on phase decomposition and mechanical properties in cast duplex stainless steels

    Energy Technology Data Exchange (ETDEWEB)

    Mburu, Sarah; Kolli, R. Prakash; Perea, Daniel E.; Schwarm, Samuel C.; Eaton, Arielle; Liu, Jia; Patel, Shiv; Bartrand, Jonah; Ankem, Sreeramamurthy

    2017-04-01

    The microstructure and mechanical properties in unaged and thermally aged (at 280 oC, 320 oC, 360 oC, and 400 oC to 4300 h) CF–3 and CF–8 cast duplex stainless steels (CDSS) are investigated. The unaged CF–8 steel has Cr-rich M23C6 carbides located at the δ–ferrite/γ– austenite heterophase interfaces that were not observed in the CF–3 steel and this corresponds to a difference in mechanical properties. Both unaged steels exhibit incipient spinodal decomposition into Fe-rich α–domains and Cr-rich α’–domains. During aging, spinodal decomposition progresses and the mean wavelength (MW) and mean amplitude (MA) of the compositional fluctuations increase as a function of aging temperature. Additionally, G–phase precipitates form between the spinodal decomposition domains in CF–3 at 360 oC and 400 oC and in CF–8 at 400 oC. The microstructural evolution is correlated to changes in mechanical properties.

  14. Thermal decomposition of dolomite under CO2: insights from TGA and in situ XRD analysis.

    Science.gov (United States)

    Valverde, Jose Manuel; Perejon, Antonio; Medina, Santiago; Perez-Maqueda, Luis A

    2015-11-28

    Thermal decomposition of dolomite in the presence of CO2 in a calcination environment is investigated by means of in situ X-ray diffraction (XRD) and thermogravimetric analysis (TGA). The in situ XRD results suggest that dolomite decomposes directly at a temperature around 700 °C into MgO and CaO. Immediate carbonation of nascent CaO crystals leads to the formation of calcite as an intermediate product of decomposition. Subsequently, decarbonation of this poorly crystalline calcite occurs when the reaction is thermodynamically favorable and sufficiently fast at a temperature depending on the CO2 partial pressure in the calcination atmosphere. Decarbonation of this dolomitic calcite occurs at a lower temperature than limestone decarbonation due to the relatively low crystallinity of the former. Full decomposition of dolomite leads also to a relatively low crystalline CaO, which exhibits a high reactivity as compared to limestone derived CaO. Under CO2 capture conditions in the Calcium-Looping (CaL) process, MgO grains remain inert yet favor the carbonation reactivity of dolomitic CaO especially in the solid-state diffusion controlled phase. The fundamental mechanism that drives the crystallographic transformation of dolomite in the presence of CO2 is thus responsible for its fast calcination kinetics and the high carbonation reactivity of dolomitic CaO, which makes natural dolomite a potentially advantageous alternative to limestone for CO2 capture in the CaL technology as well as SO2in situ removal in oxy-combustion fluidized bed reactors.

  15. Study of copper-chromium oxide catalyst . I. Thermal decomposition of copper(III) chromate, CuCrO4

    Science.gov (United States)

    Hanic, F.; Horváth, I.; Plesch, G.; Gáliková, Ľ.

    1985-09-01

    The kinetics, mechanism, and activation energy of the isothermal decomposition of CuCrO 4 was studied using an isothermal TG method and an X-ray high-temperature diffraction technique in either air or a flowing atmosphere of N 2. The enthalpy change ΔH of the decomposition reaction 2 CuCrO4→ CuO+ CuO+ CuCr2O4+ {3}/{2}O2 was determined by DSC analysis. The mechanism of the thermal decomposition of CuCrO 4 is well represented by the standard Avrami-Erofeev kinetic equation [- ln(1 - α)] {1}/{2} = kt . According to this mechanism, the reaction rate is controlled by the formation and growth of nuclei on the surface of the reactant. The activation energy EA of the process in air is EA = (248 ± 8) kJ mole -1, in flowing atmosphere of nitrogen EA = (229 ± 8) kJ mole -1. ΔH in air is 110 kJ mole -1, in flowing nitrogen 67 kJ mole -1. The lower values of ΔH and EA in the flowing atmosphere of nitrogen are due to the fast elimination of O 2 from the reaction interface. However, the decay of the crystalline portion of CuCrO 4 during its thermal decomposition, studied by the X-ray diffraction, is controlled by a different reaction mechanism (first-order kinetics). The reaction mechanism is discussed in the relation to the crystal structure of the reactants.

  16. Specific leaf area predicts dryland litter decomposition via two mechanisms

    NARCIS (Netherlands)

    Liu, Guofang; Wang, Lei; Jiang, Li; Pan, Xu; Huang, Zhenying; Dong, Ming; Cornelissen, Johannes H.C.

    2018-01-01

    Litter decomposition plays important roles in carbon and nutrient cycling. In dryland, both microbial decomposition and abiotic degradation (by UV light or other forces) drive variation in decomposition rates, but whether and how litter traits and position determine the balance between these

  17. Solid state green synthesis and catalytic activity of CuO nanorods in thermal decomposition of potassium periodate

    Science.gov (United States)

    Patel, Vinay Kumar; Bhattacharya, Shantanu

    2017-09-01

    The present study reports a facile solid state green synthesis process using the leaf extracts of Hibiscus rosa-sinensis to synthesize CuO nanorods with average diameters of 15-20 nm and lengths up to 100 nm. The as-synthesized CuO nanorods were characterized by x-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy and selected area electron diffraction. The formation mechanism of CuO nanorods has been explained by involving the individual role of amide I (amino groups) and carboxylate groups under excess hydroxyl ions released from NaOH. The catalytic activity of CuO nanorods in thermal decomposition of potassium periodate microparticles (µ-KIO4) microparticles was studied by thermo gravimetric analysis measurement. The original size (~100 µm) of commercially procured potassium periodate was reduced to microscale length scale to about one-tenth by PEG200 assisted emulsion process. The CuO nanorods prepared by solid state green route were found to catalyze the thermal decomposition of µ-KIO4 with a reduction of 18 °C in the final thermal decomposition temperature of potassium periodate.

  18. Kinetic analysis of overlapping multistep thermal decomposition comprising exothermic and endothermic processes: thermolysis of ammonium dinitramide.

    Science.gov (United States)

    Muravyev, Nikita V; Koga, Nobuyoshi; Meerov, Dmitry B; Pivkina, Alla N

    2017-01-25

    This study focused on kinetic modeling of a specific type of multistep heterogeneous reaction comprising exothermic and endothermic reaction steps, as exemplified by the practical kinetic analysis of the experimental kinetic curves for the thermal decomposition of molten ammonium dinitramide (ADN). It is known that the thermal decomposition of ADN occurs as a consecutive two step mass-loss process comprising the decomposition of ADN and subsequent evaporation/decomposition of in situ generated ammonium nitrate. These reaction steps provide exothermic and endothermic contributions, respectively, to the overall thermal effect. The overall reaction process was deconvoluted into two reaction steps using simultaneously recorded thermogravimetry and differential scanning calorimetry (TG-DSC) curves by considering the different physical meanings of the kinetic data derived from TG and DSC by P value analysis. The kinetic data thus separated into exothermic and endothermic reaction steps were kinetically characterized using kinetic computation methods including isoconversional method, combined kinetic analysis, and master plot method. The overall kinetic behavior was reproduced as the sum of the kinetic equations for each reaction step considering the contributions to the rate data derived from TG and DSC. During reproduction of the kinetic behavior, the kinetic parameters and contributions of each reaction step were optimized using kinetic deconvolution analysis. As a result, the thermal decomposition of ADN was successfully modeled as partially overlapping exothermic and endothermic reaction steps. The logic of the kinetic modeling was critically examined, and the practical usefulness of phenomenological modeling for the thermal decomposition of ADN was illustrated to demonstrate the validity of the methodology and its applicability to similar complex reaction processes.

  19. Comparative evaluation of thermal decomposition behavior and thermal stability of powdered ammonium nitrate under different atmosphere conditions.

    Science.gov (United States)

    Yang, Man; Chen, Xianfeng; Wang, Yujie; Yuan, Bihe; Niu, Yi; Zhang, Ying; Liao, Ruoyu; Zhang, Zumin

    2017-09-05

    In order to analyze the thermal decomposition characteristics of ammonium nitrate (AN), its thermal behavior and stability under different conditions are studied, including different atmospheres, heating rates and gas flow rates. The evolved decomposition gases of AN in air and nitrogen are analyzed with a quadrupole mass spectrometer. Thermal stability of AN at different heating rates and gas flow rates are studied by differential scanning calorimetry, thermogravimetric analysis, paired comparison method and safety parameter evaluation. Experimental results show that the major evolved decomposition gases in air are H2O, NH3, N2O, NO, NO2 and HNO3, while in nitrogen, H2O, NH3, NO and HNO3 are major components. Compared with nitrogen atmosphere, lower initial and end temperatures, higher heat flux and broader reaction temperature range are obtained in air. Meanwhile, higher air gas flow rate tends to achieve lower reaction temperature and to reduce thermal stability of AN. Self-accelerating decomposition temperature of AN in air is much lower than that in nitrogen. It is considered that thermostability of AN is influenced by atmosphere, heating rate and gas flow rate, thus changes of boundary conditions will influence its thermostability, which is helpful to its safe production, storage, transportation and utilization. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Temperature sensitivity and enzymatic mechanisms of soil organic matter decomposition along an altitudinal gradient on Mount Kilimanjaro.

    Science.gov (United States)

    Blagodatskaya, Еvgenia; Blagodatsky, Sergey; Khomyakov, Nikita; Myachina, Olga; Kuzyakov, Yakov

    2016-02-29

    Short-term acceleration of soil organic matter decomposition by increasing temperature conflicts with the thermal adaptation observed in long-term studies. Here we used the altitudinal gradient on Mt. Kilimanjaro to demonstrate the mechanisms of thermal adaptation of extra- and intracellular enzymes that hydrolyze cellulose, chitin and phytate and oxidize monomers ((14)C-glucose) in warm- and cold-climate soils. We revealed that no response of decomposition rate to temperature occurs because of a cancelling effect consisting in an increase in half-saturation constants (Km), which counteracts the increase in maximal reaction rates (Vmax with temperature). We used the parameters of enzyme kinetics to predict thresholds of substrate concentration (Scrit) below which decomposition rates will be insensitive to global warming. Increasing values of Scrit, and hence stronger canceling effects with increasing altitude on Mt. Kilimanjaro, explained the thermal adaptation of polymer decomposition. The reduction of the temperature sensitivity of Vmax along the altitudinal gradient contributed to thermal adaptation of both polymer and monomer degradation. Extrapolating the altitudinal gradient to the large-scale latitudinal gradient, these results show that the soils of cold climates with stronger and more frequent temperature variation are less sensitive to global warming than soils adapted to high temperatures.

  1. Quantitative structure—property relationship for thermal decomposition temperature of ionic liquids

    DEFF Research Database (Denmark)

    Gharagheizi, Farhad; Sattari, Mehdi; Ilani-Kashkouli, Poorandokht

    2012-01-01

    In this study, a wide literature survey has been conducted to gather an extensive set of thermal decomposition temperature (Td) data for ionic liquids (ILs). A data set consisting of Td data for 586 ILs was collated from 71 different literature sources. Using this data set, a reliable quantitative...

  2. Catalytic non-thermal plasma reactor for the decomposition of a ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 125; Issue 3. Catalytic non-thermal plasma reactor for the decomposition of a mixture of volatile organic compounds. B Rama Raju E Linga Reddy J Karuppiah P Manoj Kumar Reddy Ch Subrahmanyam. Volume 125 Issue 3 May 2013 pp 673-678 ...

  3. Thermal Decomposition and Phase Formation of Cerate-Zirconate Ceramics Prepared with Different Chelating Agents

    Science.gov (United States)

    Osman, Nafisah; Abdullah, Nur Athirah; Hasan, Sharizal

    2013-07-01

    Chelating agents of citric acid, lactic acid, glycine and ethylenediaminetetra acetic acid (EDTA) were used to synthesize a ceramic compound of Ba(Ce0.6Zr0.4)0.9Y0.1O2.95 (BCZY10) by a sol-gel method. Thermal decomposition and phase formation of the samples were analyzed by thermogravimetric analysis (TGA), Fourier transform infra-red (FTIR) spectroscopy and X-ray diffractometer (XRD). At heating rate of 10 °C min-1, all the samples exhibited almost similar pattern of TG-DTG profiles. A complete thermal decomposition process of the samples took place by three stages. The powders prepared using EDTA exhibited the lowest temperature for thermal decomposition since there was no significant weight loss above than 770 °C. Even after calcined at 1100 °C, the carbonate residue still remains in the samples as proven by FTIR result. The presence of this intermediate phase was also detected in XRD spectra as a small peak at 2θ≈23.9 ° corresponds to BaCO3 appeared for S1, S2 S3 and S4 samples. It was found that the chelating agents used had a decisive influence on the thermal decomposition of samples but no significant effect in reducing calcination temperature to produce a pure perovskite-like phase.

  4. Effect of pre-heating on the thermal decomposition kinetics of cotton

    Science.gov (United States)

    The effect of pre-heating at low temperatures (160-280°C) on the thermal decomposition kinetics of scoured cotton fabrics was investigated by thermogravimetric analysis under nonisothermal conditions. Isoconversional methods were used to calculate the activation energies for the pyrolysis after one-...

  5. Effect of Hydration State of Martian Perchlorate Salts on Their Decomposition Temperatures During Thermal Extraction

    Science.gov (United States)

    Royle, Samuel H.; Montgomery, Wren; Kounaves, Samuel P.; Sephton, Mark A.

    2017-12-01

    Three Mars missions have analyzed the composition of surface samples using thermal extraction techniques. The temperatures of decomposition have been used as diagnostic information for the materials present. One compound of great current interest is perchlorate, a relatively recently discovered component of Mars' surface geochemistry that leads to deleterious effects on organic matter during thermal extraction. Knowledge of the thermal decomposition behavior of perchlorate salts is essential for mineral identification and possible avoidance of confounding interactions with organic matter. We have performed a series of experiments which reveal that the hydration state of magnesium perchlorate has a significant effect on decomposition temperature, with differing temperature releases of oxygen corresponding to different perchlorate hydration states (peak of O2 release shifts from 500 to 600°C as the proportion of the tetrahydrate form in the sample increases). Changes in crystallinity/crystal size may also have a secondary effect on the temperature of decomposition, and although these surface effects appear to be minor for our samples, further investigation may be warranted. A less than full appreciation of the hydration state of perchlorate salts during thermal extraction analyses could lead to misidentification of the number and the nature of perchlorate phases present.

  6. An ab initio molecular dynamics study of thermal decomposition of 3,6-di(azido)-1,2,4,5-tetrazine.

    Science.gov (United States)

    Wu, Qiong; Zhu, Weihua; Xiao, Heming

    2014-10-21

    Ab initio molecular dynamics simulations were performed to study the thermal decomposition of isolated and crystal 3,6-di(azido)-1,2,4,5-tetrazine (DiAT). During unimolecular decomposition, the three different initiation mechanisms were observed to be N-N2 cleavage, ring opening, and isomerization, respectively. The preferential initial decomposition step is the homolysis of the N-N2 bond in the azido group. The release mechanisms of nitrogen gas are found to be very different in the early and later decomposition stages of crystal DiAT. In the early decomposition, DiAT decomposes very fast and drastically without forming any stable long-chains or heterocyclic clusters, and most of the nitrogen gases are released through rapid rupture of nitrogen-nitrogen and carbon-nitrogen bonds. But in the later decomposition stage, the release of nitrogen gas is inhibited due to low mobility, long distance from each other, and strong carbon-nitrogen bonds. To overcome the obstacles, the nitrogen gases are released through slow formation and disintegration of polycyclic networks. Our simulations suggest a new decomposition mechanism for the organic polyazido initial explosive at the atomistic level.

  7. Design and implementation of mixing chambers to improve thermal decomposition of urea for NOX abatement

    KAUST Repository

    Lee, Junggil

    2012-10-01

    Urea-selective catalytic reduction (SCR) has been reported as the most promising technique for adherence to NOX emissions regulations. In the urea-SCR process, NH3 is generated by urea thermal decomposition and hydrolysis and is then used as a reductant of NOX in the SCR catalyst. Therefore, improving the NOX conversion efficiency of urea-SCR requires enhancement of thermal decomposition upstream of the SCR catalyst. In the present work, two types of mixing chambers were designed and fabricated to improve urea thermal decomposition, and experiments with and without a mixing chamber were carried out to analyze thermal-decomposition characteristics of urea in the exhaust pipe with respect to inlet velocity (4-12μm/s) and temperature (350°C-500°C). Urea thermal decomposition is greatly enhanced at higher gas temperatures. At an inlet velocity of 6μm/s in the A-type mixing chamber, NH3 concentrations generated along the exhaust pipe were about 171% and 157% greater than those without the mixing chamber for inlet temperatures of 400°C and 500°C, respectively. In the case of the B-type mixing chamber, NH3 concentrations generated at inlet temperatures of 400°C and 500°C were about 147% and 179% greater than those without the mixing chamber, respectively. Note that the implementation of mixing chambers significantly enhanced conversion of urea to NH3 because it increased the residence time of urea in the exhaust pipe and improved mixing between urea and exhaust gas. © 2012, Mary Ann Liebert, Inc.

  8. Decomposition Criterion-based Redundancy Removal in Mechanical Structures

    Directory of Open Access Journals (Sweden)

    A. N. Bozhko

    2014-01-01

    Full Text Available The most important design solutions of production engineering for the assembly operation are an assembly sequence and assembly chart. Both are closely linked with each other and therefore are recorded in the single process flow sheet that is an assembly chart.Capability for successive order assembling and splitting into assembly units depends on a set of the product design properties from which the main ones are position mechanical connections used to locate details within a product. An adequate mathematical model of the mechanical connections of technical system is a hyper graph. It allows us to give the correct description of the location relation of variable-locality.The analysis of the array of drawings shows that many designs contain redundant mechanical connections. The inequality is a criterion of redundancy, where |X| is the number of tops of the hyper graph (details, and |R| is the number of hyper edges (full assembly bases. Excess of mutual coordination is a harmful phenomenon which at designing stage exhibits as unsolvable dimension chains, while at the assembly stage it shows as relocation. Redundant connections should be removed from a design at the earliest design-for-manufacturing stages. Removal of connections generates mechanical structures with different assembly properties. The work offers some important criteria of generation of irredundant mechanical structures. The paper considers in detail a maximum decomposition criterion, which allows us to receive structures with the greatest capability to split into assembly units. It shows that such structures exhibit high flexibility in assembling and are adaptable to various specifications and production processes.

  9. Thermal decomposition behavior of nano/micro bimodal feedstock with different solids loading

    Science.gov (United States)

    Oh, Joo Won; Lee, Won Sik; Park, Seong Jin

    2018-01-01

    Debinding is one of the most critical processes for powder injection molding. The parts in debinding process are vulnerable to defect formation, and long processing time of debinding decreases production rate of whole process. In order to determine the optimal condition for debinding process, decomposition behavior of feedstock should be understood. Since nano powder affects the decomposition behavior of feedstock, nano powder effect needs to be investigated for nano/micro bimodal feedstock. In this research, nano powder effect on decomposition behavior of nano/micro bimodal feedstock has been studied. Bimodal powders were fabricated with different ratios of nano powder, and the critical solids loading of each powder was measured by torque rheometer. Three different feedstocks were fabricated for each powder depending on solids loading condition. Thermogravimetric analysis (TGA) experiment was carried out to analyze the thermal decomposition behavior of the feedstocks, and decomposition activation energy was calculated. The result indicated nano powder showed limited effect on feedstocks in lower solids loading condition than optimal range. Whereas, it highly influenced the decomposition behavior in optimal solids loading condition by causing polymer chain scission with high viscosity.

  10. Effect of thermal decomposition of hydroxyapatite on the thermoluminescent response

    Energy Technology Data Exchange (ETDEWEB)

    Sandoval C, K. J.; Zarate M, J.; Lemus R, J. [Universidad Michoacana de San Nicolas de Hidalgo, Instituto de Investigaciones Metalurgicas, Ciudad Universitaria, Edificio U, 58060 Morelia, Michoacan (Mexico); Rivera M, T., E-mail: karlasandovalc@gmail.com [IPN, Centro de Investigacion en Ciencia Aplicada y Tecnologia Avanzada, Av. Legaria 694, Col. Irrigacion, 11500 Mexico D. F. (Mexico)

    2014-08-15

    In this work, a study on the thermoluminescence (Tl) induced by gamma radiation in synthetic hydroxyapatite (Hap) annealed at different temperatures obtained by the precipitation method is presented. Synthesis of hydroxyapatite Hap was carried out starting from inorganic precursors [Ca(NO{sub 3}){sub 2}·4H{sub 2}O and (NH{sub 4}){sub 2}HPO{sub 4}]. The precipitate was filtered, washed, dried and then the powder was calcined at different temperatures until the Hap decomposition. The structural and morphological characterization was carried out using both X-ray diffraction (XRD) and scanning electron microscopy (Sem) techniques. Thermoluminescent (Tl) properties of Hap powders were irradiated at different gamma radiation doses. According to X ray diffraction patterns, the tricalcium diphosphate phase (Tcp) appear when the Hap was calcined at 900 grades C. Tl glow curve showed two peaks located at around 200 and 300 grades C, respectively. Tl response as a function of gamma radiation dose was in a wide range from 25 to 100 Gy. The fading of the Tl response at 134 days after irradiation was measured. Experimental results showed that the synthetic hydroxyapatite obtained by precipitation technique may have dosimetric applications when is annealed at temperature of 900 grades C, where the Tcp phase appears and contributes to Tl response, which opens the possibility of using this biomaterials in the area of dosimetry, as they are generally used for biomedical implants. (author)

  11. The products of the thermal decomposition of CH{sub 3}CHO

    Energy Technology Data Exchange (ETDEWEB)

    Vasiliou, AnGayle [Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215 (United States); National Renewable Energy Laboratory, 1617 Cole Blvd., Golden, Colorado 80401 (United States); Piech, Krzysztof M.; Barney Ellison, G. [Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215 (United States); Zhang Xu [Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Drive, Pasadena, California 91109-8099 (United States); Nimlos, Mark R. [National Renewable Energy Laboratory, 1617 Cole Blvd., Golden, Colorado 80401 (United States); Ahmed, Musahid; Golan, Amir; Kostko, Oleg [Chemical Sciences Division, Lawrence Berkeley National Laboratory, MS 6R-2100, Berkeley, California 94720 (United States); Osborn, David L. [Combustion Research Facility, Sandia National Laboratories, P.O. Box 969, MS 9055, Livermore, California 94551-0969 (United States); Daily, John W. [Center for Combustion and Environmental Research, Department of Mechanical Engineering, University of Colorado at Boulder, Boulder, Colorado 80309-0427 (United States); Stanton, John F. [Institute for Theoretical Chemistry, Department of Chemistry, University of Texas, Austin, Texas 78712 (United States)

    2011-07-07

    We have used a heated 2 cm x 1 mm SiC microtubular ({mu}tubular) reactor to decompose acetaldehyde: CH{sub 3}CHO +{Delta}{yields} products. Thermal decomposition is followed at pressures of 75-150 Torr and at temperatures up to 1675 K, conditions that correspond to residence times of roughly 50-100 {mu}s in the {mu}tubular reactor. The acetaldehyde decomposition products are identified by two independent techniques: vacuum ultraviolet photoionization mass spectroscopy (PIMS) and infrared (IR) absorption spectroscopy after isolation in a cryogenic matrix. Besides CH{sub 3}CHO, we have studied three isotopologues, CH{sub 3}CDO, CD{sub 3}CHO, and CD{sub 3}CDO. We have identified the thermal decomposition products CH{sub 3} (PIMS), CO (IR, PIMS), H (PIMS), H{sub 2} (PIMS), CH{sub 2}CO (IR, PIMS), CH{sub 2}=CHOH (IR, PIMS), H{sub 2}O (IR, PIMS), and HC{identical_to}CH (IR, PIMS). Plausible evidence has been found to support the idea that there are at least three different thermal decomposition pathways for CH{sub 3}CHO; namely, radical decomposition: CH{sub 3}CHO +{Delta}{yields} CH{sub 3}+[HCO]{yields} CH{sub 3}+ H + CO; elimination: CH{sub 3}CHO +{Delta}{yields} H{sub 2}+ CH{sub 2}=C=O; isomerization/elimination: CH{sub 3}CHO +{Delta}{yields}[CH{sub 2}=CH-OH]{yields} HC{identical_to}CH + H{sub 2}O. An interesting result is that both PIMS and IR spectroscopy show compelling evidence for the participation of vinylidene, CH{sub 2}=C:, as an intermediate in the decomposition of vinyl alcohol: CH{sub 2}=CH-OH +{Delta}{yields}[CH{sub 2}=C:]+ H{sub 2}O {yields} HC{identical_to}CH + H{sub 2}O.

  12. Extraction of Curcumin Pigment from Indonesian Local Turmeric with Its Infrared Spectra and Thermal Decomposition Properties

    Science.gov (United States)

    Nandiyanto, A. B. D.; Wiryani, A. S.; Rusli, A.; Purnamasari, A.; Abdullah, A. G.; Ana; Widiaty, I.; Hurriyati, R.

    2017-03-01

    Curcumin is one of the pigments which is used as a spice in Asian cuisine, traditional cosmetic, and medicine. Therefore, process for getting curcumin has been widely studied. Here, the purpose of this study was to demonstrate the simple method for extracting curcumin from Indonesian local turmeric and investigate the infrared spectra and thermal decomposition properties. In the experimental procedure, the washed turmeric was dissolved into an ethanol solution, and then put into a rotary evaporator to enrich curcumin concentration. The result showed that the present method is effective to isolate curcumin compound from Indonesian local turmeric. Since the process is very simple, this method can be used for home industrial application. Further, understanding the thermal decomposition properties of curcumin give information, specifically relating to the selection of treatment when curcumin must face the thermal-related process.

  13. Thermal decomposition of dolomite under CO2: insights from TGA and in situ XRD analysis

    OpenAIRE

    Valverde, J.M.; Perejón, Antonio; Medina, Santiago; Pérez-Maqueda, Luis A.

    2015-01-01

    Thermal decomposition of dolomite in the presence of CO2 in a calcination environment is investigated by means of in situ X-ray diffraction (XRD) and thermogravimetric analysis (TGA). The in situ XRD results suggest that dolomite decomposes directly at a temperature around 700 °C into MgO and CaO. Immediate carbonation of nascent CaO crystals leads to the formation of calcite as an intermediate product of decomposition. Subsequently, decarbonation of this poorly crystalline calcite occurs whe...

  14. Kinetic Parameters of Thermal Decomposition Process Analyzed using a Mathematical Model

    Science.gov (United States)

    Nandiyanto, A. B. D.; Ekawati, R.; Wibawa, S. C.

    2018-01-01

    The purpose of this study was to show a mathematical analysis model for understanding kinetic parameters of thermal decomposition process. The mathematical model was derived based on phenomena happen during the thermal-related reaction. To get the kinetic parameters (i.e. reaction order, activation energy, and Arrhenius constant), the model was combined with the thermal characteristics of material gained from the thermal gravity (TG) and differential thermal analysis (DTA) curves. As an example, the model was used for analyzing the kinetic properties of trinitrotoluene. Interestingly, identical results gained from the present model with current literatures were obtained; in which these were because the present model was derived directly from the analysis of stoichiometrical and thermal analysis of the ideal chemical reaction. Since the present model confirmed to have a good agreement with current theories, further derivation from the present mathematical model can be useful for further development.

  15. Comparative evaluation of thermal oxidative decomposition for oil-plant residues via thermogravimetric analysis: Thermal conversion characteristics, kinetics, and thermodynamics.

    Science.gov (United States)

    Chen, Jianbiao; Wang, Yanhong; Lang, Xuemei; Ren, Xiu'e; Fan, Shuanshi

    2017-11-01

    Thermal oxidative decomposition characteristics, kinetics, and thermodynamics of rape straw (RS), rapeseed meal (RM), camellia seed shell (CS), and camellia seed meal (CM) were evaluated via thermogravimetric analysis (TGA). TG-DTG-DSC curves demonstrated that the combustion of oil-plant residues proceeded in three stages, including dehydration, release and combustion of organic volatiles, and chars oxidation. As revealed by combustion characteristic parameters, the ignition, burnout, and comprehensive combustion performance of residues were quite distinct from each other, and were improved by increasing heating rate. The kinetic parameters were determined by Coats-Redfern approach. The results showed that the most possible combustion mechanisms were order reaction models. The existence of kinetic compensation effect was clearly observed. The thermodynamic parameters (ΔH, ΔG, ΔS) at peak temperatures were calculated through the activated complex theory. With the combustion proceeding, the variation trends of ΔH, ΔG, and ΔS for RS (RM) similar to those for CS (CM). Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. Kinetic Study and Thermal Decomposition Behavior of Lignite Coal

    Directory of Open Access Journals (Sweden)

    Mehran Heydari

    2015-01-01

    Full Text Available A thermogravimetric analyzer was employed to investigate the thermal behavior and extract the kinetic parameters of Canadian lignite coal. The pyrolysis experiments were conducted in temperatures ranging from 298 K to 1173 K under inert atmosphere utilizing six different heating rates of 1, 6, 9, 12, 15, and 18 K min−1, respectively. There are different techniques for analyzing the kinetics of solid-state reactions that can generally be classified into two categories: model-fitting and model-free methods. Historically, model-fitting methods are broadly used in solid-state kinetics and show an excellent fit to the experimental data but produce uncertain kinetic parameters especially for nonisothermal conditions. In this work, different model-free techniques such as the Kissinger method and the isoconversional methods of Ozawa, Kissinger-Akahira-Sunose, and Friedman are employed and compared in order to analyze nonisothermal kinetic data and investigate thermal behavior of a lignite coal. Experimental results showed that the activation energy values obtained by the isoconversional methods were in good agreement, but Friedman method was considered to be the best among the model-free methods to evaluate kinetic parameters for solid-state reactions. These results can provide useful information to predict kinetic model of coal pyrolysis and optimization of the process conditions.

  17. Kinetic study of the thermal decomposition of poly(vinyl alcohol)/kraft lignin derivative blends

    Energy Technology Data Exchange (ETDEWEB)

    Fernandes, D.M. [Departamento de Quimica, Universidade Estadual de Maringa, Av. Colombo 5790, 87020-900 Maringa, PR (Brazil); Hechenleitner, A.A. Winkler [Departamento de Quimica, Universidade Estadual de Maringa, Av. Colombo 5790, 87020-900 Maringa, PR (Brazil); Pineda, E.A. Gomez [Departamento de Quimica, Universidade Estadual de Maringa, Av. Colombo 5790, 87020-900 Maringa, PR (Brazil)]. E-mail: eagpineda@uem.br

    2006-02-01

    A kraft lignin derivative (KLD) obtained by reaction with p-aminobenzoic acid/phthalic anhydride, was blended with poly(vinyl alcohol) (PVA) by solution casting from DMSO. PVA and PVA/KLD films were exposed to ultraviolet radiation (Hg lamp, 96 h) and analyzed by thermogravimetry (TG) in inert and oxidative atmosphere. Typical multi-step decomposition profiles were obtained. The apparent activation energy (E {sub a}) of the thermal degradation of the samples was computed by the Vyazovkin method. The KLD degradation presented only small intervals of decomposition deg.ree with constant E {sub a} values. PVA and blends showed intervals of up to 50% in decomposition deg.ree with nearly constant E {sub a}, and smaller intervals in which E {sub a} varies drastically. The influences of samples irradiation and of surrounding gas in TG analysis on E {sub a} are also shown.

  18. Thermal decomposition of MgCO3 during the atmospheric entry of micrometeoroids

    Science.gov (United States)

    Micca Longo, G.; Longo, S.

    2017-10-01

    In this paper, a first study of the atmospheric entry of carbonate micrometeoroids, in an astrobiological perspective, is performed. Therefore an entry model, which includes two-dimensional dynamics, non-isothermal atmosphere, ablation and radiation losses, is build and benchmarked to literature data for silicate micrometeoroids. A thermal decomposition model of initially pure magnesium carbonate is proposed, and it includes thermal energy, mass loss and the effect of changing composition as the carbonate grain is gradually converted into oxide. Several scenarios are obtained by changing the initial speed, entry angle and grain diameter, producing a systematic comparison of silicate and carbonate grain. The results of the composite model show that the thermal behaviour of magnesium carbonate is markedly different from that of the corresponding silicate, much lower equilibration temperatures being reached in the first stages of the entry. At the same time, the model shows that the limit of a thermal protection scenario, based on magnesium carbonate, is the very high decomposition speed even at moderate temperatures, which results in the total loss of carbon already at about 100 km altitude. The present results show that, although decomposition and associated cooling are important effects in the entry process of carbonate grains, the specific scenario of pure MgCO3 micrograin does not allow complex organic matter delivery to the lower atmosphere. This suggests us to consider less volatile carbonates for further studies.

  19. Thermal decomposition of 1-chloropropane behind the reflected ...

    Indian Academy of Sciences (India)

    effects such as stratospheric ozone depletion. Such problems can be reduced by minimizing the production ... as a method of destruction.1–4 Therefore, it is essential to understand the complete mechanism of .... such as real gas effects, boundary layer effects and exo or endothermicity of the chemical reactions. To esti-.

  20. Thermal decomposition of selected chlorinated hydrocarbons during gas combustion in fluidized bed

    Science.gov (United States)

    2013-01-01

    Background The process of thermal decomposition of dichloromethane (DCM) and chlorobenzene (MCB) during the combustion in an inert, bubbling fluidized bed, supported by LPG as auxiliary fuel, have been studied. The concentration profiles of C6H5CI, CH2Cl2, CO2, CO, NOx, COCl2, CHCl3, CH3Cl, C2H2, C6H6, CH4 in the flue gases were specified versus mean bed temperature. Results The role of preheating of gaseous mixture in fluidized bed prior to its ignition inside bubbles was identified as important factor for increase the degree of conversion of DCM and MCB in low bed temperature, in comparison to similar process in the tubular reactor. Conclusions Taking into account possible combustion mechanisms, it was identified that autoignition in bubbles rather than flame propagation between bubbles is needed to achieve complete destruction of DCM and MCB. These condition occurs above 900°C causing the degree of conversion of chlorine compounds of 92-100%. PMID:23289764

  1. Thermal decomposition of selected chlorinated hydrocarbons during gas combustion in fluidized bed

    Directory of Open Access Journals (Sweden)

    Olek Malgorzata

    2013-01-01

    Full Text Available Abstract Background The process of thermal decomposition of dichloromethane (DCM and chlorobenzene (MCB during the combustion in an inert, bubbling fluidized bed, supported by LPG as auxiliary fuel, have been studied. The concentration profiles of C6H5CI, CH2Cl2, CO2, CO, NOx, COCl2, CHCl3, CH3Cl, C2H2, C6H6, CH4 in the flue gases were specified versus mean bed temperature. Results The role of preheating of gaseous mixture in fluidized bed prior to its ignition inside bubbles was identified as important factor for increase the degree of conversion of DCM and MCB in low bed temperature, in comparison to similar process in the tubular reactor. Conclusions Taking into account possible combustion mechanisms, it was identified that autoignition in bubbles rather than flame propagation between bubbles is needed to achieve complete destruction of DCM and MCB. These condition occurs above 900°C causing the degree of conversion of chlorine compounds of 92-100%.

  2. Kinetics of thermal decomposition of hydrated minerals associated with hematite ore in a fluidized bed reactor

    Science.gov (United States)

    Beuria, P. C.; Biswal, S. K.; Mishra, B. K.; Roy, G. G.

    2017-03-01

    The kinetics of removal of loss on ignition (LOI) by thermal decomposition of hydrated minerals present in natural iron ores (i.e., kaolinite, gibbsite, and goethite) was investigated in a laboratory-scale vertical fluidized bed reactor (FBR) using isothermal methods of kinetic analysis. Experiments in the FBR in batch processes were carried out at different temperatures (300 to 1200°C) and residence time (1 to 30 min) for four different iron ore samples with various LOIs (2.34wt% to 9.83wt%). The operating velocity was maintained in the range from 1.2 to 1.4 times the minimum fluidization velocity ( U mf). We observed that, below a certain critical temperature, the FBR did not effectively reduce the LOI to a desired level even with increased residence time. The results of this study indicate that the LOI level could be reduced by 90% within 1 min of residence time at 1100°C. The kinetics for low-LOI samples (controlled physical moisture removal), followed by a higher activation energy (chemically controlled removal of LOI). In the case of high-LOI samples, three different kinetics mechanisms prevail at different temperature regimes. At temperature up to 450°C, diffusion kinetics prevails (removal of physical moisture); at temperature from 450 to 650°C, chemical kinetics dominates during removal of matrix moisture. At temperatures greater than 650°C, nucleation and growth begins to influence the rate of removal of LOI.

  3. Synthesis and Characterization of [60]Fullerene-Glycidyl Azide Polymer and Its Thermal Decomposition

    Directory of Open Access Journals (Sweden)

    Ting Huang

    2015-05-01

    Full Text Available A new functionalized [60]fullerene-glycidyl azide polymer (C60-GAP was synthesized for the first time using a modified Bingel reaction of [60]fullerene (C60 and bromomalonic acid glycidyl azide polymer ester (BM-GAP. The product was characterized by Fourier transform infrared (FTIR, ultraviolet-visible (UV-Vis, and nuclear magnetic resonance spectroscopy (NMR analyses. Results confirmed the successful preparation of C60-GAP. Moreover, the thermal decomposition of C60-GAP was analyzed by differential scanning calorimetry (DSC, thermogravimetric analysis coupled with infrared spectroscopy (TGA-IR, and in situ FTIR. C60-GAP decomposition showed a three-step thermal process. The first step was due to the reaction of the azide group and fullerene at approximately 150 °C. The second step was ascribed to the remainder decomposition of the GAP main chain and N-heterocyclic at approximately 240 °C. The final step was attributed to the burning decomposition of amorphous carbon and carbon cage at around 600 °C.

  4. Exothermic Behavior of Thermal Decomposition of Sodium Percarbonate: Kinetic Deconvolution of Successive Endothermic and Exothermic Processes.

    Science.gov (United States)

    Nakano, Masayoshi; Wada, Takeshi; Koga, Nobuyoshi

    2015-09-24

    This study focused on the kinetic modeling of the thermal decomposition of sodium percarbonate (SPC, sodium carbonate-hydrogen peroxide (2/3)). The reaction is characterized by apparently different kinetic profiles of mass-loss and exothermic behavior as recorded by thermogravimetry and differential scanning calorimetry, respectively. This phenomenon results from a combination of different kinetic features of the reaction involving two overlapping mass-loss steps controlled by the physico-geometry of the reaction and successive endothermic and exothermic processes caused by the detachment and decomposition of H2O2(g). For kinetic modeling, the overall reaction was initially separated into endothermic and exothermic processes using kinetic deconvolution analysis. Then, both of the endothermic and exothermic processes were further separated into two reaction steps accounting for the physico-geometrically controlled reaction that occurs in two steps. Kinetic modeling through kinetic deconvolution analysis clearly illustrates the appearance of the net exothermic effect is the result of a slight delay of the exothermic process to the endothermic process in each physico-geometrically controlled reaction step. This demonstrates that kinetic modeling attempted in this study is useful for interpreting the exothermic behavior of solid-state reactions such as the oxidative decomposition of solids and thermal decomposition of oxidizing agent.

  5. Thermal Decomposition of Tetrazene at 90 deg C

    Science.gov (United States)

    1978-03-01

    led to its widespread use in percussion primer and stab detonator mixtures. In a recent study [1] it was concluded that the very low mechanical...Superintendent, Aeronatical Research Laboratories Senior Librarian, Defence Res rch Centre , Salisbury Librarian, R.A.N. Research Labdratory Document...Exchange Centre , DIR (16 copies) Principal Librarian, Campbell Park Library ADSATIS Annex Central Office, Directorate of Quality Assurance - Air Force

  6. Silver Nanoparticles and Graphitic Carbon Through Thermal Decomposition of a Silver/Acetylenedicarboxylic Salt

    Directory of Open Access Journals (Sweden)

    Komninou Philomela

    2009-01-01

    Full Text Available Abstract Spherically shaped silver nanoparticles embedded in a carbon matrix were synthesized by thermal decomposition of a Ag(I/acetylenedicarboxylic acid salt. The silver nanoparticles, which are formed either by pyrolysis at 300 °C in an autoclave or thermolysis in xylene suspension at reflux temperature, are acting catalytically for the formation of graphite layers. Both reactions proceed through in situ reduction of the silver cations and polymerization of the central acetylene triple bonds and the exact temperature of the reaction can be monitored through DTA analysis. Interestingly, the thermal decomposition of this silver salt in xylene partly leads to a minor fraction of quasicrystalline silver, as established by HR-TEM analysis. The graphitic layers covering the silver nanoparticles are clearly seen in HR-TEM images and, furthermore, established by the presence of sp2carbon at the Raman spectrum of both samples.

  7. Thermal conductivity decomposition in two-dimensional materials: Application to graphene

    Science.gov (United States)

    Fan, Zheyong; Pereira, Luiz Felipe C.; Hirvonen, Petri; Ervasti, Mikko M.; Elder, Ken R.; Donadio, Davide; Ala-Nissila, Tapio; Harju, Ari

    2017-04-01

    Two-dimensional materials have unusual phonon spectra due to the presence of flexural (out-of-plane) modes. Although molecular dynamics simulations have been extensively used to study heat transport in such materials, conventional formalisms treat the phonon dynamics isotropically. Here, we decompose the microscopic heat current in atomistic simulations into in-plane and out-of-plane components, corresponding to in-plane and out-of-plane phonon dynamics, respectively. This decomposition allows for direct computation of the corresponding thermal conductivity components in two-dimensional materials. We apply this decomposition to study heat transport in suspended graphene, using both equilibrium and nonequilibrium molecular dynamics simulations. We show that the flexural component is responsible for about two-thirds of the total thermal conductivity in unstrained graphene, and the acoustic flexural component is responsible for the logarithmic divergence of the conductivity when a sufficiently large tensile strain is applied.

  8. First-Principles Thermochemistry for the Thermal Decomposition of Titanium Tetraisopropoxide.

    Science.gov (United States)

    Buerger, Philipp; Nurkowski, Daniel; Akroyd, Jethro; Mosbach, Sebastian; Kraft, Markus

    2015-07-30

    The thermal decomposition of titanium tetraisopropoxide (TTIP) is investigated using quantum chemistry, statistical thermodynamics, and equilibrium composition analysis. A set of 981 Ti-containing candidate species are proposed systematically on the basis of the thermal breakage of bonds within a TTIP molecule. The ground state geometry, vibrational frequencies and hindrance potentials are calculated for each species at the B97-1/6-311+G(d,p) level of theory. Thermochemical data are computed by applying statistical thermodynamics and, if unknown, the standard enthalpy of formation is estimated using balanced reactions. Equilibrium composition calculations are performed under typical combustion conditions for premixed flames. The thermodynamically stable decomposition products for different fuel mixtures are identified. A strong positive correlation is found between the mole fractions of Ti species containing carbon and the TTIP precursor concentration.

  9. Synthesis of Copper Nanoparticles by Thermal Decomposition and Their Antimicrobial Properties

    Directory of Open Access Journals (Sweden)

    R. Betancourt-Galindo

    2014-01-01

    Full Text Available Copper nanoparticles were synthesized by thermal decomposition using copper chloride, sodium oleate, and phenyl ether as solvent agents. The formation of nanoparticles was evidenced by the X-ray diffraction and transmission electron microscopy. The peaks in the XRD pattern correspond to the standard values of the face centered cubic (fcc structure of metallic copper and no peaks of other impurity crystalline phases were detected. TEM analysis showed spherical nanoparticles with sizes in the range of 4 to 18 nm. The antibacterial properties of copper nanoparticles were evaluated in vitro against strains of Staphylococcus aureus and Pseudomonas aeruginosa. The antibacterial activity of copper nanoparticles synthesized by thermal decomposition showed significant inhibitory effect against these highly multidrug-resistant bacterial strains.

  10. A Property Extracted by Composition / Thermal Decomposition Analyses of Various Biomass Resources and Its Correlation

    Science.gov (United States)

    Mizuno, Satoru; Morita, Akihiro; Ida, Tamio; Namba, Kunihiko; Fuchihata, Manabu; Sawai, Toru

    Effective utilization of biomass resource rapidly has been promoting since the government adopted the ‘Biomass Nippon’ strategy at a cabinet meeting in 2002. Especially, the energy conversion technology of applying biomass has been expected from a point of view of environment and resource conservation. However, the energy conversion technologies are developed only for woody and herby biomass, and not for all of biomass. A stable supply of large quantity of biomass will be pressed in the future because the conversion technology must expand to use a variety of biomass. This study is to consider ways by various quantitative correlation analyses between the atomic composition and thermal decomposition of various biomass samples. The results found that thermal decomposition analyses of various biomass resources have correlations between atomic composition properties and exothermic properties.

  11. Solar production of catalytic filamentous carbon by thermal decomposition of hydrocarbons and carbon monoxide

    Energy Technology Data Exchange (ETDEWEB)

    Kirillov, V.A.; Kuvshinov, G.G.; Mogilnykh, Yu.I. [Boreskov Institute of Catalysis, Novosibirsk (Russian Federation); Reller, A. [University of Hamburg (Germany); Steinfeld, A.; Weidenkaff, A.; Meier, A. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    Concentrated solar radiation was used as the clean source of process heat for the production of Catalytic Filamentous Carbon (CFC) by thermal decomposition of gaseous hydrocarbons and by CO disproportionation in the presence of small metal catalyst particles. Depending on the catalyst, two different types of CFC, namely nano tubes and nano fibers, were obtained in solar experiments at the PSI solar furnace. (author) 2 figs., 1 tab., 7 refs.

  12. Critical Rate of Thermal Decomposition of Pure and Impregnated Lignocellulosic Materials

    Science.gov (United States)

    Chrebet, Tomáš; Balog, Karol

    2010-01-01

    Contribution deals with monitoring the impact of airflow velocity around the sample, the oven temperature during thermal decomposition and nature of the sample for the minimum mass flux rate needed to initiate flame combustion. We used the samples of lignocellulosic materials, particularly spruce wood, pure cellulose, flax, cellulose impregnated by 5%, 10%, 15% water solution of KHCO3 and by 5%, 10%, 15% water solution of (NH4)2HPO4.

  13. Aging Effects and Estimating Degradation Mechanisms of Thermally Upgraded Paper in Mineral Oil

    Science.gov (United States)

    Miyagi, Katsunori; Oe, Etsuo; Yamagata, Naoki

    The life of a transformer is limited to the deterioration of its solid insulation. Winding conductors and other solid insulation materials in oil-immersed transformers have been insulated using cellulose products. For many years, manufacturers have met the needs of special applications by designing transformers using thermally upgraded materials to achieve lighter weight, higher power density and increased life. Recently, the effect of thermally upgraded insulation on diagnostic techniques such as gas-in oil analysis, and their indication of insulation degradation have been reviewed. This paper describes evaluations of the thermal degradation characteristics and decomposition reactions in mineral transformer oil of amine-impregnated thermally upgraded paper insulation. The thermal resistance of the thermally upgraded paper is evaluated by comparison with Kraft paper insulation. Further, aging degradation mechanisms of decompositional degradation of the thermally upgraded paper due to aging in mineral transformer oil are proposed.

  14. Physical pretreatments of wastewater algae to reduce ash content and improve thermal decomposition characteristics.

    Science.gov (United States)

    Chen, Wan-Ting; Ma, Junchao; Zhang, Yuanhui; Gai, Chao; Qian, Wanyi

    2014-10-01

    Previous study showed high ash content in wastewater algae (WA) has a negative effect on bio-crude oil formation in hydrothermal liquefaction (HTL). This study explored the effect of different pretreatments on ash reduction and the thermal decomposition of WA. Single-stage (e.g. centrifugation) and two-stage pretreatments (e.g. centrifugation followed by ultrasonication, C+U) were used. The apparent activation energy of the thermal decomposition (E(a)) of pretreated algae was determined. HTL was conducted to study how different pretreatments may impact on bio-crude oil formation. Compared to untreated samples, the ash content of algae with centrifugation was reduced from 28.6% to 18.6%. With C+U pretreatments, E(a) was decreased from 50.2 kJ/mol to 35.9 kJ/mol and the bio-crude oil yield was increased from 30% to 55%. These results demonstrate that pretreatments of C+U can improve the thermal decomposition behavior of WA and enhance the bio-crude oil conversion efficiency. Copyright © 2014 Elsevier Ltd. All rights reserved.

  15. Thermal Analysis of the Decomposition of Ammonium Uranyl Carbonate (AUC) in Different Atmospheres

    DEFF Research Database (Denmark)

    Hälldahl, L.; Sørensen, Ole Toft

    1979-01-01

    The intermediate products formed during thermal decomposition of ammonium uranyl carbonate (AUC) in different atmospheres, (air, helium and hydrogen) have been determined by thermal analysis, (TG, and DTA) and X-ray analysis. The endproducts observed are U3O8 and UO2 in air/He and hydrogen......, respectively. The following intermediate products were observed in all atmospheres: http://www.sciencedirect.com.globalproxy.cvt.dk/cache/MiamiImageURL/B6THV-44K80TV-FB-1/0?wchp=dGLzVlz-zSkWW X-ray diffraction analysis showed that these phases were amorphous....

  16. Thermal decomposition and kinetics of plastic bonded explosives based on mixture of HMX and TATB with polymer matrices

    Directory of Open Access Journals (Sweden)

    Arjun Singh

    2017-02-01

    Full Text Available This work describes thermal decomposition behaviour of plastic bonded explosives (PBXs based on mixture of l,3,5,7-tetranitro- 1,3,5,7-tetrazocane (HMX and 2,4,6- triamino-1,3,5-trinitrobenzene (TATB with Viton A as polymer binder. Thermal decomposition of PBXs was undertaken by applying simultaneous thermal analysis (STA and differential scanning calorimetry (DSC to investigate influence of the HMX amount on thermal behavior and its kinetics. Thermogravimetric analysis (TGA indicated that the thermal decomposition of PBXs based on mixture of HMX and TATB was occurred in a three-steps. The first step was mainly due to decomposition of HMX. The second step was ascribed due to decomposition of TATB, while the third step was occurred due to decomposition of the polymer matrices. The thermal decomposition % was increased with increasing HMX amount. The kinetics related to thermal decomposition were investigated under non-isothermal for a single heating rate measurement. The variation in the activation energy of PBXs based on mixture of HMX and TATB was observed with varying the HMX amount. The kinetics from the results of TGA data at various heating rates under non-isothermal conditions were also calculated by Flynn–Wall–Ozawa (FWO and Kissinger-Akahira-Sunose (KAS methods. The activation energies calculated by employing FWO method were very close to those obtained by KAS method. The mean activation energy calculated by FWO and KAS methods was also a good agreement with the activation energy obtained from single heating rate measurement in the first step decomposition.

  17. Soft Thermal Sensor with Mechanical Adaptability.

    Science.gov (United States)

    Yang, Hui; Qi, Dianpeng; Liu, Zhiyuan; Chandran, Bevita K; Wang, Ting; Yu, Jiancan; Chen, Xiaodong

    2016-11-01

    A soft thermal sensor with mechanical adaptability is fabricated by the combination of single-wall carbon nanotubes with carboxyl groups and self-healing polymers. This study demonstrates that this soft sensor has excellent thermal response and mechanical adaptability. It shows tremendous promise for improving the service life of soft artificial-intelligence robots and protecting thermally sensitive electronics from the risk of damage by high temperature. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Excited electronic state decomposition mechanisms of clusters of ...

    Indian Academy of Sciences (India)

    In this report, electronically non-adiabatic decomposition pathways of clusters of dimethylnitramine and aluminum (DMNA-Al and DMNA-Al2) are discussed in comparison to isolated dimethylnitramine (DMNA). Electronically excited state processes of DMNA-Al and DMNA-Al2 are explored using the complete active space ...

  19. Peculiarities of obtaining a catalyst for the synthesis of nanostructured carbon materials via thermal decomposition

    Science.gov (United States)

    Dyachkova, Tatyana; Besperstova, Galina; Burakova, Elena; Rukhov, Artem; Tugolukov, Evgeny

    2017-11-01

    The paper presents the peculiarities of catalysts preparation through thermal decomposition and calcination. We propose methods for the evaluation of reagents solubility and decomposition degree that allow eliminating and adapting (NH4)6Mo7O24.4H2O, which does not meet the reagent solubility requirements contain (NH4)2MoO4, to obtain catalyst used to synthesize carbon nanotubes (CNTs) with a diameter of 5-30 nm via chemical vapor deposition. The density (1510…1515 kg/m3) and electrical conductivity (1.54….1.72 µS/cm) experimentally found for the initial solution make it possible to control the pre-catalyst quality prior to the thermal decomposition stage. With the help of obtained Co-Mo/Al2O3-MgO catalyst CNTs yield was achieved as 10.3… 11.9 and 20.3…23.0 [gram of CNTs / gram of catalysts] when using ethylene and propane-butane mixture as a carbon-containing gas, respectively.

  20. Synthesis and thermal decomposition of a novel zirconium acetato-propionate cluster: [Zr12

    Science.gov (United States)

    Petit, Sarah; Morlens, Stéphanie; Yu, Zeming; Luneau, Dominique; Pilet, Guillaume; Soubeyroux, Jean-Louis; Odier, Philippe

    2011-03-01

    This work reports a novel Zirconium acetato-propionate complex herein called [Zr12] obtained by reaction of zirconium acetylacetonate Zr(acac) 4 with propionic acid. The molecular structure has been determined by X-ray diffraction on single crystals and proposed to be [Zr 12(μ 3-O) 16(CH 3CH 2CO 2) 12(CH 3CO 2) 8(μ 2-CH 3CH 2CO 2) 4]. This cluster involves oxo/hydroxo bonds in the direct surrounding of the metallic center. The decomposition of [Zr12] has been studied by thermal analysis and compared to Zr(acac) 4. Its temperature of decomposition is much lower than for acetylacetonate derivative. In consequence, the formation of ZrO 2 is easier from [Zr12] than from Zr(acac) 4. This phenomenon highlights the influence of the molecular structure on the process of decomposition. The local surrounding of Zr in [Zr12] and in ZrO 2 are very close, while it is markedly different in Zr(acac) 4.This difference of environment of the metallic ions is at the origin of the huge difference of thermal behavior of both compounds.

  1. Vibrational Order, Structural Properties, and Optical Gap of ZnO Nanostructures Sintered through Thermal Decomposition

    Directory of Open Access Journals (Sweden)

    Alejandra Londono-Calderon

    2014-01-01

    Full Text Available The sintering of different ZnO nanostructures by the thermal decomposition of zinc acetate is reported. Morphological changes from nanorods to nanoparticles are exhibited with the increase of the decomposition temperature from 300 to 500°C. The material showed a loss in the crystalline order with the increase in the temperature, which is correlated to the loss of oxygen due to the low heating rate used. Nanoparticles have a greater vibrational freedom than nanorods which is demonstrated in the rise of the main Raman mode E 2(high during the transformation. The energy band gap of the nanostructured material is lower than the ZnO bulk material and decreases with the rise in the temperature.

  2. Synthesis, Optical Characterization, and Thermal Decomposition of Complexes Based on Biuret Ligand

    Directory of Open Access Journals (Sweden)

    Mei-Ling Wang

    2016-01-01

    Full Text Available Four complexes were synthesized in methanol solution using nickel acetate or nickel chloride, manganese acetate, manganese chloride, and biuret as raw materials. The complexes were characterized by elemental analyses, UV, FTIR, Raman spectra, X-ray powder diffraction, and thermogravimetric analysis. The compositions of the complexes were [Ni(bi2(H2O2](Ac2·H2O (1, [Ni(bi2Cl2] (2, [Mn(bi2(Ac2]·1.5H2O (3, and [Mn(bi2Cl2] (4 (bi = NH2CONHCONH2, respectively. In the complexes, every metal ion was coordinated by oxygen atoms or chlorine ions and even both. The nickel and manganese ions were all hexacoordinated. The thermal decomposition processes of the complexes under air included the loss of water molecule, the pyrolysis of ligands, and the decomposition of inorganic salts, and the final residues were nickel oxide and manganese oxide, respectively.

  3. Simultaneous differential scanning calorimetry and thermal desorption spectroscopy measurements for the study of the decomposition of metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez, J.F.; Cuevas, F.; Sanchez, C. [Univ. Autonoma, Madrid (Spain). Dept de Fisica de Materiales C-IV

    2000-02-28

    An innovative experimental method to investigate the thermal decomposition of metal hydrides is presented. The method is based on an experimental setup composed of a differential scanning calorimeter connected through a capillary tube to a mass spectrometer. The experimental system allows the simultaneous determination of the heat absorbed and the hydrogen evolved from a metal hydride during thermal decomposition. This arrangement constitutes a coupled differential scanning calorimetry (DSC) and thermal desorption spectroscopy (TDS) technique. It has been applied to metal hydride materials to demonstrate the capability of the experimental system. A method to obtain the heat of decomposition of metal hydrides is described. It involves the measurement of an apparent decomposition heat as a function of the carrier gas flow. (orig.)

  4. Mass spectrometry characterization of the thermal decomposition/digestion (TDD) at cysteine in peptides and proteins in the condensed phase.

    Science.gov (United States)

    Basile, Franco; Zhang, Shaofeng; Kandar, Sujit Kumar; Lu, Liang

    2011-11-01

    We report on the characterization by mass spectrometry (MS) of a rapid, reagentless and site-specific cleavage at the N-terminus of the amino acid cysteine (C) in peptides and proteins induced by the thermal decomposition at 220-250 °C for 10 s in solid samples. This thermally induced cleavage at C occurs under the same conditions and simultaneously to our previously reported thermally induced site-specific cleavage at the C-terminus of aspartic acid (D) (Zhang, S.; Basile, F. J. Proteome Res. 2007, 6, (5), 1700-1704). The C cleavage proceeds through cleavage of the nitrogen and α-carbon bond (N-terminus) of cysteine and produces modifications at the cleavage site with an amidation (-1 Da) of the N-terminal thermal decomposition product and a -32 Da mass change of the C-terminal thermal decomposition product, the latter yielding either an alanine or β-alanine residue at the N-terminus site. These modifications were confirmed by off-line thermal decomposition electrospray ionization (ESI)-MS, tandem MS (MS/MS) analyses and accurate mass measurements of standard peptides. Molecular oxygen was found to be required for the thermal decomposition and cleavage at C as it induced an initial cysteine thiol side chain oxidation to sulfinic acid. Similar to the thermally induced D cleavage, missed cleavages at C were also observed. The combined thermally induced digestion process at D and C, termed thermal decomposition/digestion (TDD), was observed on several model proteins tested under ambient conditions and the site-specificity of the method confirmed by MS/MS.

  5. Some peculiarities of zirconium tungstate synthesis by thermal decomposition of hydrothermal precursors

    Energy Technology Data Exchange (ETDEWEB)

    Gubanov, Alexander I., E-mail: gubanov@niic.nsc.su [Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, Akad. Lavrentiev Prospekt 3, 630090 Novosibirsk (Russian Federation); Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk (Russian Federation); Dedova, Elena S. [Institute of Strength Physics and Materials Science, Siberian Branch of the Russian Academy of Sciences, pr. Akademicheskii 2/4, 634021 Tomsk (Russian Federation); Tomsk Polytechnic University, Lenin Avenue 30, 634050 Tomsk (Russian Federation); Plyusnin, Pavel E.; Filatov, Eugeny Y. [Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, Akad. Lavrentiev Prospekt 3, 630090 Novosibirsk (Russian Federation); Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk (Russian Federation); Kardash, Tatyana Y. [Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Akad. Lavrentiev Prospekt 5, 630090 Novosibirsk (Russian Federation); Korenev, Sergey V. [Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, Akad. Lavrentiev Prospekt 3, 630090 Novosibirsk (Russian Federation); Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk (Russian Federation); Kulkov, Sergey N. [Institute of Strength Physics and Materials Science, Siberian Branch of the Russian Academy of Sciences, pr. Akademicheskii 2/4, 634021 Tomsk (Russian Federation); Tomsk Polytechnic University, Lenin Avenue 30, 634050 Tomsk (Russian Federation)

    2014-12-10

    Highlights: • Synthesis of ZrW{sub 2}O{sub 8} using hydrothermal method. • On hydrothermal synthesis optimal conc. of HCl in the reaction mixture is 2.3 M. • Thermal decomposition of ZrW{sub 2}O{sub 7}((OH){sub 1.5},Cl{sub 0.5})·2H{sub 2}O begins are 200 °S. • Amorphous intermediate crystallizes into cubic single-phase ZrW{sub 2}O{sub 8} above 550 °S. • ZrW{sub 2}O{sub 8} destructed at temperatures above 700 °S. - Abstract: This article discusses some peculiarities of the synthesis of ZrW{sub 2}O{sub 8} (1) using thermal decomposition of the precursor ZrW{sub 2}O{sub 7}((OH){sub 1.5},Cl{sub 0.5})·2H{sub 2}O (2) prepared by hydrothermal method. On hydrothermal synthesis of 2 the optimal concentration of hydrochloric acid in the reaction mixture is about 2.3 M. TG approach to determine the chemical composition of the precursor was suggested. It has been found that the precursor for the synthesis of zirconium tungstate has chemical formula 2. Thermal decomposition of the precursor 2 begins at 200 °S and affords an amorphous intermediate, which crystallizes as a cubic phase 1 above 550 °S with an exoeffect. The temperature of the beginning of the transition from amorphous to the crystalline state is 350 ± 25 °S.

  6. Ab initio investigation of the thermal decomposition of n-butylcyclohexane.

    Science.gov (United States)

    Ali, Mohamad Akbar; Dillstrom, V Tyler; Lai, Jason Y W; Violi, Angela

    2014-02-13

    Environmental and energy security concerns have motivated an increased focus on developing clean, efficient combustors, which increasingly relies on insight into the combustion chemistry of fuels. In particular, naphthenes (cycloalkanes and alkylcycloalkanes) are important chemical components of distillate fuels, such as diesel and jet fuels. As such, there is a growing interest in describing napthene reactivity with kinetic mechanisms. Use of these mechanisms in predictive combustion models aids in the development of combustors. This study focuses on the pyrolysis of n-butylcyclohexane (n-BCH), an important representative of naphthenes in jet fuels. Seven different unimolecular decomposition pathways of C-C bond fission were explored utilizing ab initio/DFT methods. Accurate reaction energies were computed using the high-level quantum composite G3B3 method. Variational transition state theory, Rice-Ramsperger-Kassel-Marcus/master equation simulations provided temperature- and pressure-dependent rate constants. Implementation of these pathways into an existing chemical kinetic mechanism improved the prediction of experimental OH radical and H2O speciation in shock tube oxidation. Simulations of this combustion showed a change in the expected decomposition chemistry of n-BCH, predicting increased production of cyclic alkyl radicals instead of straight-chain alkenes. The most prominent reaction pathway for the decomposition of n-BCH is n-BCH = C3H7 + C7H13. The results of this study provide insight into the combustion of n-BCH and will aid in the future development of naphthene kinetic mechanisms.

  7. High-temperature Raman study of L-alanine, L-threonine and taurine crystals related to thermal decomposition

    Energy Technology Data Exchange (ETDEWEB)

    Cavaignac, A.L.O. [Centro de Ciências Sociais, Saúde e Tecnologia, Universidade Federal do Maranhão, Imperatriz, MA 65900-410 (Brazil); Lima, R.J.C., E-mail: ricardo.lima.ufma@gmail.com [Centro de Ciências Sociais, Saúde e Tecnologia, Universidade Federal do Maranhão, Imperatriz, MA 65900-410 (Brazil); Façanha Filho, P.F. [Centro de Ciências Sociais, Saúde e Tecnologia, Universidade Federal do Maranhão, Imperatriz, MA 65900-410 (Brazil); Moreno, A.J.D. [Coordenação de Ciências Naturais, Universidade Federal do Maranhão, Bacabal, MA 65700-000 (Brazil); Freire, P.T.C. [Departamento de Física, Universidade Federal do Ceará, Fortaleza, CE 60455-760 (Brazil)

    2016-03-01

    In this work high-temperature Raman spectra are used to compare temperature dependence of the lattice mode wavenumber of L-alanine, L-threonine and taurine crystals. Anharmonic effects observed are associated with intermolecular N-H· · ·O hydrogen bond that plays an important role in thermal decomposition process of these materials. Short and strong hydrogen bonds in L-alanine crystal were associated with anharmonic effects in lattice modes leading to low thermal stability compared to taurine crystals. Connection between thermal decomposition process and anharmonic effects is furnished for the first time.

  8. Theoretical study of the pressure dependent rate constants of the thermal decomposition of β-propiolactone

    Directory of Open Access Journals (Sweden)

    Abolfazl Shiroudi

    2015-09-01

    Full Text Available A theoretical study of the thermal decomposition of β-propiolactone is carried out using ab initio molecular orbital (MO methods at the MP2/6-311+G∗∗ level and Rice–Ramsperger–Kassel–Marcus (RRKM theory. The reported experimental results showed that decomposition of β-propiolactone occurred by three competing homogeneous and first order reactions. For the three reactions, the calculation was also performed at the MP2/6-311+G∗∗ level of theory, as well as by single-point calculations at the B3LYP/6-311+G∗∗//MP2/6-311+G∗∗, and MP4/6-311+G∗∗//MP2/6-311+G∗∗ levels of theory. The fall-off pressures for the decomposition in these reactions are found to be 2.415, 9.423 × 10−2 and 3.676 × 10−3 mmHg, respectively.

  9. Decomposition of acetylcholine with ethylene formation in vitro. Possible free radical mechanism of acetylcholine action.

    Science.gov (United States)

    Kurchii, V M; Kurchii, B A

    2000-01-01

    Experiments were designed to investigate the effect of different buffered solutions, Fenton reagent and hydrogen peroxide on acetylcholine decomposition with ethylene formation. The data of the present study suggests that acetylcholine is decomposed in vitro to form ethylene by interacting with the free radicals or in the Hofmann's splitting reaction. It is found that free radicals are required for the fast decomposition of acetylcholine to form ethylene. A general mechanism to explain the rapid biological effects that can be influenced by the free radicals was proposed. We have concluded that endogenous metabolic free radicals can be involved in the decomposition of acetylcholine as well in the biological activation of formed ethylene in vivo.

  10. Waste energy harvesting mechanical and thermal energies

    CERN Document Server

    Ling Bing, Kong; Hng, Huey Hoon; Boey, Freddy; Zhang, Tianshu

    2014-01-01

    Waste Energy Harvesting overviews the latest progress in waste energy harvesting technologies, with specific focusing on waste thermal mechanical energies. Thermal energy harvesting technologies include thermoelectric effect, storage through phase change materials and pyroelectric effect. Waste mechanical energy harvesting technologies include piezoelectric (ferroelectric) effect with ferroelectric materials and nanogenerators. The book aims to strengthen the syllabus in energy, materials and physics and is well suitable for students and professionals in the fields.

  11. Kinetic Study of anti-HIV drugs by Thermal Decomposition Analysis: A Multilayer Artificial Neural Network Propose

    CERN Document Server

    Ferreira, B D L; Sebastião, R C O; Yoshida, M I; Mussel, W N; Fialho, S L; Barbosa, J

    2016-01-01

    Kinetic study by thermal decomposition of antiretroviral drugs, Efavirenz (EFV) and Lamivudine (3TC), usually present in the HIV cocktail, can be done by individual adjustment of the solid decomposition models. However, in some cases unacceptable errors are found using this methodology. To circumvent this problem, here is proposed to use a multilayer perceptron neural network (MLP), with an appropriate algorithm, which constitutes a linearization of the network by setting weights between the input layer and the intermediate one and the use of Kinetic models as activation functions of neurons in the hidden layer. The interconnection weights between that intermediate layer and output layer determines the contribution of each model in the overall fit of the experimental data. Thus, the decomposition is assumed to be a phenomenon that can occur following different kinetic processes. In the investigated data, the kinetic thermal decomposition process was best described by R1 and D4 model for all temperatures to EF...

  12. Evolution of different morphologies of CdS nanoparticles by thermal decomposition of bis(thiourea)cadmium chloride in various solvents

    Energy Technology Data Exchange (ETDEWEB)

    Gaur, Rama; Jeevanandam, P., E-mail: jeevafcy@iitr.ernet.in, E-mail: jeevafcy@iitr.ac.in [Indian Institute of Technology Roorkee, Department of Chemistry (India)

    2015-03-15

    CdS nanoparticles with different morphologies have been synthesized by thermal decomposition of bis(thiourea)cadmium chloride in different solvents without the use of any ligand/surfactant. CdS nanoparticles with pyramid, sponge-like and hexagonal disc-like morphologies were obtained in diphenyl ether (DPE), 1-octadecene (ODE) and ethylene glycol (EG), respectively. In addition, CdS nanoparticles with unique morphologies were obtained when the decomposition of the complex was carried out in mixed solvents (DPE–EG and ODE–EG). Extensive characterization of the CdS nanoparticles was carried out using powder X-ray diffraction, FT-IR spectroscopy, thermal analysis, field-emission scanning electron microscopy, diffuse reflectance spectroscopy and photoluminescence spectroscopy, and detailed mechanism of the formation of CdS nanoparticles with different morphologies in various solvents has been proposed.

  13. Evolution of different morphologies of CdS nanoparticles by thermal decomposition of bis(thiourea)cadmium chloride in various solvents

    Science.gov (United States)

    Gaur, Rama; Jeevanandam, P.

    2015-03-01

    CdS nanoparticles with different morphologies have been synthesized by thermal decomposition of bis(thiourea)cadmium chloride in different solvents without the use of any ligand/surfactant. CdS nanoparticles with pyramid, sponge-like and hexagonal disc-like morphologies were obtained in diphenyl ether (DPE), 1-octadecene (ODE) and ethylene glycol (EG), respectively. In addition, CdS nanoparticles with unique morphologies were obtained when the decomposition of the complex was carried out in mixed solvents (DPE-EG and ODE-EG). Extensive characterization of the CdS nanoparticles was carried out using powder X-ray diffraction, FT-IR spectroscopy, thermal analysis, field-emission scanning electron microscopy, diffuse reflectance spectroscopy and photoluminescence spectroscopy, and detailed mechanism of the formation of CdS nanoparticles with different morphologies in various solvents has been proposed.

  14. Investigation of thermodynamic parameters in the thermal decomposition of plastic waste-waste lube oil compounds.

    Science.gov (United States)

    Kim, Yong Sang; Kim, Young Seok; Kim, Sung Hyun

    2010-07-01

    Thermal decomposition properties of plastic waste-waste lube oil compounds were investigated under nonisothermal conditions. Polyethylene (PE), polypropylene (PP), polystyrene (PS), and polyethylene terephthalate (PET) were selected as representative household plastic wastes. A plastic waste mixture (PWM) and waste lube oil (WLO) were mixed with mixing ratios of 33, 50, and 67 (w/w) % on a PWM weight basis, and thermogravimetric (TG) experiments were performed from 25 to 600 degrees C. The Flynn-Wall method and the Ozawa-Flynn-Wall method were used for analyses of thermodynamic parameters. In this study, activation energies of PWM/WLO compounds ranged from 73.4 to 229.6 kJ/mol between 0.2 and 0.8 of normalized mass conversions, and the 50% PWM/WLO compound had lower activation energies and enthalpies among the PWM/WLO samples at each mass conversion. At the point of maximum differential mass conversion, the analyzed activation energies, enthalpies, entropies, and Gibbs free energies indicated that mixing PWM and WLO has advantages in reducing energy to decrease the degree of disorder. However, no difference in overall energy that would require overcoming both thermal decomposition reactions and degree of disorder was observed among PWM/WLO compounds under these experimental conditions.

  15. Synthesis of seaweed based carbon acid catalyst by thermal decomposition of ammonium sulfate for biodiesel production

    Science.gov (United States)

    Ee, Tang Zo; Lim, Steven; Ling, Pang Yean; Huei, Wong Kam; Chyuan, Ong Hwai

    2017-04-01

    Experiment was carried out to study the feasibility of biomass derived solid acid catalyst for the production of biodiesel using Palm Fatty Acid Distillate (PFAD). Malaysia indigenous seaweed was selected as the biomass to be carbonized as the catalyst support. Sulfonation of seaweed based carbon material was carried out by thermal decomposition of ammonium sulfate, (NH4)2SO4. The effects of carbonization temperature at 200 to 600°C on the catalyst physical and chemical properties were studied. The effect of reaction parameters on the fatty acid methyl ester (FAME) yield was studied by varying the concentration of ammonium sulfate (5.0 to 40.0 w/v%) and thermal decomposition time (15 to 90 min). Characterizations of catalyst were carried out to study the catalyst surface morphology with Scanning Electron Microscope (SEM), acid density with back titration and functional group attached with FT-IR. Results showed that when the catalyst sulfonated with 10.0 w/v% ammonium sulfate solution and heated to 235°C for 30 min, the highest FAME yield achieved was 23.7% at the reaction condition of 5.0 wt.% catalyst loading, esterification time of 4 h, methanol to PFAD molar ratio of 20:1 at 100°C reaction temperature.

  16. Thermal decomposition of sugarcane straw, kinetics and heat of reaction in synthetic air.

    Science.gov (United States)

    Rueda-Ordóñez, Yesid Javier; Tannous, Katia

    2016-07-01

    The aim of this work was to analyze the thermal decomposition, kinetics and heat of reaction of sugarcane straw in synthetic air by thermogravimetry (TG) and differential scanning calorimetry (DSC). The TG and DSC experiments were carried out using heating rates of 2.5°C/min, 5°C/min, and 10°C/min, and particle diameter of 0.250mm. In the study of the smoldering reaction were identified three consecutive stages, drying, oxidative pyrolysis, and combustion. Thus, the kinetic pathway was composed by six independent parallel reactions, three for each stage after drying, in which the activation energies were 176, 313, 150, 80, 150, and 100kJ/mol. The heat of reaction in synthetic air was completely exothermic releasing 8MJ/kg. The modeled curves of thermal decomposition of sugarcane straw presented good agreement with experimental data. Then, the kinetic parameters obtained could be used to analyze different processes involving smoldering. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Reaction mechanism of methylamine decomposition on Ru(0001): a density functional theory study.

    Science.gov (United States)

    Lv, Cun-Qin; Liu, Jian-Hong; Song, Xiao-Fei; Guo, Yong; Wang, Gui-Chang

    2014-03-01

    The reaction mechanism of methylamine decomposition on Ru(0001) has been systematically investigated by density functional theory slab calculations. The decomposition network has also been described. The adsorption energies under the most stable configuration of the possible species and the energy barriers of the possible elementary reactions involved are obtained. Desorption is preferred for adsorbing methylamine and hydrogen, whereas for the other species, decomposition is more favorable. Our calculated results show that methylamine decomposition on Ru(0001) starts with H₂CNH₂ formation from methyl dehydrogenation, followed by subsequent methylene dehydrogenation, bond breaking of N--H and C--N in HCNH₂, CH dehydrogenation and C-N bond cleavage in HCNH, and dehydrogenation of NH₂, NH, and CH.

  18. Catalyst Effects of Nanometer CuCr2O4 on the Thermal Decomposition of TEGDN Propellant

    Science.gov (United States)

    Yan, Shi; Kou, Chenxia; Li, Yanchun; Cheng, Yi

    2012-04-01

    The catalyst effects of nanometer CuCr2O4 on the thermal decomposition of triethyleneglycol dinitrate (TEGDN) propellant were investigated using thermogravimetric analysis, differential scanning calorimetry, mass spectrometry, and Fourier transform infrared spectroscopy. The Ozawa equation and step integral equation were used to calculate the activation energy. The results showed that the thermal decomposition reaction of TEGDN propellant can be seen as two reactions. Nanometer CuCr2O4 added in TEGDN propellant reduced the activation energy of the second reaction step; therefore, the second reaction step was sped up. Mass spectrometry, Fourier transform infrared spectrometry and the combustion residue analysis results also supported this conclusion.

  19. Alumina-Supported Manganese Catalysts for Soot Combustion Prepared by Thermal Decomposition of KMnO4

    Directory of Open Access Journals (Sweden)

    Agustin Bueno-López

    2012-09-01

    Full Text Available Alumina-supported manganese catalysts with cryptomelane and/or birnessite structure have been prepared using a simple method based on the thermal decomposition of potassium permanganate. The samples have been characterized by XRD, FTIR, TGA, DSC, N2 adsorption at −196 °C, SEM, H2-TPR and XPS, and their catalytic activity for soot combustion has been tested and compared to that of a reference Pt/alumina catalyst. The thermal decomposition of alumina-supported KMnO4 yields a mixture of supported birnessite and potassium manganate which is the most effective, among those prepared, to lower the soot combustion temperature. However, this material is not useful for soot combustion because the accelerating effect is not based on a catalytic process but on the oxidation of soot by potassium manganate. A suitable soot combustion catalyst is obtained after potassium manganate is removed by water washing, yielding only the birnessite phase on the γ-Al2O3 support. This birnessite phase can be transformed into cryptomelane by calcination at 600 °C. These two samples, γ-Al2O3-supported birnessite and cryptomelane are suitable catalysts for soot combustion in NOx/O2 mixtures, as their catalytic activity is based on the NO2-assited mechanism, that is, both catalysts accelerate the oxidation of NO to NO2 and NO2 promotes soot oxidation. The soot combustion temperatures obtained with these birnessite/cryptomelane alumina-supported catalysts are similar to that obtained with the reference Pt/alumina catalyst.

  20. Thermal decomposition rate of MgCO3 as an inorganic astrobiological matrix in meteorites

    Science.gov (United States)

    Bisceglia, E.; Longo, G. Micca; Longo, S.

    2017-04-01

    Carbonate minerals, likely of hydrothermal origins and included into orthopyroxenite, have been extensively studied in the ALH84001 meteorite. In this meteorite, nanocrystals comparable with those produced by magnetotactic bacteria have been found into a carbonate matrix. This leads naturally to a discussion of the role of such carbonates in panspermia theories. In this context, the present work sets the basis of a criterion to evaluate whether a carbonate matrix in a meteor entering a planetary atmosphere would be able to reach the surface. As a preliminary step, the composition of carbonate minerals in the ALH84001 meteorite is reviewed; in view of the predominance of Mg in these carbonates, pure magnesite (MgCO3) is proposed as a mineral model. This mineral is much more sensitive to high temperatures reached during an entry process, compared with silicates, due to facile decomposition into MgO and gaseous carbon dioxide (CO2). A most important quantity for further studies is therefore the decomposition rate expressed as CO2 evaporation rate J (molecules/m2 s). An analytical expression for J(T) is given using the Langmuir law, based on CO2 pressure in equilibrium with MgCO3 and MgO at the surface temperature T. Results suggest that carbonate minerals rich in magnesium may offer much better thermal protection to embedded biological matter than silicates and significantly better than limestone, which was considered in previous studies, in view of the heat absorbed by their decomposition even at moderate temperatures. This first study can be extended in the future to account for more complex compositions, including Fe and Ca.

  1. The thermal decomposition of the benzyl radical in a heated micro-reactor. I. Experimental findings

    Science.gov (United States)

    Buckingham, Grant T.; Ormond, Thomas K.; Porterfield, Jessica P.; Hemberger, Patrick; Kostko, Oleg; Ahmed, Musahid; Robichaud, David J.; Nimlos, Mark R.; Daily, John W.; Ellison, G. Barney

    2015-01-01

    The pyrolysis of the benzyl radical has been studied in a set of heated micro-reactors. A combination of photoionization mass spectrometry (PIMS) and matrix isolation infrared (IR) spectroscopy has been used to identify the decomposition products. Both benzyl bromide and ethyl benzene have been used as precursors of the parent species, C6H5CH2, as well as a set of isotopically labeled radicals: C6H5CD2, C6D5CH2, and C6H513CH2. The combination of PIMS and IR spectroscopy has been used to identify the earliest pyrolysis products from benzyl radical as: C5H4=C=CH2, H atom, C5H4—C ≡ CH, C5H5, HCCCH2, and HC ≡ CH. Pyrolysis of the C6H5CD2, C6D5CH2, and C6H513CH2 benzyl radicals produces a set of methyl radicals, cyclopentadienyl radicals, and benzynes that are not predicted by a fulvenallene pathway. Explicit PIMS searches for the cycloheptatrienyl radical were unsuccessful, there is no evidence for the isomerization of benzyl and cycloheptatrienyl radicals: C6H5CH2⇋C7H7. These labeling studies suggest that there must be other thermal decomposition routes for the C6H5CH2 radical that differ from the fulvenallene pathway.

  2. Thermal Decomposition Study on CuInSe2 Single Crystals

    Science.gov (United States)

    Chauhan, Sanjaysinh M.; Chaki, Sunil H.; Deshpande, M. P.; Malek, Tasmira J.; Tailor, J. P.

    2018-01-01

    The thermal analysis of the chemical vapor transport (CVT)-grown CuInSe2 single crystals was carried out by recording the thermogravimetric, differential thermogravimetric and differential thermal analysis curves. All the three thermo-curves were recorded simultaneously by thermal analyzer in the temperature range of ambient to 1080 K in inert nitrogen atmosphere. The thermo-curves were recorded for four heating rates of 5 K \\cdot min^{-1}, 10 K \\cdot min^{-1}, 15 K \\cdot min^{-1} and 20 K \\cdot min^{-1}. The TG curve analysis showed negligible mass loss in the temperature range of ambient to 600 K, stating the sample material to be thermally stable in this temperature range. Above 601 K to the temperature of 1080 K, the sample showed continuous mass loss. The DTG curves showed two peaks in the temperature range of 601 K to 1080 K. The corresponding DTA showed initial minor exothermic nature followed by endothermic nature up to nearly 750 K and above it showed exothermic nature. The initial exothermic nature is due to absorbed water converting to water vapor, whereas the endothermic nature states the absorption of heat by the sample up to nearly 950 K. Above nearly 950 K the exothermic nature is due to the decomposition of sample material. The absorption of heat in the endothermic region is substantiated by corresponding weight loss in TG. The thermal kinetic parameters of the CVT-grown CuInSe2 single crystals were determined employing the non-mechanistic Kissinger relation. The determined kinetic parameters support the observations of the thermo-curves.

  3. Thermal Analysis of porous fin with uniform magnetic field using Adomian decomposition Sumudu transform method

    Science.gov (United States)

    Patel, Trushit; Meher, Ramakanta

    2017-09-01

    In this paper, we consider a Roseland approximation to radiate heat transfer, Darcy's model to simulate the flow in porous media and finite-length fin with insulated tip to study the thermal performance and to predict the temperature distribution in a vertical isothermal surface. The energy balance equations of the porous fin with several temperature dependent properties are solved using the Adomian Decomposition Sumudu Transform Method (ADSTM). The effects of various thermophysical parameters, such as the convection-conduction parameter, Surface-ambient radiation parameter, Rayleigh numbers and Hartman number are determined. The results obtained from the ADSTM are further compared with the fourth-fifth order Runge-Kutta-Fehlberg method and Least Square Method(LSM) (Hoshyar et al. 2016 ) to determine the accuracy of the solution.

  4. Studies on Thermal Decomposition of Aluminium Sulfate to Produce Alumina Nano Structure

    Directory of Open Access Journals (Sweden)

    M. Jafar-Tafreshi

    2012-12-01

    Full Text Available Aluminum sulfate nano structures have been prepared by solution combustion synthesis using aluminum nitrate nonahydrate (Al(NO33.9H2O and ammonium sulfate ((NH42SO4. The resultant aluminum sulfate nano structures were calcined at different temperatures to study thermal  decomposition of aluminum sulfate. The crystallinity and phase of  the as-synthesized and calcined samples were characterized by both X- ray diffraction and FTIR measurements. These two analyses determined the temperature at which the aluminum sulfate is converted to γ-alumina nano particles. The specific surface area and pore size distribution for  γ-alumina nano particles were determined by BET measurement. TEM measurement confirmed the size of the particles obtained by XRD and BET analyses.

  5. Thermal decomposition of wood in oxidizing atmosphere: A kinetic study from non-isothermal TG experiments

    Energy Technology Data Exchange (ETDEWEB)

    Cordero, T.; Rodriguez-Maroto, F.G.; Rodriguez, J.J. (Univ. of Malaga (Spain))

    1991-11-22

    The kinetics of thermal decomposition of four wood species in oxygen-bearing atmospheres of 5, 10 and 20% molar O{sub 2} concentrations have been studied from temperature-programmed experiments carried out at 5, 10 and 20 K min{sup {minus}1} heating rate. Devolatilization as well as combustion of the reamining solid have been considered to analyze the weight loss curves. The homogeneous volume reaction (VR) model has been used to describe devolatilization, whereas for solid combustion the grain model has been also checked. A two-stage approach has been used to fit the conversion-time curves and to derive the corresponding apparent kinetic parameters. The VR/VR (pyrolysis/combustion) combination provided a better description of the experimental {alpha}-t curves than the VR/grain combination. Holm oak and cork oak showed very close reactivities, whereas some differences were observed for aleppo pine and eucalyptus. 6 figs. 8 tabs., 20 refs.

  6. Fabrication of Lotus-Type Porous Aluminum through Thermal Decomposition Method

    Science.gov (United States)

    Kim, S. Y.; Park, J. S.; Nakajima, H.

    2009-04-01

    Lotus-type porous aluminum with cylindrical pores was fabricated by unidirectional solidification through thermal decomposition of calcium hydroxide, sodium bicarbonate, or titanium hydride. The pore-forming gas decomposed from calcium hydroxide, sodium bicarbonate, and titanium hydride is identified as hydrogen. The elongated pores are evolved due to the solubility gap between liquid and solid when the melt dissolving hydrogen is solidified unidirectionally. The porosity of lotus aluminum is as high as 20 pct despite the type of the compounds. The pore size decreases and the pore density increases with increasing amount of calcium hydroxide, which is explained by an increase in the number of pore nucleation sites. The porosity and pore size in lotus aluminum fabricated using calcium hydroxide decrease with increasing argon pressure, which is explained by Boyle’s law. It is suggested that this fabrication method is simple and safe, which makes it superior to the conventional technique using high-pressure hydrogen gas.

  7. Chemical kinetics on thermal decompositions of cumene hydroperoxide in cumene studied by calorimetry: An overview

    Energy Technology Data Exchange (ETDEWEB)

    Duh, Yih-Shing, E-mail: yihshingduh@yahoo.com.tw [Department of Occupation Safety and Health, Jen-Teh Junior College of Medicine, Nursing and Management, Miaoli, 35664, Taiwan, ROC (China); Department of Safety, Health and Environmental Engineering, National United University, No. 1 Lien-Da, Miaoli, 36052, Taiwan, ROC (China)

    2016-08-10

    Highlights: • Chemical kinetics on thermal decompositions of CHP are conducted and summarized. • Kinetics agrees well between data from DSC and adiabatic calorimetry. • Ea is determined to be about 120 kJ mol{sup −1} by various calorimetry. • LogA (A in s{sup −1}) is determined to be about 11.8 by various calorimetry. - Abstract: Study on chemical kinetics related to the thermal decomposition of cumene hydoperoxide (CHP) in cumene is summarized in this work. It is of great importance to gather and compare the differences between these kinetic parameters for further substantial applications in the chemical industry and process safety. CHP has been verified to possess an autocatalytic behavior by using microcalorimetry (such as TAM and C-80) operated at isothermal mode in the temperature range from 70 °C to 120 °C. However, it exhibits a reaction of n-th order detected by non-isothermal DSC scanning and adiabatic calorimeter. By the isothermal aging tests, activation energy and frequency factor in logA(s{sup −1}) were averaged to be (117.3 ± 5.9) kJ mol{sup −1}and (11.4 ± 0.3), respectively. Kinetic parameters acquired from data of interlaboratories by using heat-flow calorimetry, the averaged activation energy and frequency factor in logA(s{sup −1}) were (119.3 ± 11.3) kJ mol{sup −1}and (12.0 ± 0.2), respectively. On the analogy of results from adiabatic calorimetry, the activation energy and frequency factor in logA(s{sup −1}) were respectively averaged to be (122.4 ± 9.2) kJ mol{sup −1}and (11.8 ± 0.8). Five sets of kinetic models in relation to autocatalytic reactions are collected and discussed as well.

  8. Mechanism of thermal toluene autoxidation.

    Science.gov (United States)

    Hermans, Ive; Peeters, Jozef; Vereecken, Luc; Jacobs, Pierre A

    2007-12-21

    Aerobic oxidation of toluene (PhCH3) is investigated by complementary experimental and theoretical methodologies. Whereas the reaction of the chain-carrying benzylperoxyl radicals with the substrate produces predominantly benzyl hydroperoxide, benzyl alcohol and benzaldehyde originate mainly from subsequent propagation of the hydroperoxide product. Nevertheless, a significant fraction of benzaldehyde is also produced in primary PhCH3 propagation, presumably via proton rather than hydrogen transfer. An equimolar amount of benzyl alcohol, together with benzoic acid, is additionally produced in the tertiary propagation of PhCHO with benzylperoxyl radicals. The "hot" oxy radicals generated in this step can also abstract aromatic hydrogen atoms from PhCH3, and this results in production of cresols, known inhibitors of radical-chain reactions. The very fast benzyl peroxyl-initiated co-oxidation of benzyl alcohol generates HO2* radicals, along with benzaldehyde. This reaction also causes a decrease in the overall oxidation rate, due to the fast chain-terminating reaction of HO2*with the benzylperoxyl radicals, which causes a loss of chain carriers. Moreover, due to the fast equilibrium PhCH2OOH+HO2* right harpoon over left harpoonPhCH2OO* + H2O2, and the much lower reactivity of H2O2 compared to PhCH2OOH, the fast co-oxidation of the alcohol means that HO2* gradually takes over the role of benzylperoxyl as principal chain carrier. This drastically changes the autoxidation mechanism and, among other things, causes a sharp decrease in the hydroperoxide yield.

  9. Causal mechanisms of soil organic matter decomposition: Deconstructing salinity and flooding impacts in coastal wetlands

    Science.gov (United States)

    Stagg, Camille L.; Schoolmaster, Donald; Krauss, Ken W.; Cormier, Nicole; Conner, William H.

    2017-01-01

    Coastal wetlands significantly contribute to global carbon storage potential. Sea-level rise and other climate change-induced disturbances threaten coastal wetland sustainability and carbon storage capacity. It is critical that we understand the mechanisms controlling wetland carbon loss so that we can predict and manage these resources in anticipation of climate change. However, our current understanding of the mechanisms that control soil organic matter decomposition, in particular the impacts of elevated salinity, are limited, and literature reports are contradictory. In an attempt to improve our understanding of these complex processes, we measured root and rhizome decomposition and developed a causal model to identify and quantify the mechanisms that influence soil organic matter decomposition in coastal wetlands that are impacted by sea-level rise. We identified three causal pathways: 1) a direct pathway representing the effects of flooding on soil moisture, 2) a direct pathway representing the effects of salinity on decomposer microbial communities and soil biogeochemistry, and 3) an indirect pathway representing the effects of salinity on litter quality through changes in plant community composition over time. We used this model to test the effects of alternate scenarios on the response of tidal freshwater forested wetlands and oligohaline marshes to short- and long-term climate-induced disturbances of flooding and salinity. In tidal freshwater forested wetlands, the model predicted less decomposition in response to drought, hurricane salinity pulsing, and long-term sea-level rise. In contrast, in the oligohaline marsh, the model predicted no change in response to sea-level rise, and increased decomposition following a drought or a hurricane salinity pulse. Our results show that it is critical to consider the temporal scale of disturbance and the magnitude of exposure when assessing the effects of salinity intrusion on carbon mineralization in coastal

  10. Synthesis of CNTs/CuO and its catalytic performance on the thermal decomposition of ammonium perchlorate

    Directory of Open Access Journals (Sweden)

    Ping Cui

    2016-05-01

    Full Text Available Copper oxide (CuO nanoparticles were successfully deposited on carbon nanotubes’ (CNTs surface via complex-precipitation method, the nanocomposite was characterized by transmission electron microscopy (TEM, scanning electron microscopy (SEM, X-ray photoelectron spectroscopy (XPS, X-ray powder diffraction (XRD, Raman spectroscopy, Fourier transform infrared (FT-IR and Brunauer–Emmett–Teller (BET. The catalytic performance of CNTs/CuO on ammonium perchlorate (AP decomposition was analyzed by differential thermal analyzer (DTA, the DTA results showed its excellent catalytic effect on AP decomposition, as 8 wt.% CNTs/CuO was added in AP, the second exothermic peak temperature decreased by 158 °C. Such composite may be a promising candidate for catalyzing the AP thermal decomposition.

  11. Analysis of the Compounds from the BTEX Group, Emitted During Thermal Decomposition of Alkyd Resin

    Directory of Open Access Journals (Sweden)

    M. Kubecki

    2012-09-01

    Full Text Available Suitability of the given binding agent for the moulding sands preparation depends on the one hand on the estimation of technological properties of the sand and the mould made of it and the obtained casting quality and on the other hand on the assessment of this sand influence on the natural and working environment. Out of moulding sands used in the foundry industry, sands with organic binders deserve a special attention. These binders are based on synthetic resins, which ensure obtaining the proper technological properties and sound castings, however, they negatively influence the environment. If in the initial state these resins are not very dangerous for people and for the environment, thus under an influence of high temperatures they generate very harmful products, being the result of their thermal decomposition. Depending on the kind of the applied resin (phenol-formaldehyde, urea, furfuryl, urea–furfuryl, alkyd under an influence of a temperature such compounds as: furfuryl alcohol, formaldehyde, phenol, BTEX group (benzene, toluene, ethylbenzene, xylene, and also polycyclic aromatic hydrocarbons (PAH can be formed and released.The aim of the study was the development of the method, selection of analytical methods and the determination of optimal conditionsof formation compounds from the BTEX group. An emission of these components constitutes one of the basic criteria of the harmfulnessassessment of binders applied for moulding and core sands. Investigations were carried out in the specially designed set up for the thermal decomposition of organic substances in a temperature range: 5000C – 13000C at the laboratory scale. The object for testing was alkyd resin applied as a binding material for moulding sands. Within investigations the minimal amount of adsorbent necessary for the adsorption of compounds released during the decomposition of the resin sample of a mass app. 15 mg was selected. Also the minimal amount of solvent needed for

  12. Kinetics evaluation and thermal decomposition characteristics of co-pyrolysis of municipal sewage sludge and hazelnut shell.

    Science.gov (United States)

    Zhao, Bing; Xu, Xinyang; Li, Haibo; Chen, Xi; Zeng, Fanqiang

    2018-01-01

    Hazelnut shell, as novel biomass, has lower ash content and abundant hydrocarbon, which can be utilized resourcefully with municipal sewage sludge (MSS) by co-pyrolyisis to decrease total content of pollution. The co-pyrolysis of MSS and hazelnut shell blend was analyzed by a method of multi-heating rates and different blend ratios with TG-DTG-MS under N2 atmosphere. The apparent activation energy of co-pyrolysis was calculated by three iso-conversional methods. Satava-Sestak method was used to determine mechanism function G(α) of co-pyrolysis, and Lorentzian function was used to simulate multi-peaks curves. The results showed there were four thermal decomposition stages, and the biomass were cracked and evolved at different temperature ranges. The apparent activation energy increased from 123.99 to 608.15kJ/mol. The reaction mechanism of co-pyrolysis is random nucleation and nuclei growth. The apparent activation energy and mechanism function afford a theoretical groundwork for co-pyrolysis technology. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. Thermal decomposition of a molecular material {N(n-C4H94[FeIIFeIII(C2O43]}∞ leading to ferrite: A reaction kinetics study

    Directory of Open Access Journals (Sweden)

    Bhattacharjee Ashis

    2013-01-01

    Full Text Available A multi-step thermal decomposition of a molecular precursor, {N(n-C4H94[FeIIFeIII(C2O43}∞ has been studied using non-isothermal thermogravimetry (TG measurements in the temperature range 300 to ~800 K at multiple heating rates (5, 10 and 20 K min-1. The thermal decomposition of the oxalate-based complex proceeds stepwise through a series of intermediate reactions. Two different isoconversional methods, namely, improved iterative method and model-free method are employed to evaluate the kinetic parameters: activation energy and rate of reaction, and the most probable reaction mechanism of thermal decomposition is also determined. The different reaction pathways leading to different steps in the TG profile have also been explored which are supplemented by earlier experimental observations of the present authors.

  14. COMPOSITE POLYMERICADDITIVESDESIGNATED FORCONCRETEMIXES BASED ONPOLYACRYLATES, PRODUCTS OF THERMAL DECOMPOSITION OF POLYAMIDE-6 AND LOW-MOLECULAR POLYETHYLENE

    Directory of Open Access Journals (Sweden)

    Polyakov Vyacheslav Sergeevich

    2012-07-01

    4 the optimal composite additive that increases the time period of stiffening of the cement grout , improves the water resistance and the compressive strength of concrete, represents the composition of polyacrylates and polymethacrylates, products of thermal decomposition of polyamide-6 and low-molecular polyethylene in the weight ratio of 1:1:0.5.

  15. The glassy behaviour of poorly crystalline Fe2O3 nanorods obtained by thermal decomposition of ferrous oxalate

    Czech Academy of Sciences Publication Activity Database

    Perović, M.; Kusigerski, V.; Mrakovic, A.; Spasojevic, V.; Blanusa, J.; Nikolic, V.; Schneeweiss, Oldřich; David, Bohumil; Pizúrová, Naděžda

    2015-01-01

    Roč. 26, č. 11 (2015), Art. n. 115705 ISSN 0957-4484 Institutional support: RVO:68081723 Keywords : Thermal decomposition * Nanorods * Iron oxide * Spin glass like * Memory effects Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.573, year: 2015

  16. Deployment Mechanism for Thermal Pointing System

    Science.gov (United States)

    Koski, Kraig

    2014-01-01

    The Deployment Mechanism for the Total and Spectral Solar Irradiance Sensor (TSIS) is responsible for bringing the Thermal Pointing System (TPS) from its stowed, launch locked position to the on-orbit deployed, operational position. The Deployment Mechanism also provides structural support for the TSIS optical bench and two-axis gimbal. An engineering model of the Deployment Mechanism has been environmentally qualified and life tested. This paper will give an overview of the TSIS mission and then describe the development, design, and testing of the Deployment Mechanism.

  17. Thermal integrity in mechanics and engineering

    CERN Document Server

    Shorr, Boris F

    2015-01-01

    The book is targeted at engineers, university lecturers, postgraduates, and final year undergraduate students involved in computational modelling and experimental and theoretical analysis of the high-temperature behavior of engineering structures. It will also be of interest to researchers developing the thermal strength theory as a branch of continuum mechanics. Thermal integrity is a multidisciplinary field combining the expertise of mechanical engineers, material scientists and applied mathematicians, each approaching the problem from their specific viewpoint. This monograph draws on the research of a broad scientific community including the author’s contribution. The scope of thermal strength analysis was considerably extended thanks to modern computers and the implementation of FEM codes. However, the author believes that some material models adopted in the advanced high-performance software, are not sufficiently justificated due to lack of easy-to-follow books on the theoretical and experimental aspec...

  18. Thermal decomposition of ammonium perchlorate in the presence of Al(OH){sub 3}·Cr(OH){sub 3} nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, WenJing [Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Li, Ping, E-mail: lipinggnipil@home.ipe.ac.cn [Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Xu, HongBin; Sun, Randi; Qing, Penghui; Zhang, Yi [Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China)

    2014-03-01

    Highlights: • The amorphous Al(OH){sub 3}·Cr(OH){sub 3} nanoparticles containing surface hydroxyls were prepared by a hydrolytic co-precipitation method. • The Al(OH){sub 3}·Cr(OH){sub 3} nanoparticles show excellent catalytic ability for AP decomposition. • The surface hydroxyls and amorphous form of Al(OH){sub 3}·Cr(OH){sub 3} nanoparticles promote ammonia oxidation of AP. - Abstract: An Al(OH){sub 3}·Cr(OH){sub 3} nanoparticle preparation procedure and its catalytic effect and mechanism on thermal decomposition of ammonium perchlorate (AP) were investigated using transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric analysis and differential scanning calorimetry (TG-DSC), X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis and mass spectroscopy (TG-MS). In the preparation procedure, TEM, SAED, and FT-IR showed that the Al(OH){sub 3}·Cr(OH){sub 3} particles were amorphous particles with dimensions in the nanometer size regime containing a large amount of surface hydroxyl under the controllable preparation conditions. When the Al(OH){sub 3}·Cr(OH){sub 3} nanoparticles were used as additives for the thermal decomposition of AP, the TG-DSC results showed that the addition of Al(OH){sub 3}·Cr(OH){sub 3} nanoparticles to AP remarkably decreased the onset temperature of AP decomposition from approximately 450 °C to 245 °C. The FT-IR, RS and XPS results confirmed that the surface hydroxyl content of the Al(OH){sub 3}·Cr(OH){sub 3} nanoparticles decreased from 67.94% to 63.65%, and Al(OH){sub 3}·Cr(OH){sub 3} nanoparticles were limitedly transformed from amorphous to crystalline after used as additives for the thermal decomposition of AP. Such behavior of Al(OH){sub 3}·Cr(OH){sub 3} nanoparticles promoted the oxidation of NH{sub 3} of AP to decompose to N{sub 2}O first, as indicated by the TG-MS results, accelerating the AP thermal decomposition.

  19. On the dynamic equivalence of planar mechanisms : An inertia decomposition method

    NARCIS (Netherlands)

    de Jong, J. J.; van Dijk, J.; Herder, J. L.; Wenger, Philippe; Flores, Paulo

    2016-01-01

    In this paper the dynamic equivalence of planar mechanisms is investigated by decomposition of inertia into point masses. For a planar rigid body, two point masses can fully describe its dynamic behavior. The location of one these points can be chosen freely, fixing the second point. By locating one

  20. Plasmonic Thermal Decomposition/Digestion of Proteins: A Rapid On-Surface Protein Digestion Technique for Mass Spectrometry Imaging.

    Science.gov (United States)

    Zhou, Rong; Basile, Franco

    2017-09-05

    A method based on plasmon surface resonance absorption and heating was developed to perform a rapid on-surface protein thermal decomposition and digestion suitable for imaging mass spectrometry (MS) and/or profiling. This photothermal process or plasmonic thermal decomposition/digestion (plasmonic-TDD) method incorporates a continuous wave (CW) laser excitation and gold nanoparticles (Au-NPs) to induce known thermal decomposition reactions that cleave peptides and proteins specifically at the C-terminus of aspartic acid and at the N-terminus of cysteine. These thermal decomposition reactions are induced by heating a solid protein sample to temperatures between 200 and 270 °C for a short period of time (10-50 s per 200 μm segment) and are reagentless and solventless, and thus are devoid of sample product delocalization. In the plasmonic-TDD setup the sample is coated with Au-NPs and irradiated with 532 nm laser radiation to induce thermoplasmonic heating and bring about site-specific thermal decomposition on solid peptide/protein samples. In this manner the Au-NPs act as nanoheaters that result in a highly localized thermal decomposition and digestion of the protein sample that is independent of the absorption properties of the protein, making the method universally applicable to all types of proteinaceous samples (e.g., tissues or protein arrays). Several experimental variables were optimized to maximize product yield, and they include heating time, laser intensity, size of Au-NPs, and surface coverage of Au-NPs. Using optimized parameters, proof-of-principle experiments confirmed the ability of the plasmonic-TDD method to induce both C-cleavage and D-cleavage on several peptide standards and the protein lysozyme by detecting their thermal decomposition products with matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). The high spatial specificity of the plasmonic-TDD method was demonstrated by using a mask to digest designated sections of

  1. Thermalized solutions, statistical mechanics and turbulence: An ...

    Indian Academy of Sciences (India)

    Thermalized solutions, statistical mechanics and turbulence only for an interval of time O(KG. −2/3). By using arguments of phase mixing, we can see that coherent structures can happen only at spatial points where the fluid velocity differs from the resonance velocity (the velocity of the shock) by an amount v such that v ≲.

  2. Thermalized solutions, statistical mechanics and turbulence: An ...

    Indian Academy of Sciences (India)

    2015-02-20

    Feb 20, 2015 ... In this study, we examine the intriguing connection between turbulence and equilibrium statistical mechanics. There are several recent works which emphasize this connection. Thus in the last few years, the first manifestations of the thermalization, predicted by T D Lee in 1952, was seen and a theoretical ...

  3. Molecular mechanism of metal-independent decomposition of lipid hydroperoxide 13-HPODE by halogenated quinoid carcinogens.

    Science.gov (United States)

    Qin, Hao; Huang, Chun-Hua; Mao, Li; Xia, Hai-Ying; Kalyanaraman, Balaraman; Shao, Jie; Shan, Guo-Qiang; Zhu, Ben-Zhan

    2013-10-01

    Halogenated quinones are a class of carcinogenic intermediates and newly identified chlorination disinfection by-products in drinking water. 13-Hydroperoxy-9,11-octadecadienoic acid (13-HPODE) is the most extensively studied endogenous lipid hydroperoxide. Although it is well known that the decomposition of 13-HPODE can be catalyzed by transition metal ions, it is not clear whether halogenated quinones could enhance its decomposition independent of metal ions and, if so, what the unique characteristics and similarities are. Here we show that 2,5-dichloro-1,4-benzoquinone (DCBQ) could markedly enhance the decomposition of 13-HPODE and formation of reactive lipid alkyl radicals such as pentyl and 7-carboxyheptyl radicals, and the genotoxic 4-hydroxy-2-nonenal (HNE), through the complementary application of ESR spin trapping, HPLC-MS, and GC-MS methods. Interestingly, two chloroquinone-lipid alkoxyl conjugates were also detected and identified from the reaction between DCBQ and 13-HPODE. Analogous results were observed with other halogenated quinones. This represents the first report that halogenated quinoid carcinogens can enhance the decomposition of the endogenous lipid hydroperoxide 13-HPODE and formation of reactive lipid alkyl radicals and genotoxic HNE via a novel metal-independent nucleophilic substitution coupled with homolytic decomposition mechanism, which may partly explain their potential genotoxicity and carcinogenicity. Copyright © 2013 Elsevier Inc. All rights reserved.

  4. Kinetic study of the thermal decomposition of uranium metaphosphate, U(PO3)4, into uranium pyrophosphate, UP2O7

    Science.gov (United States)

    Yang, Hee-Chul; Kim, Hyung-Ju; Lee, Si-Young; Yang, In-Hwan; Chung, Dong-Yong

    2017-06-01

    The thermochemical properties of uranium compounds have attracted much interest in relation to thermochemical treatments and the safe disposal of radioactive waste bearing uranium compounds. The characteristics of the thermal decomposition of uranium metaphosphate, U(PO3)4, into uranium pyrophosphate, UP2O7, have been studied from the view point of reaction kinetics and acting mechanisms. A mixture of U(PO3)4 and UP2O7 was prepared from the pyrolysis residue of uranium-bearing spent TBP. A kinetic analysis of the reaction of U(PO3)4 into UP2O7 was conducted using an isoconversional method and a master plot method on the basis of data from a non-isothermal thermogravimetric analysis. The thermal decomposition of U(PO3)4 into UP2O7 followed a single-step reaction with an activation energy of 175.29 ± 1.58 kJ mol-1. The most probable kinetic model was determined as a type of nucleation and nuclei-growth models, the Avrami-Erofeev model (A3), which describes that there are certain restrictions on nuclei growth of UP2O7 during the solid-state decomposition of U(PO3)4.

  5. Thermal, dielectric and mechanical study of poly(vinyl chloride/olive pomace composites

    Directory of Open Access Journals (Sweden)

    2007-12-01

    Full Text Available Composites from PVC and chemically treated olive pomace have been prepared. The effect of the incorporation of virgin and benzylated olive pomace in the poly(vinyl chloride matrix on dielectric, mechanical and thermal stability properties, of /olive pomace composites was studied. The mechanical properties of the benzylated composites were improved. Furthermore, the thermal characterization of the different samples carried out by thermogravimetric analysis revealed an increase in the onset temperatures of decomposition for the treated composites. The dielectric investigation indicated that the samples containing olive pomace treated with the benzyl chloride can be used in electrical applications as insulators.

  6. Formation of a metallic glass by thermal decomposition of Fe(CO)5

    DEFF Research Database (Denmark)

    Wonterghem, Jacques van; Mørup, Steen; Charles, Stuart W.

    1985-01-01

    Iron pentacarbonyl has been thermally decomposed in an organic liquid. Mössbauer spectroscopy and x-ray diffraction studies show that the sample contains small particles of a metallic glass. Annealing of the particles at 523 K results in crystallization of the particles into a mixture of α-Fe and......-Fe5C2. The mechanism of glass formation is discussed....

  7. High-energy coordination polymers (CPs) exhibiting good catalytic effect on the thermal decomposition of ammonium dinitramide

    Science.gov (United States)

    Li, Xin; Han, Jing; Zhang, Sheng; Zhai, Lianjie; Wang, Bozhou; Yang, Qi; Wei, Qing; Xie, Gang; Chen, Sanping; Gao, Shengli

    2017-09-01

    High-energy coordination polymers (CPs) not only exhibit good energetic performances but also have a good catalytic effect on the thermal decomposition of energetic materials. In this contribution, two high-energy CPs Cu2(DNBT)2(CH3OH)(H2O)3·3H2O (1) and [Cu3(DDT)2(H2O)2]n (2) (H2DNBT = 3,3‧-dinitro-5,5‧-bis(1H-1,2,4-triazole and H3DDT = 4,5-bis(1H-tetrazol-5-yl)-2H-1,2,3-triazole) were synthesized and structurally characterized. Furthermore, 1 was thermos-dehydrated to produce Cu2(DNBT)2(CH3OH)(H2O)3 (1a). The thermal decomposition kinetics of 1, 1a and 2 were studied by Kissinger's method and Ozawa's method. Thermal analyses and sensitivity tests show that all compounds exhibit high thermal stability and low sensitivity for external stimuli. Meanwhile, all compounds have large positive enthalpy of formation, which are calculated as being (1067.67 ± 2.62) kJ mol-1 (1), (1464.12 ± 3.12) kJ mol-1 (1a) and (3877.82 ± 2.75) kJ mol-1 (2), respectively. The catalytic effects of 1a and 2 on the thermal decomposition of ammonium dinitramide (ADN) were also investigated.

  8. The thermal decomposition of the benzyl radical in a heated micro-reactor. I. Experimental findings

    Energy Technology Data Exchange (ETDEWEB)

    Buckingham, Grant T.; Ormond, Thomas K. [Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215 (United States); National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401 (United States); Porterfield, Jessica P.; Ellison, G. Barney [Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215 (United States); Hemberger, Patrick [Molecular Dynamics Group, Paul Scherrer Institut, CH-5232 Villigen-PSI (Switzerland); Kostko, Oleg; Ahmed, Musahid [Chemical Sciences Division, Lawrence Berkeley National Laboratories, Berkeley, California 94720 (United States); Robichaud, David J.; Nimlos, Mark R. [National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401 (United States); Daily, John W. [Department of Mechanical Engineering, Center for Combustion and Environmental Research,University of Colorado, Boulder, Colorado 80309-0427 (United States)

    2015-01-28

    The pyrolysis of the benzyl radical has been studied in a set of heated micro-reactors. A combination of photoionization mass spectrometry (PIMS) and matrix isolation infrared (IR) spectroscopy has been used to identify the decomposition products. Both benzyl bromide and ethyl benzene have been used as precursors of the parent species, C{sub 6}H{sub 5}CH{sub 2}, as well as a set of isotopically labeled radicals: C{sub 6}H{sub 5}CD{sub 2}, C{sub 6}D{sub 5}CH{sub 2}, and C{sub 6}H{sub 5}{sup 13}CH{sub 2}. The combination of PIMS and IR spectroscopy has been used to identify the earliest pyrolysis products from benzyl radical as: C{sub 5}H{sub 4}=C=CH{sub 2}, H atom, C{sub 5}H{sub 4}—C ≡ CH, C{sub 5}H{sub 5}, HCCCH{sub 2}, and HC ≡ CH. Pyrolysis of the C{sub 6}H{sub 5}CD{sub 2}, C{sub 6}D{sub 5}CH{sub 2}, and C{sub 6}H{sub 5}{sup 13}CH{sub 2} benzyl radicals produces a set of methyl radicals, cyclopentadienyl radicals, and benzynes that are not predicted by a fulvenallene pathway. Explicit PIMS searches for the cycloheptatrienyl radical were unsuccessful, there is no evidence for the isomerization of benzyl and cycloheptatrienyl radicals: C{sub 6}H{sub 5}CH{sub 2}⇋C{sub 7}H{sub 7}. These labeling studies suggest that there must be other thermal decomposition routes for the C{sub 6}H{sub 5}CH{sub 2} radical that differ from the fulvenallene pathway.

  9. Thermal Decomposition Synthesis of Iron Oxide Nanoparticles with Diminished Magnetic Dead Layer by Controlled Addition of Oxygen.

    Science.gov (United States)

    Unni, Mythreyi; Uhl, Amanda M; Savliwala, Shehaab; Savitzky, Benjamin H; Dhavalikar, Rohan; Garraud, Nicolas; Arnold, David P; Kourkoutis, Lena F; Andrew, Jennifer S; Rinaldi, Carlos

    2017-02-28

    Decades of research focused on size and shape control of iron oxide nanoparticles have led to methods of synthesis that afford excellent control over physical size and shape but comparatively poor control over magnetic properties. Popular synthesis methods based on thermal decomposition of organometallic precursors in the absence of oxygen have yielded particles with mixed iron oxide phases, crystal defects, and poorer than expected magnetic properties, including the existence of a thick "magnetically dead layer" experimentally evidenced by a magnetic diameter significantly smaller than the physical diameter. Here, we show how single-crystalline iron oxide nanoparticles with few defects and similar physical and magetic diameter distributions can be obtained by introducing molecular oxygen as one of the reactive species in the thermal decomposition synthesis. This is achieved without the need for any postsynthesis oxidation or thermal annealing. These results address a significant challenge in the synthesis of nanoparticles with predictable magnetic properties and could lead to advances in applications of magnetic nanoparticles.

  10. Quantum mechanical evolution towards thermal equilibrium

    OpenAIRE

    Linden, Noah; Popescu, Sandu; Short, Anthony J.; Winter, Andreas

    2008-01-01

    The circumstances under which a system reaches thermal equilibrium, and how to derive this from basic dynamical laws, has been a major question from the very beginning of thermodynamics and statistical mechanics. Despite considerable progress, it remains an open problem. Motivated by this issue, we address the more general question of equilibration. We prove, with virtually full generality, that reaching equilibrium is a universal property of quantum systems: Almost any subsystem in interacti...

  11. Effect of composting on the thermal decomposition behavior and kinetic parameters of pig manure-derived solid waste.

    Science.gov (United States)

    Dhyani, Vaibhav; Kumar Awasthi, Mukesh; Wang, Quan; Kumar, Jitendra; Ren, Xiuna; Zhao, Junchao; Chen, Hongyu; Wang, Meijing; Bhaskar, Thallada; Zhang, Zengqiang

    2017-12-27

    In this work, the influence of composting on the thermal decomposition behavior and decomposition kinetics of pig manure-derived solid wastes was analyzed using thermogravimetry. Wheat straw, biochar, zeolite, and wood vinegar were added to pig manure during composting. The composting was done in the 130 L PVC reactors with 100 L effective volume for 50 days. The activation energy of pyrolysis of samples before and after composting was calculated using Friedman's method, while the pre-exponential factor was calculated using Kissinger's equation. It was observed that composting decreased the volatile content of all the samples. The additives when added together in pig manure lead to a reduction in the activation energy of decomposition, advocating the presence of simpler compounds in the compost material in comparison with the complex feedstock. Copyright © 2017 Elsevier Ltd. All rights reserved.

  12. Mechanical and Thermal Characterization of Silica Nanocomposites

    Science.gov (United States)

    Cunningham, Anthony Lamar

    Polymer nanocomposites are a class of materials containing nanoparticles with a large interfacial surface area. Only a small quantity of nanoparticles are needed to provide superior multifunctional properties; such as mechanical, thermal, electrical, and moisture absorption properties in polymers. Nanoparticles tend to agglomerate, so special techniques are required for homogeneous distribution. Nanosilica is now readily available as colloidal sols, for example; Nanopox RTM F400 (supplied by Evonik Nanoresins AG, Germany). The nanoparticles are first synthesized from aqueous sodium silicate solution, and then undergo a surface modification process with organosilane and matrix exchange. F400 contains 40%wt silica nanoparticles colloidally dispersed in a DGEBA epoxy resin. The mean particle diameter is about 20 nm with a narrow distribution range of about 5 to 35 nm. The objectives of this study are to develop a reproducible processing method for nanosilica enhanced resin systems used in the manufacturing of fiber reinforced composites that will be characterized for mechanical and thermal properties. Research has concluded that shows improvements in the properties of the matrix material when processed in loading variations of 0 to 25%wt silica nanoparticles. The loadings were also used to manufacture fiberglass reinforced nanocomposite laminates and also tested for mechanical and thermal properties.

  13. Non-Fourier based thermal-mechanical tissue damage prediction for thermal ablation.

    Science.gov (United States)

    Li, Xin; Zhong, Yongmin; Smith, Julian; Gu, Chengfan

    2017-01-02

    Prediction of tissue damage under thermal loads plays important role for thermal ablation planning. A new methodology is presented in this paper by combing non-Fourier bio-heat transfer, constitutive elastic mechanics as well as non-rigid motion of dynamics to predict and analyze thermal distribution, thermal-induced mechanical deformation and thermal-mechanical damage of soft tissues under thermal loads. Simulations and comparison analysis demonstrate that the proposed methodology based on the non-Fourier bio-heat transfer can account for the thermal-induced mechanical behaviors of soft tissues and predict tissue thermal damage more accurately than classical Fourier bio-heat transfer based model.

  14. A Deep Insight into the Details of the Interisomerization and Decomposition Mechanism of o-Quinolyl and o-Isoquinolyl Radicals. Quantum Chemical Calculations and Computer Modeling.

    Science.gov (United States)

    Dubnikova, Faina; Tamburu, Carmen; Lifshitz, Assa

    2016-09-29

    The isomerization of o-quinolyl ↔ o-isoquinolyl radicals and their thermal decomposition were studied by quantum chemical methods, where potential energy surfaces of the reaction channels and their kinetics rate parameters were determined. A detailed kinetics scheme containing 40 elementary steps was constructed. Computer simulations were carried out to determine the isomerization mechanism and the distribution of reaction products in the decomposition. The calculated mole percent of the stable products was compared to the experimental values that were obtained in this laboratory in the past, using the single pulse shock tube. The agreement between the experimental and the calculated mole percents was very good. A map of the figures containing the mole percent's of eight stable products of the decomposition plotted vs T are presented. The fast isomerization of o-quinolyl → o-isoquinolyl radicals via the intermediate indene imine radical and the attainment of fast equilibrium between these two radicals is the reason for the identical product distribution regardless whether the reactant radical is o-quinolyl or o-isoquinolyl. Three of the main decomposition products of o-quinolyl radical, are those containing the benzene ring, namely, phenyl, benzonitrile, and phenylacetylene radicals. They undergo further decomposition mainly at high temperatures via two types of reactions: (1) Opening of the benzene ring in the radicals, followed by splitting into fragments. (2) Dissociative attachment of benzonitrile and phenyl acetylene by hydrogen atoms to form hydrogen cyanide and acetylene.

  15. Feedback processes in cellulose thermal decomposition: implications for fire-retarding strategies and treatments

    Science.gov (United States)

    Ball, R.; McIntosh, A. C.; Brindley, J.

    2004-06-01

    A simple dynamical system that models the competitive thermokinetics and chemistry of cellulose decomposition is examined, with reference to evidence from experimental studies indicating that char formation is a low activation energy exothermal process and volatilization is a high activation energy endothermal process. The thermohydrolysis chemistry at the core of the primary competition is described. Essentially, the competition is between two nucleophiles, a molecule of water and an -OH group on C6 of an end glucosyl cation, to form either a reducing chain fragment with the propensity to undergo the bond-forming reactions that ultimately form char, or a levoglucosan end-fragment that depolymerizes to volatile products. The results of this analysis suggest that promotion of char formation under thermal stress can actually increase the production of flammable volatiles. Thus, we would like to convey an important safety message in this paper: in some situations where heat and mass transfer is restricted in cellulosic materials, such as furnishings, insulation, and stockpiles, the use of char-promoting treatments for fire retardation may have the effect of increasing the risk of flaming combustion.

  16. Case study for model validation : assessing a model for thermal decomposition of polyurethane foam.

    Energy Technology Data Exchange (ETDEWEB)

    Dowding, Kevin J.; Leslie, Ian H. (New Mexico State University, Las Cruces, NM); Hobbs, Michael L.; Rutherford, Brian Milne; Hills, Richard Guy (New Mexico State University, Las Cruces, NM); Pilch, Martin M.

    2004-10-01

    A case study is reported to document the details of a validation process to assess the accuracy of a mathematical model to represent experiments involving thermal decomposition of polyurethane foam. The focus of the report is to work through a validation process. The process addresses the following activities. The intended application of mathematical model is discussed to better understand the pertinent parameter space. The parameter space of the validation experiments is mapped to the application parameter space. The mathematical models, computer code to solve the models and its (code) verification are presented. Experimental data from two activities are used to validate mathematical models. The first experiment assesses the chemistry model alone and the second experiment assesses the model of coupled chemistry, conduction, and enclosure radiation. The model results of both experimental activities are summarized and uncertainty of the model to represent each experimental activity is estimated. The comparison between the experiment data and model results is quantified with various metrics. After addressing these activities, an assessment of the process for the case study is given. Weaknesses in the process are discussed and lessons learned are summarized.

  17. Thermoanalytical studies of carbamazepine: hydration/dehydration, thermal decomposition, and solid phase transitions

    Directory of Open Access Journals (Sweden)

    Mônia Aparecida Lemos Pinto

    2014-12-01

    Full Text Available Carbamazepine (CBZ, a widely used anticonvulsant drug, can crystallize and exhibits four polymorphic forms and one dihydrate. Anhydrous CBZ can spontaneously absorb water and convert to the hydrate form whose different crystallinity leads to lower biological activity. The present study was concerned to the possibility of recovering the hydrated form by heating. The thermal behavior of spontaneously hydrated carbamazepine was investigated by TG/DTG-DTA and DSC in dynamic atmospheres of air and nitrogen, which revealed that the spontaneous hydration of this pharmaceutical resulted in a Form III hydrate with 1.5 water molecules. After dehydration, this anhydrous Form III converted to Form I, which melted and decomposed in a single event, releasing isocyanic acid, as shown by evolved gas analysis using TG-FTIR. Differential scanning calorimetry analyses revealed that Form III melted and crystallized as Form I, and that subsequent cooling cycles only generated Form I by crystallization. Solid state decomposition kinetic studies showed that there was no change in the substance after the elimination of water by heating to 120 °C. Activation energies of 98 ± 2 and 93 ± 2 kJ mol-1 were found for the hydrated and dried samples, respectively, and similar profiles of activation energy as a function of conversion factor were observed for these samples.

  18. Analysis of the Compounds from the BTEX Group, Emitted During Thermal Decomposition of Alkyd Resin

    Directory of Open Access Journals (Sweden)

    Kubecki M.

    2012-09-01

    Full Text Available Suitability of the given binding agent for the moulding sands preparation depends on the one hand on the estimation of technological properties of the sand and the mould made of it and the obtained casting quality and on the other hand on the assessment of this sand influence on the natural and working environment. Out of moulding sands used in the foundry industry, sands with organic binders deserve a special attention. These binders are based on synthetic resins, which ensure obtaining the proper technological properties and sound castings, however, they negatively influence the environment. If in the initial state these resins are not very dangerous for people and for the environment, thus under an influence of high temperatures they generate very harmful products, being the result of their thermal decomposition. Depending on the kind of the applied resin (phenol-formaldehyde, urea, furfuryl, urea-furfuryl, alkyd under an influence of a temperature such compounds as: furfuryl alcohol, formaldehyde, phenol, BTEX group (benzene, toluene, ethylbenzene, xylene, and also polycyclic aromatic hydrocarbons (PAH can be formed and released.

  19. Numerical study of hydrogen peroxide thermal decomposition in a shock tube

    Science.gov (United States)

    Bhatti, Muhammad Rizwan; Sheikh, Nadeem Ahmed; Manzoor, Shehryar; Khan, Muhammad Mahabat; Ali, Muzaffar

    2017-06-01

    Hydrogen peroxide (H2O2) has its significance during the combustion of heavy hydrocarbons in the internal combustion (IC) engines. Owing to its importance the measurements of H2O2 dissociation rate have been reported mostly using the shock tube apparatus. These types of experimental measurements are although quite reliable but require high cost. On the other hand, numerical simulations provide low cost and reliable solutions especially using computation fluid dynamics (CFD) software. In the current study an experimental shock tube flow is modeled using open access platform OpenFOAM to investigate the thermal decomposition of H2O2. Using two different convective schemes, limitedLinear and upwind, the propagation of shock wave and resultant dissociation reaction are simulated. The results of the simulations are compared with the experimental data. It is observed that the rate constant measured using the simulation data deviates from the experimental results in the low temperature range and approaches the experimental values as the temperature is raised.

  20. Pyrolysis kinetics and thermal decomposition behavior of polycarbonate - a TGA-FTIR study

    Directory of Open Access Journals (Sweden)

    Apaydin-Varol Esin

    2014-01-01

    Full Text Available This study covers the thermal degradation of polycarbonate by means of Thermogravimetric Analyzer coupled with Fourier transform infrared spectrometer (TGA-FTIR. Thermogravimetric analysis of polycarbonate was carried out at four different heating rates of 5, 10, 15, and 20°C per minute from 25°C to 1000°C under nitrogen atmosphere. The results indicated that polycarbonate was decomposed in the temperature range of 425-600°C. The kinetic parameters, such as activation energy, pre-exponential factor and reaction order were determined using five different kinetic models; namely Coast-Redfern, Friedman, Kissinger, Flynn-Wall-Ozawa (FWO, and Kissinger-Akahira-Sunose (KAS. Overall decomposition reaction order was determined by Coats-Redfern method as 1.5. Average activation energy was calculated as 150.42, 230.76, 216.97, and 218.56 kJ/mol by using Kissinger, Friedman, FWO, and KAS models, respectively. Furthermore, the main gases released during the pyrolysis of polycarbonate were determined as CO2, CH4, CO, H2O, and other lower molecular weight hydrocarbons such as aldehydes, ketones and carbonyls by using thermogravimetric analyzer coupled with Fourier transform infrared spectrometer.

  1. L1(0)-FePd nanocluster wires by template-directed thermal decomposition and subsequent hydrogen reduction

    Energy Technology Data Exchange (ETDEWEB)

    Cui, BZ; Marinescu, M; Liu, JF

    2013-12-14

    This paper reports the nanostructure, formation mechanism, and magnetic properties of tetragonal L1(0)-type Fe55Pd45 (at. %) nanocluster wires (NCWs) fabricated by thermal decomposition of metal nitrates and subsequent hydrogen reduction in nanoporous anodized aluminum oxide templates. The as-synthesized NCWs have diameters in the range of 80-300 nm, and lengths in the range of 0.5-10 mu m. The NCWs are composed of roughly round-shaped nanoclusters in the range of 3-30 nm in size and a weighted average size of 10 nm with a mixture of single-crystal and poly-crystalline structures. The obtained intrinsic coercivity H-i(c) of 3.32 kOe at room temperature for the tetragonal Fe55Pd45 NCWs is higher than those of electrodeposited Fe-Pd solid nanowires while among the highest values reported so far for L1(0)-type FePd nanoparticles. (C) 2013 AIP Publishing LLC.

  2. Monitoring the formation of carbide crystal phases during the thermal decomposition of 3d transition metal dicarboxylate complexes

    Energy Technology Data Exchange (ETDEWEB)

    Huba, ZJ; Carpenter, EE

    2014-06-06

    Single molecule precursors can help to simplify the synthesis of complex alloys by minimizing the amount of necessary starting reagents. However, single molecule precursors are time consuming to prepare with very few being commercially available. In this study, a simple precipitation method is used to prepare Fe, Co, and Ni fumarate and succinate complexes. These complexes were then thermally decomposed in an inert atmosphere to test their efficiency as single molecule precursors for the formation of metal carbide phases. Elevated temperature X-ray diffraction was used to identify the crystal phases produced upon decomposition of the metal dicarboxylate complexes. Thermogravimetric analysis coupled with an infrared detector was used to identify the developed gaseous decomposition products. All complexes tested showed a reduction from the starting M2+ oxidation state to the M oxidation state, upon decomposition. Also, each complex tested showed CO2 and H2O as gaseous decomposition products. Nickel succinate, iron succinate, and iron fumarate complexes were found to form carbide phases upon decomposition. This proves that transition metal dicarboxylate salts can be employed as efficient single molecule precursors for the formation of metal carbide crystal phases.

  3. Study of incompatibility of ammonium nitrate and its mechanism of decomposition by theoretical approach

    OpenAIRE

    Cagnina, Stefania; ROTUREAU, Patricia; Adamo, Carlo

    2013-01-01

    International audience; The dramatic accident involving ammonium nitrate (AN) that took place at Toulouse in September 2001 has once again focused attention to the complex hazards pertaining to this chemical. Despite the significant efforts made to increase AN safety over the whole supply chain, we are still facing insufficient knowledge of the actual mechanisms of ammonium nitrate decomposition that may take place in abnormal situations. The paper proposes a theoretical study of chemical inc...

  4. Resonance-Based Sparse Signal Decomposition and its Application in Mechanical Fault Diagnosis: A Review.

    Science.gov (United States)

    Huang, Wentao; Sun, Hongjian; Wang, Weijie

    2017-06-03

    Mechanical equipment is the heart of industry. For this reason, mechanical fault diagnosis has drawn considerable attention. In terms of the rich information hidden in fault vibration signals, the processing and analysis techniques of vibration signals have become a crucial research issue in the field of mechanical fault diagnosis. Based on the theory of sparse decomposition, Selesnick proposed a novel nonlinear signal processing method: resonance-based sparse signal decomposition (RSSD). Since being put forward, RSSD has become widely recognized, and many RSSD-based methods have been developed to guide mechanical fault diagnosis. This paper attempts to summarize and review the theoretical developments and application advances of RSSD in mechanical fault diagnosis, and to provide a more comprehensive reference for those interested in RSSD and mechanical fault diagnosis. Followed by a brief introduction of RSSD's theoretical foundation, based on different optimization directions, applications of RSSD in mechanical fault diagnosis are categorized into five aspects: original RSSD, parameter optimized RSSD, subband optimized RSSD, integrated optimized RSSD, and RSSD combined with other methods. On this basis, outstanding issues in current RSSD study are also pointed out, as well as corresponding instructional solutions. We hope this review will provide an insightful reference for researchers and readers who are interested in RSSD and mechanical fault diagnosis.

  5. Shock tube study on the thermal decomposition of fluoroethane using infrared laser absorption detection of hydrogen fluoride.

    Science.gov (United States)

    Matsugi, Akira; Shiina, Hiroumi

    2014-08-28

    Motivated by recent shock tube studies on the thermal unimolecular decomposition of fluoroethanes, in which unusual trends have been reported for collisional energy-transfer parameters, the rate constants for the thermal decomposition of fluoroethane were investigated using a shock tube/laser absorption spectroscopy technique. The rate constants were measured behind reflected shock waves by monitoring the formation of HF by IR absorption at the R(1) transition in the fundamental vibrational band near 2476 nm using a distributed-feedback diode laser. The peak absorption cross sections of this absorption line have also been determined and parametrized using the Rautian-Sobel'man line shape function. The rate constant measurements covered a wide temperature range of 1018-1710 K at pressures from 100 to 290 kPa, and the derived rate constants were successfully reproduced by the master equation calculation with an average downward energy transfer, ⟨ΔEdown⟩, of 400 cm(-1).

  6. An optimized ensemble local mean decomposition method for fault detection of mechanical components

    Science.gov (United States)

    Zhang, Chao; Li, Zhixiong; Hu, Chao; Chen, Shuai; Wang, Jianguo; Zhang, Xiaogang

    2017-03-01

    Mechanical transmission systems have been widely adopted in most of industrial applications, and issues related to the maintenance of these systems have attracted considerable attention in the past few decades. The recently developed ensemble local mean decomposition (ELMD) method shows satisfactory performance in fault detection of mechanical components for preventing catastrophic failures and reducing maintenance costs. However, the performance of ELMD often heavily depends on proper selection of its model parameters. To this end, this paper proposes an optimized ensemble local mean decomposition (OELMD) method to determinate an optimum set of ELMD parameters for vibration signal analysis. In OELMD, an error index termed the relative root-mean-square error (Relative RMSE) is used to evaluate the decomposition performance of ELMD with a certain amplitude of the added white noise. Once a maximum Relative RMSE, corresponding to an optimal noise amplitude, is determined, OELMD then identifies optimal noise bandwidth and ensemble number based on the Relative RMSE and signal-to-noise ratio (SNR), respectively. Thus, all three critical parameters of ELMD (i.e. noise amplitude and bandwidth, and ensemble number) are optimized by OELMD. The effectiveness of OELMD was evaluated using experimental vibration signals measured from three different mechanical components (i.e. the rolling bearing, gear and diesel engine) under faulty operation conditions.

  7. Thermal Decomposition of Potential Ester Biofuels. Part I: Methyl Acetate and Methyl Butanoate

    Energy Technology Data Exchange (ETDEWEB)

    Porterfield, Jessica P.; Bross, David H.; Ruscic, Branko; Thorpe, James H.; Nguyen, Thanh Lam; Baraban, Joshua H.; Stanton, John F.; Daily, John W.; Ellison, G. Barney

    2017-06-09

    Two methyl esters have been examined as models for the pyrolysis of biofuels. Dilute samples (0.06 - 0.13%) of methyl acetate (CH3COOCH3) and methyl butanoate (CH3CH2CH2COOCH3) were entrained in (He, Ar) carrier gas and decomposed in a set of flash-pyrolysis micro-reactors. The pyrolysis products resulting from the methyl esters were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by matrix infrared absorption spectroscopy. Pyrolysis pressures in the pulsed micro-reactor were roughly 20 Torr and residence times through the reactors were approximately 25 - 150 µs. Reactor temperatures of 300 – 1600 K were explored. Decomposition of CH3COOCH3 commences at 1000 K and the initial products are (CH2=C=O and CH3OH). As the micro-reactor is heated to 1300 K, a mixture of (CH2=C=O and CH3OH, CH3, CH2=O, H, CO, CO2) appears. The thermal cracking of CH3CH2CH2COOCH3 begins at 800 K with the formation of (CH3CH2CH=C=O, CH3OH). By 1300 K, the pyrolysis of methyl butanoate yields a complex mixture of (CH3CH2CH=C=O, CH3OH, CH3, CH2=O, CO, CO2, CH3CH=CH2, CH2CHCH2, CH2=C=CH2, HCCCH2, CH2=C=C=O, CH2=CH2, HCΞCH, CH2=C=O). Based on the results from the thermal cracking of methyl acetate and methyl butanoate, we predict several important decomposition channels for the pyrolysis of fatty acid methyl esters, R CH2-COOCH3. The lowest energy fragmentation will be a 4-center elimination of methanol to form the ketene, RCH=C=O. At higher temperatures, concerted

  8. Thermal Decomposition of Potential Ester Biofuels. Part I: Methyl Acetate and Methyl Butanoate.

    Science.gov (United States)

    Porterfield, Jessica P; Bross, David H; Ruscic, Branko; Thorpe, James H; Nguyen, Thanh Lam; Baraban, Joshua H; Stanton, John F; Daily, John W; Ellison, G Barney

    2017-06-22

    Two methyl esters were examined as models for the pyrolysis of biofuels. Dilute samples (0.06-0.13%) of methyl acetate (CH3COOCH3) and methyl butanoate (CH3CH2CH2COOCH3) were entrained in (He, Ar) carrier gas and decomposed in a set of flash-pyrolysis microreactors. The pyrolysis products resulting from the methyl esters were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by matrix infrared absorption spectroscopy. Pyrolysis pressures in the pulsed microreactor were about 20 Torr and residence times through the reactors were roughly 25-150 μs. Reactor temperatures of 300-1600 K were explored. Decomposition of CH3COOCH3 commences at 1000 K, and the initial products are (CH2═C═O and CH3OH). As the microreactor is heated to 1300 K, a mixture of CH2═C═O and CH3OH, CH3, CH2═O, H, CO, and CO2 appears. The thermal cracking of CH3CH2CH2COOCH3 begins at 800 K with the formation of CH3CH2CH═C═O and CH3OH. By 1300 K, the pyrolysis of methyl butanoate yields a complex mixture of CH3CH2CH═C═O, CH3OH, CH3, CH2═O, CO, CO2, CH3CH═CH2, CH2CHCH2, CH2═C═CH2, HCCCH2, CH2═C═C═O, CH2═CH2, HC≡CH, and CH2═C═O. On the basis of the results from the thermal cracking of methyl acetate and methyl butanoate, we predict several important decomposition channels for the pyrolysis of fatty acid methyl esters, R-CH2-COOCH3. The lowest-energy fragmentation will be a 4-center elimination of methanol to form the ketene RCH═C═O. At higher temperatures, concerted fragmentation to radicals will ensue to produce a mixture of species: (RCH2 + CO2 + CH3) and (RCH2 + CO + CH2═O + H). Thermal cracking of the β C-C bond of the methyl ester will generate the radicals (R and H) as well as CH2═C═O + CH2═O. The thermochemistry of methyl acetate and its fragmentation products were obtained via the Active Thermochemical Tables (ATcT) approach, resulting in ΔfH298(CH3COOCH3) = -98

  9. Direct Growth of CuO Nanorods on Graphitic Carbon Nitride with Synergistic Effect on Thermal Decomposition of Ammonium Perchlorate

    Directory of Open Access Journals (Sweden)

    Linghua Tan

    2017-05-01

    Full Text Available Novel graphitic carbon nitride/CuO (g-C3N4/CuO nanocomposite was synthesized through a facile precipitation method. Due to the strong ion-dipole interaction between copper ions and nitrogen atoms of g-C3N4, CuO nanorods (length 200–300 nm, diameter 5–10 nm were directly grown on g-C3N4, forming a g-C3N4/CuO nanocomposite, which was confirmed via X-ray diffraction (XRD, transmission electron microscopy (TEM, field emission scanning electron microscopy (FESEM, and X-ray photoelectron spectroscopy (XPS. Finally, thermal decomposition of ammonium perchlorate (AP in the absence and presence of the prepared g-C3N4/CuO nanocomposite was examined by differential thermal analysis (DTA, and thermal gravimetric analysis (TGA. The g-C3N4/CuO nanocomposite showed promising catalytic effects for the thermal decomposition of AP. Upon addition of 2 wt % nanocomposite with the best catalytic performance (g-C3N4/20 wt % CuO, the decomposition temperature of AP was decreased by up to 105.5 °C and only one decomposition step was found instead of the two steps commonly reported in other examples, demonstrating the synergistic catalytic activity of the as-synthesized nanocomposite. This study demonstrated a successful example regarding the direct growth of metal oxide on g-C3N4 by ion-dipole interaction between metallic ions, and the lone pair electrons on nitrogen atoms, which could provide a novel strategy for the preparation of g-C3N4-based nanocomposite.

  10. Fabrication of ammonium perchlorate/copper-chromium oxides core-shell nanocomposites for catalytic thermal decomposition of ammonium perchlorate

    Energy Technology Data Exchange (ETDEWEB)

    Eslami, Abbas, E-mail: eslami@umz.ac.ir [Department of Inorganic Chemistry, Faculty of Chemistry, University of Mazandaran, P.O.Box 47416-95447, Babolsar (Iran, Islamic Republic of); Juibari, Nafise Modanlou [Department of Inorganic Chemistry, Faculty of Chemistry, University of Mazandaran, P.O.Box 47416-95447, Babolsar (Iran, Islamic Republic of); Hosseini, Seyed Ghorban [Department of Chemistry, Malek Ashtar University of Technology, P.O. Box 16765-3454, Tehran (Iran, Islamic Republic of)

    2016-09-15

    The ammonium perchlorate/Cu(II)-Cr(III)-oxides(AP/Cu-Cr-O) core-shell nanocomposites were in-situ prepared by deposition of copper and chromium oxides on suspended ammonium perchlorate particles in ethyl acetate as solvent. The results of differential scanning calorimetery (DSC) and thermal gravimetric analysis (TGA) experiments showed that the nanocomposites have excellent catalytic effect on the thermal decomposition of AP, so that the released heat increases up to about 3-fold over initial values, changing from 450 J/g for pure AP to 1510 J/g for most appropriate mixture. For better comparison, single metal oxide/AP core-shell nanocomposite have also been prepared and the results showed that they have less catalytic effect respect to mixed metal oxides system. Scanning electron microscopy (SEM) results revealed homogenous deposition of nanoparticles on the surface of AP and fabrication of core-shell structures. The kinetic parameters of thermal decomposition of both pure AP and AP/Cu-Cr-O samples have been calculated by Kissinger method and the results showed that the values of pre-exponential factor and activation energy are higher for AP/Cu-Cr-O nanocomposite. The better catalytic effect of Cu-Cr-O nanocomposites is probably attributed to the synergistic effect between Cu{sup 2+} and Cr{sup 3+} in the nanocomposites, smaller particle size and more crystal defect. - Highlights: • The Cu-Cr-O nanoparticles were synthesized by chemical liquid deposition method. • Then, the AP/Cu-Cr-O core-shell nanocomposites were prepared. • The core-shell samples showed high catalytic activity for AP decomposition. • Thermal decomposition of samples occurs at lower temperature range.

  11. Quantum mechanical evolution towards thermal equilibrium.

    Science.gov (United States)

    Linden, Noah; Popescu, Sandu; Short, Anthony J; Winter, Andreas

    2009-06-01

    The circumstances under which a system reaches thermal equilibrium, and how to derive this from basic dynamical laws, has been a major question from the very beginning of thermodynamics and statistical mechanics. Despite considerable progress, it remains an open problem. Motivated by this issue, we address the more general question of equilibration. We prove, with virtually full generality, that reaching equilibrium is a universal property of quantum systems: almost any subsystem in interaction with a large enough bath will reach an equilibrium state and remain close to it for almost all times. We also prove several general results about other aspects of thermalization besides equilibration, for example, that the equilibrium state does not depend on the detailed microstate of the bath.

  12. Influence of aging time of oleate precursor on the magnetic relaxation of cobalt ferrite nanoparticles synthesized by the thermal decomposition method

    Energy Technology Data Exchange (ETDEWEB)

    Herrera, Adriana P.; Polo-Corrales, Liliana [Department of Chemical Engineering, University of Puerto Rico, Mayagueez, Puerto Rico, PR 00681-9000 (United States); Chavez, Ermides; Cabarcas-Bolivar, Jari [Department of Physics, University of Puerto Rico, Mayagueez, Puerto Rico, PR 00681-9000 (United States); Uwakweh, Oswald N.C. [Department of General Engineering, University of Puerto Rico, Mayagueez, Puerto Rico, PR 00681-9000 (United States); Rinaldi, Carlos, E-mail: crinaldi@uprm.edu [Department of Chemical Engineering, University of Puerto Rico, Mayagueez, Puerto Rico, PR 00681-9000 (United States)

    2013-02-15

    Cobalt ferrite nanoparticles are of interest because of their room temperature coercivity and high magnetic anisotropy constant, which make them attractive in applications such as sensors based on the Brownian relaxation mechanism and probes to determine the mechanical properties of complex fluids at the nanoscale. These nanoparticles can be synthesized with a narrow size distribution by the thermal decomposition of an iron-cobalt oleate precursor in a high boiling point solvent. We studied the influence of aging time of the iron-cobalt oleate precursor on the structure, chemical composition, size, and magnetic relaxation of cobalt ferrite nanoparticles synthesized by the thermal decomposition method. The structure and thermal behavior of the iron-cobalt oleate was studied during the aging process. Infrared spectra indicated a shift in the coordination state of the oleate and iron/cobalt ions from bidentate to bridging coordination. Aging seemed to influence the thermal decomposition of the iron-cobalt oleate as determined from thermogravimmetric analysis and differential scanning calorimetry, where shifts in the temperatures corresponding to decomposition events and a narrowing of the endotherms associated with these events were observed. Aging promoted formation of the spinel crystal structure, as determined from X-ray diffraction, and influenced the nanoparticle magnetic properties, resulting in an increase in blocking temperature and magnetocrystalline anisotropy. Mossbauer spectra also indicated changes in the magnetic properties resulting from aging of the precursor oleate. Although all samples exhibited some degree of Brownian relaxation, as determined from complex susceptibility measurements in a liquid medium, aging of the iron-cobalt oleate precursor resulted in crossing of the in-phase {chi} Prime and out-of-phase {chi} Double-Prime components of the complex susceptibility at the frequency of the Brownian magnetic relaxation peak, as expected for

  13. Total control of chromium in tanneries - thermal decomposition of filtration cake from enzymatic hydrolysis of chrome shavings.

    Science.gov (United States)

    Kocurek, P; Kolomazník, K; Bařinová, M; Hendrych, J

    2017-04-01

    This paper deals with the problem of chromium recovery from chrome-tanned waste and thus with reducing the environmental impact of the leather industry. Chrome-tanned waste was transformed by alkaline enzymatic hydrolysis promoted by magnesium oxide into practically chromium-free, commercially applicable collagen hydrolysate and filtration cake containing a high portion of chromium. The crude and magnesium-deprived chromium cakes were subjected to a process of thermal decomposition at 650°C under oxygen-free conditions to reduce the amount of this waste and to study the effect of magnesium removal on the resulting products. Oxygen-free conditions were applied in order to prevent the oxidation of trivalent chromium into the hazardous hexavalent form. Thermal decomposition products from both crude and magnesium-deprived chrome cakes were characterized by high chromium content over 50%, which occurred as eskolaite (Cr2O3) and magnesiochromite (MgCr2O4) crystal phases, respectively. Thermal decomposition decreased the amount of chrome cake dry feed by 90%. Based on the performed experiments, a scheme for the total control of chromium in the leather industry was designed.

  14. Mass transfer in fuel cells. [electron microscopy of components, thermal decomposition of Teflon, water transport, and surface tension of KOH solutions

    Science.gov (United States)

    Walker, R. D., Jr.

    1973-01-01

    Results of experiments on electron microscopy of fuel cell components, thermal decomposition of Teflon by thermogravimetry, surface area and pore size distribution measurements, water transport in fuel cells, and surface tension of KOH solutions are described.

  15. Kinetics of diffusive decomposition in the case of several mass transfer mechanisms

    Science.gov (United States)

    Alexandrov, D. V.

    2017-01-01

    An analytical description of the final stage of diffusive decomposition leaning upon the Slezov theory is developed for several mass transfer mechanisms. The process of formation and relaxation of the crystal size distribution function from the initial ripening stage to its final state corresponding to the universal distribution is studied. The boundary points of a transition region responsible for the tails of the distribution functions on the right of the relevant stopping points are found analytically. The explicit time-dependent analytical expressions for the distribution function and particle growth rates are derived with allowance for the plausible mechanisms of mass transfer.

  16. Biodegradable compounds: Rheological, mechanical and thermal properties

    Science.gov (United States)

    Nobile, Maria Rossella; Lucia, G.; Santella, M.; Malinconico, M.; Cerruti, P.; Pantani, R.

    2015-12-01

    Recently great attention from industry has been focused on biodegradable polyesters derived from renewable resources. In particular, PLA has attracted great interest due to its high strength and high modulus and a good biocompatibility, however its brittleness and low heat distortion temperature (HDT) restrict its wide application. On the other hand, Poly(butylene succinate) (PBS) is a biodegradable polymer with a low tensile modulus but characterized by a high flexibility, excellent impact strength, good thermal and chemical resistance. In this work the two aliphatic biodegradable polyesters PBS and PLA were selected with the aim to obtain a biodegradable material for the industry of plastic cups and plates. PBS was also blended with a thermoplastic starch. Talc was also added to the compounds because of its low cost and its effectiveness in increasing the modulus and the HDT of polymers. The compounds were obtained by melt compounding in a single screw extruder and the rheological, mechanical and thermal properties were investigated. The properties of the two compounds were compared and it was found that the values of the tensile modulus and elongation at break measured for the PBS/PLA/Talc compound make it interesting for the production of disposable plates and cups. In terms of thermal resistance the compounds have HDTs high enough to contain hot food or beverages. The PLA/PBS/Talc compound can be, then, considered as biodegradable substitute for polystyrene for the production of disposable plates and cups for hot food and beverages.

  17. Synthesis of phase-pure and monodisperse iron oxide nanoparticles by thermal decomposition.

    Science.gov (United States)

    Hufschmid, Ryan; Arami, Hamed; Ferguson, R Matthew; Gonzales, Marcela; Teeman, Eric; Brush, Lucien N; Browning, Nigel D; Krishnan, Kannan M

    2015-07-07

    Superparamagnetic iron oxide nanoparticles (SPIONs) are used for a wide range of biomedical applications requiring precise control over their physical and magnetic properties, which are dependent on their size and crystallographic phase. Here we present a comprehensive template for the design and synthesis of iron oxide nanoparticles with control over size, size distribution, phase, and resulting magnetic properties. We investigate critical parameters for synthesis of monodisperse SPIONs by organic thermal decomposition. Three different, commonly used, iron containing precursors (iron oleate, iron pentacarbonyl, and iron oxyhydroxide) are evaluated under a variety of synthetic conditions. We compare the suitability of these three kinetically controlled synthesis protocols, which have in common the use of iron oleate as a starting precursor or reaction intermediate, for producing nanoparticles with specific size and magnetic properties. Monodisperse particles were produced over a tunable range of sizes from approximately 2-30 nm. Reaction parameters such as precursor concentration, addition of surfactant, temperature, ramp rate, and time were adjusted to kinetically control size and size-distribution, phase, and magnetic properties. In particular, large quantities of excess surfactant (up to 25 : 1 molar ratio) alter reaction kinetics and result in larger particles with uniform size; however, there is often a trade-off between large particles and a narrow size distribution. Iron oxide phase, in addition to nanoparticle size and shape, is critical for establishing magnetic properties such as differential susceptibility (dm/dH) and anisotropy. As an example, we show the importance of obtaining the required size and iron oxide phase for application to Magnetic Particle Imaging (MPI), and describe how phase purity can be controlled. These results provide much of the information necessary to determine which iron oxide synthesis protocol is best suited to a particular

  18. Hydrogen and Carbon Black Production from Thermal Decomposition of Sub-Quality Natural Gas

    Directory of Open Access Journals (Sweden)

    M. Javadi

    2010-03-01

    Full Text Available The objective of this paper is computational investigation of the hydrogen and carbon black production through thermal decomposition of waste gases containing CH4 and H2S, without requiring a H2S separation process. The chemical reaction model, which involves solid carbon, sulfur compounds and precursor species for the formation of carbon black, is based on an assumed Probability Density Function (PDF parameterized by the mean and variance of mixture fraction and β-PDF shape. The effects of feedstock mass flow rate and reactor temperature on hydrogen, carbon black, S2, SO2, COS and CS2 formation are investigated. The results show that the major factor influencing CH4 and H2S conversions is reactor temperature. For temperatures higher than 1100° K, the reactor CH4 conversion reaches 100%, whilst H2S conversion increases in temperatures higher than 1300° K. The results reveal that at any temperature, H2S conversion is less than that of CH4. The results also show that in the production of carbon black from sub-quality natural gas, the formation of carbon monoxide, which is occurring in parallel, play a very significant role. For lower values of feedstock flow rate, CH4 mostly burns to CO and consequently, the production of carbon black is low. The results show that the yield of hydrogen increases with increasing feedstock mass flow rate until the yield reaches a maximum value, and then drops with further increase in the feedstock mass flow rate.

  19. HEAVY AND THERMAL OIL RECOVERY PRODUCTION MECHANISMS

    Energy Technology Data Exchange (ETDEWEB)

    Anthony R. Kovscek

    2003-01-01

    This technical progress report describes work performed from October 1 through December 31, 2002 , for the project ''Heavy and Thermal Oil Recovery Production Mechanisms.'' In this project, a broad spectrum of research is undertaken related to thermal and heavy-oil recovery. The research tools and techniques used are varied and span from pore-level imaging of multiphase fluid flow to definition of reservoir-scale features through streamline-based history-matching techniques. During this period, experimental data regarding multidimensional imbibition was analyzed to obtain shape factors appropriate for dual-porosity simulation. It is shown that the usual assumption of constant, time-independent shape factors is incorrect. In other work, we continued to study the mechanisms by which oil is produced from fractured media at high pressure and high temperature. High temperature significantly increased the apparent wettability and affected water relative permeability of cores used in previous experiments. A phenomenological and mechanistic cause for this behavior is sought. Our work in the area of primary production of heavy oil continues with field cores and crude oil. On the topic of reservoir definition, work continued on developing techniques that integrate production history into reservoir models using streamline-based properties.

  20. HEAVY AND THERMAL OIL RECOVERY PRODUCTION MECHANISMS

    Energy Technology Data Exchange (ETDEWEB)

    Anthony R. Kovscek

    2002-07-01

    This technical progress report describes work performed from April 1 through June 30, 2002, for the project ''Heavy and Thermal Oil Recovery Production Mechanisms.'' We investigate a broad spectrum of topics related to thermal and heavy-oil recovery. Significant results were obtained in the areas of multiphase flow and rock properties, hot-fluid injection, improved primary heavy oil recovery, and reservoir definition. The research tools and techniques used are varied and span from pore-level imaging of multiphase fluid flow to definition of reservoir-scale features through streamline-based history-matching techniques. Briefly, experiments were conducted to image at the pore level matrix-to-fracture production of oil from a fractured porous medium. This project is ongoing. A simulation studied was completed in the area of recovery processes during steam injection into fractured porous media. We continued to study experimentally heavy-oil production mechanisms from relatively low permeability rocks under conditions of high pressure and high temperature. High temperature significantly increased oil recovery rate and decreased residual oil saturation. Also in the area of imaging production processes in laboratory-scale cores, we use CT to study the process of gas-phase formation during solution gas drive in viscous oils. Results from recent experiments are reported here. Finally, a project was completed that uses the producing water-oil ratio to define reservoir heterogeneity and integrate production history into a reservoir model using streamline properties.

  1. Thermal decomposition of UO{sub 3}-2H{sub 2}0

    Energy Technology Data Exchange (ETDEWEB)

    Flament, T.A.

    1998-02-26

    The first part of the report summarizes the literature data regarding the uranium trioxide water system. In the second part, the experimental aspects are presented. An experimental program has been set up to determine the steps and species involved in decomposition of uranium oxide di-hydrate. Particular attention has been paid to determine both loss of free water (moisture in the fuel) and loss of chemically bound water (decomposition of hydrates). The influence of water pressure on decomposition has been taken into account.

  2. Thermal decomposition of energetic materials. 2. Deuterium isotope effects and isotopic scrambling in condensed-phase decomposition of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine. Technical report

    Energy Technology Data Exchange (ETDEWEB)

    Behrens, R.; Bulusu, S.

    1993-02-01

    The products formed in the thermal decomposition of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) have been traced to using mixtures of different isotopically labeled analogues of HMX. The isotopic analogues of HMX used in the experiments include 2H, 13C, 15NO2, 15N sub ring, and 18O. The fraction of isotopic scrambling and the extent of the deuterium kinetic isotope effect (DKIE) are reported for the different thermal decomposition products. Isotopic scrambling is not observed for the N-N bond in N2O and the C-H bonds in CH2O. Only one of the C-N bonds in N-methylformamide (NMFA) undergoes isotopic scrambling. The lack of complete isotopic scrambling of the N-NO bond in 1-nitroso-3,5,7-trinitro-1,3,5,7-tetrazocine (ONTNTA) is shown to imply that some HMX decomposition occurs in the lattice. The behavior of the DKIE in different mixtures of isotopic analogues of HMX suggests that water probably acts as a catalyst in the decomposition. The results demonstrate that decomposition of HMX in the condensed phase has several reaction branches.... DKIE, Isotope effect, Isotopic scrambling, HMX, NMFA, ONTNTA, Thermal decomposition.

  3. A simple thermal decomposition-nitridation route to nanocrystalline boron nitride (BN) from a single N and B source precursor

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Hong; Chen Youjian [College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang 325027 (China); Ma Jianhua, E-mail: mjh820@ustc.edu [College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang 325027 (China); Nanomaterials and Chemistry Key Laboratory, Advanced Materials Research Center of Wenzhou, Wenzhou University, Wenzhou, Zhejiang 325027 (China); Tong Hanxuan; Yang Jiang; Ni Danwei; Hu Huiming; Zheng Fangqing [Oujiang College, Wenzhou University, Wenzhou, Zhejiang 325027 (China)

    2011-06-09

    Graphical abstract: Display Omitted Highlights: > Nanocrystalline BN was synthesized via a thermal decomposition-nitridation route. > B and N sources come from a single cheap safe precursor NH{sub 4}HB{sub 4}O{sub 7}.3H{sub 2}O. > The reaction could be carried out in an autoclave at 650 deg. C for 8 h. > X-ray powder diffraction patterns indicate that the product is hexagonal BN. > The product has good thermal stability and oxidation resistance below 900 deg. C. - Abstract: Nanocrystalline boron nitride (BN) was synthesized via a simple thermal decomposition-nitridation route by the reaction of hydrated ammonium tetraborate (NH{sub 4}HB{sub 4}O{sub 7}.3H{sub 2}O) and metallic magnesium powders in an autoclave at 650 deg. C. The crystal phase, morphology, grain size, and chemical composition of the as-prepared products were characterized in detail by X-ray powder diffraction (XRD), energy dispersion spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), field-emission scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM). The products were also studied by FT-IR and the thermogravimetric analysis (TGA). Results revealed that the as-synthesized nanocrystalline were h-BN, and they had diameters within 100 nm. They had good thermal stability and oxidation resistance in high temperature.

  4. Modified Graphene with SnO2 Nanocomposites Using Thermal Decomposition Method and Sensing Behavior Towards NO2 Gas

    Science.gov (United States)

    Sharma, Vikram

    2017-11-01

    This is the first time the graphene sample has been functionalized with metal oxide nanoparticles by thermal decomposition process. In this paper, graphene has been synthesized from natural resources using flower petals as carbon feedstock by thermal exfoliation technique at temperatures 1300 °C and the synthesis of graphene-tin oxide (SnO2) nanocomposites has been done using chemical treatment followed by thermal decomposition method. The response versus time condition has been investigated for the fabricated sample. The electrical resistance w.r.t. temperature could be explained by the thermal generation of electron-hole pairs and carrier scattering by acoustic phonons. The structural, morphological and chemical composition studies of the nanocomposites were carried out by the Raman spectroscopy, x-ray diffraction spectroscopy, scanning electron microscopy (SEM), x-ray photoelectron spectroscopy and high-resolution transmission electron microscopy (HRTEM). The evidence of good-quality graphene is obtained from Raman spectroscopy studies. The SEM and HRTEM images have shown that SnO2 nanoparticles are well distributed in the multilayer electron transparent graphene films. The sensor response was found to lie between 8.25 and 9.36% at 500 ppm of nitrogen dioxide, and also resistance recovered quickly without any application of heat. We believe such chemical treatment of graphene could potentially be used to manufacture a new generation of low-power nano-NO2 sensors.

  5. Kinetics of thermal decomposition of some biomasses in an inert environment. An investigation of the effect of lead loaded by biosorption.

    Science.gov (United States)

    Martín-Lara, María Ángeles; Iáñez-Rodríguez, Irene; Blázquez, Gabriel; Quesada, Lucía; Pérez, Antonio; Calero, Mónica

    2017-12-01

    The thermal behavior of some types of raw and lead-polluted biomasses typical in south Spain was studied by non-isothermal thermogravimetry. Experiments were carried out in nitrogen atmosphere at three heating rates (5, 10 and 20°C/min). The results of thermogravimetric tests carried out proved that the presence of lead did not change the main degradation pathways of selected biomass (almond shell (AS) and olive pomace (OP)). However, from a point of view of mass loss, lead-polluted samples showed higher decomposition temperatures and decomposition at higher rate. The determination of activation energies was performed by isoconversional methods of Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS) and Friedman (FR). In general, lead-polluted samples showed lower activation energies than raw ones. Then, Coast-Redfern method was applied to determine kinetic function. The kinetic function that seems to determine the mechanism of thermal degradation of main components of all samples was nth order reaction. Finally, a model based on three parallel reactions (for three pseudocomponents) that fit to nth order reactions was evaluated. This model was appropriate to predict the pyrolysis behavior of the raw and lead-polluted samples in all pyrolysis conditions studied. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. [Real-time analysis of polyvinyl chloride thermal decomposition/combustion products with single photon ionization/photoelectron ionization online mass spectrometer].

    Science.gov (United States)

    Chen, Wen-Dong; Hou, Ke-Yong; Chen, Ping; Li, Fang-Long; Zhao, Wu-Duo; Cui, Hua-Peng; Hua, Lei; Xie, Yuan-Yuan; Li, Hai-Yang

    2013-01-01

    With the features of a broad range of ionizable compounds, reduced fragments and simple mass spectrum, a homemade magnetic field enhanced photoelectron ionization (MEPEI) source combined with single photon ionization (SPI) for time-of-flight mass spectrometer was built and applied to analyze thermal decomposition/combustion products of polyvinyl chloride (PVC). The combined ion source can be switched very fast between SPI mode and SPI-MEPEI mode for detecting different targeted compounds, and only adjusting the voltage of the electrode in the ionization region to trigger the switch. Among the PVC thermal decomposition/combustion products, HCl and CO2, which ionization energies (12.74 eV, 13.77 eV respectively) were higher than the energy of photon (10.60 eV), were ionized by MEPEI, while alkenes, dichloroethylene, benzene and its homologs, monochlorobenzene, styrene, indane, naphthalene and its homologs were ionized by SPI and MEPEI simultaneously. Spectra of interested products as a function of temperatures indicated that products are formed via two main mechanisms: (1) dechlorination and intramolecular cyclization can lead to the formation of HCl, benzene and naphthalene at 250-370 degrees C; (2) intermolecular crosslinking leads to the formation of alkyl aromatics such as toluene and xylene/ethylbenzene at 380-510 degrees C. The experimental results show that the combined ion source of SPI/ SPI-MEPEI for TOF-MS has broad application prospects in the online analysis field.

  7. Thermal-mechanical deformation modelling of soft tissues for thermal ablation.

    Science.gov (United States)

    Li, Xin; Zhong, Yongmin; Jazar, Reza; Subic, Aleksandar

    2014-01-01

    Modeling of thermal-induced mechanical behaviors of soft tissues is of great importance for thermal ablation. This paper presents a method by integrating the heating process with thermal-induced mechanical deformations of soft tissues for simulation and analysis of the thermal ablation process. This method combines bio-heat transfer theories, constitutive elastic material law under thermal loads as well as non-rigid motion dynamics to predict and analyze thermal-mechanical deformations of soft tissues. The 3D governing equations of thermal-mechanical soft tissue deformation are discretized by using the finite difference scheme and are subsequently solved by numerical algorithms. Experimental results show that the proposed method can effectively predict the thermal-induced mechanical behaviors of soft tissues, and can be used for the thermal ablation therapy to effectively control the delivered heat energy for cancer treatment.

  8. Insight to the Thermal Decomposition and Hydrogen Desorption Behaviors of NaNH2-NaBH4 Hydrogen Storage Composite.

    Science.gov (United States)

    Pei, Ziwei; Bai, Ying; Wang, Yue; Wu, Feng; Wu, Chuan

    2017-09-20

    The lightweight compound material NaNH2-NaBH4 is regarded as a promising hydrogen storage composite due to the high hydrogen density. Mechanical ball milling was employed to synthesize the composite NaNH2-NaBH4 (2/1 molar ratio), and the samples were investigated utilizing thermogravimetric-differential thermal analysis-mass spectroscopy (TG-DTA-MS), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) analyses. The full-spectrum test (range of the ratio of mass to charge: 0-200) shows that the released gaseous species contain H2, NH3, B2H6, and N2 in the heating process from room temperature to 400 °C, and possibly the impurity gas B6H12 also exists. The TG/DTA analyses show that the composite NaNH2-NaBH4 (2/1 molar ratio) is conductive to generate hydrogen so that the dehydrogenation process can be finished before 400 °C. Moreover, the thermal decomposition process from 200 to 400 °C involves two-step dehydrogenation reactions: (1) Na3(NH2)2BH4 hydride decomposes into Na3BN2 and H2 (200-350 °C); (2) remaining Na3(NH2)2BH4 reacts with NaBH4 and Na3BN2, generating Na, BN, NH3, N2, and H2 (350-400 °C). The better mechanism understanding of the thermal decomposition pathway lays a foundation for tailoring the hydrogen storage performance of the composite complex hydrides system.

  9. On the dynamic equivalence of planar mechanisms: An inertia decomposition method

    OpenAIRE

    de Jong, J. J.; van Dijk, J.; J. L. Herder; Wenger, Philippe; Flores, Paulo

    2016-01-01

    In this paper the dynamic equivalence of planar mechanisms is investigated by decomposition of inertia into point masses. For a planar rigid body, two point masses can fully describe its dynamic behavior. The location of one these points can be chosen freely, fixing the second point. By locating one of the two point masses of a link on a revolute joint, this link can be fully described by the one remaining point mass. By applying this approach throughout the mechanism’s chain, a reduced param...

  10. Mechanical and assembly units of viral capsids identified via quasi-rigid domain decomposition.

    Directory of Open Access Journals (Sweden)

    Guido Polles

    Full Text Available Key steps in a viral life-cycle, such as self-assembly of a protective protein container or in some cases also subsequent maturation events, are governed by the interplay of physico-chemical mechanisms involving various spatial and temporal scales. These salient aspects of a viral life cycle are hence well described and rationalised from a mesoscopic perspective. Accordingly, various experimental and computational efforts have been directed towards identifying the fundamental building blocks that are instrumental for the mechanical response, or constitute the assembly units, of a few specific viral shells. Motivated by these earlier studies we introduce and apply a general and efficient computational scheme for identifying the stable domains of a given viral capsid. The method is based on elastic network models and quasi-rigid domain decomposition. It is first applied to a heterogeneous set of well-characterized viruses (CCMV, MS2, STNV, STMV for which the known mechanical or assembly domains are correctly identified. The validated method is next applied to other viral particles such as L-A, Pariacoto and polyoma viruses, whose fundamental functional domains are still unknown or debated and for which we formulate verifiable predictions. The numerical code implementing the domain decomposition strategy is made freely available.

  11. Effects of Martian Surface Materials on the Thermal Decomposition of Hydrogen Peroxide

    Science.gov (United States)

    Dame, Rudger H.; Archer, Paul Douglas; Hogancamp, Joanna C.

    2017-10-01

    While hydrogen peroxide (H2O2) has been detected in the martian atmosphere, it has not been detected in surface materials. Since the Viking lander mission, we have sent instruments to Mars with the capability to detect H2O2. The Sample Analysis at Mars (SAM) instrument onboard the Curiosity Rover and Thermal and Evolved Gas Analyzer (TEGA) instrument on the Phoenix lander both detected water and oxygen releases from analyzed sediments but whether or not peroxide could be the source of these gases has not been investigated. We are investigating the possible presence of H2O2 in martian materials by analyzing Mars-relevant minerals that have been mixed with hydrogen peroxide using lab instruments configured as analogs to Mars mission instruments.The object of this research is to use lab instruments to find the effects of Mars analog minerals on hydrogen peroxide gas release temperatures, specifically gas releases of water and oxygen and also determine the effect of the peroxide on the minerals. Data that we get from the lab can then be compared to the data collected from Mars.The minerals hematite, siderite, San Carlos olivine, magnetite and nontronite were chosen as our Mars analog minerals. ~20 mg of analog Mars minerals with 5µl of 50% H2O2, and were either run immediately or placed in a sealed tube for 2, 4, or 9 days to look for changes over time with two reps being done at each time step to determine repeatability. Each sample was heated from -60 °C to 500 °C at 20 °C/min and the evolved gases were monitored with a mass spectrometer. Each sample was also analyzed with an X-ray diffraction instrument to look for changes in mineralogy.Preliminary results show three potential outcomes: 1) peroxide has no effect on the sample (e.g., hematite), 2) the mineral is unaffected but catalyzes peroxide decomposition (magnetite, siderite), or 3) peroxide alters the mineral (pyrrhotite, San Carlos olivine).

  12. Effects of Martian Surface Materials on the Thermal Decomposition of Hydrogen Peroxide

    Science.gov (United States)

    Archer, P. D., Jr.

    2017-01-01

    While hydrogen peroxide (H2O2) has been detected in the martian atmosphere, it has not been detected in surface materials. Since the Viking lander mission, we have sent instruments to Mars with the capability to detect H2O2. The Sample Analysis at Mars (SAM) instrument onboard the Curiosity Rover and Thermal and Evolved Gas Analyzer (TEGA) instrument on the Phoenix lander both detected water and oxygen releases from analyzed sediments but whether or not peroxide could be the source of these gases has not been investigated. We are investigating the possible presence of H2O2 in martian materials by analyzing Mars-relevant minerals that have been mixed with hydrogen peroxide using lab instruments configured as analogs to Mars mission instruments. The object of this research is to use lab instruments to find the effects of Mars analog minerals on hydrogen peroxide gas release temperatures, specifically gas releases of water and oxygen and also determine the effect of the peroxide on the minerals. Data that we get from the lab can then be compared to the data collected from Mars. The minerals hematite, siderite, San Carlos olivine, magnetite and nontronite were chosen as our Mars analog minerals. 20 mg of analog Mars minerals with 5µl of 50% H2O2, and were either run immediately or placed in a sealed tube for 2, 4, or 9 days to look for changes over time with two reps being done at each time step to determine repeatability. Each sample was heated from -60 degC to 500 degC at 20 degC/min and the evolved gases were monitored with a mass spectrometer. Each sample was also analyzed with an X-ray diffraction instrument to look for changes in mineralogy. Preliminary results show three potential outcomes: 1) peroxide has no effect on the sample (e.g., hematite), 2) the mineral is unaffected but catalyzes peroxide decomposition (magnetite, siderite), or 3) peroxide alters the mineral (pyrrhotite, San Carlos olivine).

  13. Deformation due to mechanical and thermal sources in generalised ...

    Indian Academy of Sciences (India)

    R. Narasimhan (Krishtel eMaging) 1461 1996 Oct 15 13:05:22

    dimensional problem of thermoelasticity has been considered to investigate the disturbance due to mechanical (horizontal or verti- cal) and thermal source in a homogeneous, thermally conducting orthorhombic material. Laplace–Fourier ...

  14. Thermal Decomposition Characteristics of Orthorhombic Ammonium Perchlorate (o-AP) and an 0-AP/HTPB-Based Propellant

    Energy Technology Data Exchange (ETDEWEB)

    BEHRENS JR.,RICHARD; MINIER,LEANNA M.G.

    1999-10-25

    A study to characterize the low-temperature reactive processes for o-AP and an AP/HTPB-based propellant (class 1.3) is being conducted in the laboratory using the techniques of simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS) and scanning electron microscopy (SEM). The results presented in this paper are a follow up of the previous work that showed the overall decomposition to be complex and controlled by both physical and chemical processes. The decomposition is characterized by the occurrence of one major event that consumes up to {approx}35% of the AP, depending upon particle size, and leaves behind a porous agglomerate of AP. The major gaseous products released during this event include H{sub 2}O, O{sub 2}, Cl{sub 2}, N{sub 2}O and HCl. The recent efforts provide further insight into the decomposition processes for o-AP. The temporal behaviors of the gas formation rates (GFRs) for the products indicate that the major decomposition event consists of three chemical channels. The first and third channels are affected by the pressure in the reaction cell and occur at the surface or in the gas phase above the surface of the AP particles. The second channel is not affected by pressure and accounts for the solid-phase reactions characteristic of o-AP. The third channel involves the interactions of the decomposition products with the surface of the AP. SEM images of partially decomposed o-AP provide insight to how the morphology changes as the decomposition progresses. A conceptual model has been developed, based upon the STMBMS and SEM results, that provides a basic description of the processes. The thermal decomposition characteristics of the propellant are evaluated from the identities of the products and the temporal behaviors of their GFRs. First, the volatile components in the propellant evolve from the propellant as it is heated. Second, the hot AP (and HClO{sub 4}) at the AP-binder interface oxidize the binder through reactions that

  15. Mechanism of decomposition of the human defense factor hypothiocyanite near physiological pH.

    Science.gov (United States)

    Kalmár, József; Woldegiorgis, Kelemu L; Biri, Bernadett; Ashby, Michael T

    2011-12-14

    Relatively little is known about the reaction chemistry of the human defense factor hypothiocyanite (OSCN(-)) and its conjugate acid hypothiocyanous acid (HOSCN), in part because of their instability in aqueous solutions. Herein we report that HOSCN/OSCN(-) can engage in a cascade of pH- and concentration-dependent comproportionation, disproportionation, and hydrolysis reactions that control its stability in water. On the basis of reaction kinetic, spectroscopic, and chromatographic methods, a detailed mechanism is proposed for the decomposition of HOSCN/OSCN(-) in the range of pH 4-7 to eventually give simple inorganic anions including CN(-), OCN(-), SCN(-), SO(3)(2-), and SO(4)(2-). Thiocyanogen ((SCN)(2)) is proposed to be a key intermediate in the hydrolysis; and the facile reaction of (SCN)(2) with OSCN(-) to give NCS(═O)SCN, a previously unknown reactive sulfur species, has been independently investigated. The mechanism of the aqueous decomposition of (SCN)(2) around pH 4 is also reported. The resulting mechanistic models for the decomposition of HOSCN and (SCN)(2) address previous empirical observations, including the facts that the presence of SCN(-) and/or (SCN)(2) decreases the stability of HOSCN/OSCN(-), that radioisotopic labeling provided evidence that under physiological conditions decomposing OSCN(-) is not in equilibrium with (SCN)(2) and SCN(-), and that the hydrolysis of (SCN)(2) near neutral pH does not produce OSCN(-). Accordingly, we demonstrate that, during the human peroxidase-catalyzed oxidation of SCN(-), (SCN)(2) cannot be the precursor of the OSCN(-) that is produced. © 2011 American Chemical Society

  16. Degradation mechanism and thermal stability of urea nitrate below the melting point

    Energy Technology Data Exchange (ETDEWEB)

    Desilets, Sylvain, E-mail: sylvain.desilets@drdc-rddc.gc.ca [Defence R and D Canada, Valcartier, 2459 Pie-XI Blvd North, Val-Belair, Quebec, Canada G3J 1X5 (Canada); Brousseau, Patrick; Chamberland, Daniel [Defence R and D Canada, Valcartier, 2459 Pie-XI Blvd North, Val-Belair, Quebec, Canada G3J 1X5 (Canada); Singh, Shanti; Feng, Hongtu; Turcotte, Richard [Canadian Explosives Research Laboratory, 1 Haanel Dr. Ottawa, Quebec, Canada K1A 1M1 (Canada); Anderson, John [Defence R and D Canada, Suffield, Box 4000, stn Main, Medicine Hat, Alberta, Canada T1A 8K6 (Canada)

    2011-07-10

    Highlights: {yields} Decomposition mechanism of urea nitrate. {yields} Spectral characterization of the decomposition mechanism. {yields} Thermal stability of urea nitrate at 50, 70 and 100 {sup o}C. {yields} Chemical balance of decomposed products released. - Abstract: Aging and degradation of urea nitrate below the melting point, at 100 {sup o}C, was studied by using thermal analysis and spectroscopic methods including IR, Raman, {sup 1}H and {sup 13}C NMR techniques. It was found that urea nitrate was completely degraded after 72 h at 100 {sup o}C into a mixture of solids (69%) and released gaseous species (31%). The degradation mechanism below the melting point was clearly identified. The remaining solid mixture was composed of ammonium nitrate, urea and biuret while unreacted residual nitric and isocyanic acids as well as traces of ammonia were released as gaseous species at 100 {sup o}C. The thermal stability of urea nitrate, under extreme storage conditions (50 {sup o}C), was also examined by isothermal nano-calorimetry.

  17. Preparation and thermal decomposition of copper(II, zinc(II and cadmium(II chelates with 8-hydroxyquinoline

    Directory of Open Access Journals (Sweden)

    Crespi Marisa S.

    1999-01-01

    Full Text Available When the compounds are heated in an inert atmosphere it can be verified the consecutive partial sublimation, fusion, partial volatilization and partial thermal decomposition of the anhydrous complexes. When in an oxidating atmosphere the above process is only verified to Cu(II chelates. Anhydrous copper(II complexes present a monoclinic structure in the b form and the volatilized compound in a a form. Zinc(II and cadmium(II hydrated complexes are isomorphous and they present different cell dimensions from those reported previously.

  18. Thermal behavior and decomposition of cerium(III) butanoate, pentanoate and hexanoate salts upon heating in argon

    DEFF Research Database (Denmark)

    Grivel, Jean-Claude; Suarez Guevara, Maria Josefina; Yue, Zhao

    2017-01-01

    The thermal behavior and decomposition of Ce-butanoate monohydrate (Ce(C3H7CO2)3·H2O), Ce-pentanoate (Ce(C4H9CO2)3) and Ce-hexanoate (Ce(C5H11CO2)3) were studied in a flow of argon while heating at 5 °C/min. By means of several techniques such as simultaneous TG-DTA, FTIR evolved gas analysis, in...

  19. Kinetics and mechanism of the exothermic first-stage decomposition reaction of 1,3-bis(2,2,2-trinitroethyl)-1,3-diazacyclopentanone-2.

    Science.gov (United States)

    Rong-zu, Hu; De-suo, Yang; Sheng-li, Gao; San-ping, Chen; Hong-an, Zhao; Qi-zhen, Shi

    2003-08-29

    The thermal behavior, mechanism and kinetic parameters of the exothermic first-stage decomposition reaction of the title compound in a temperature-programmed mode have been investigated by means of DSC, TG-DTG and IR. The reaction mechanism was proposed. The kinetic model function in differential form, apparent activation energy (E(a)) and pre-exponential factor (A) of this reaction are (1-alpha)(2), 178.41 kJ mol(-1) and 10(17.06)s(-1), respectively. The critical temperature of thermal explosion of the compound is 184.99 degrees C. The values of DeltaS( not equal ), DeltaH( not equal ) and DeltaG( not equal ) of this reaction are 91.54 J mol(-1)K(-1), 176.86 kJ mol(-1) and 135.83 kJ mol(-1), respectively.

  20. Thermal decomposition of solder flux activators under simulated wave soldering conditions

    DEFF Research Database (Denmark)

    Piotrowska, Kamila; Jellesen, Morten Stendahl; Ambat, Rajan

    2017-01-01

    Purpose:The aim of this work is to investigate the decomposition behaviour of the activator species commonly used in the wave solder no-clean flux systems and to estimate the residue amount left after subjecting the samples to simulated wave soldering conditions. Design/methodology/approach: Chan......Purpose:The aim of this work is to investigate the decomposition behaviour of the activator species commonly used in the wave solder no-clean flux systems and to estimate the residue amount left after subjecting the samples to simulated wave soldering conditions. Design......-malic). The decomposition patterns of solder flux activators depend on their chemical nature, time of heat exposure and substrate materials. Evaporation of the residue from the surface of different materials (laminate with solder mask, copper surface or glass surface) was found to be more pronounced for succinic...

  1. Decomposition mechanisms of trinitroalkyl compounds: a theoretical study from aliphatic to aromatic nitro compounds.

    Science.gov (United States)

    Fayet, Guillaume; Rotureau, Patricia; Minisini, Benoit

    2014-04-14

    The chemical mechanisms involved in the decomposition of trinitroethyl compounds were studied for both aliphatic and aromatic derivatives using density functional theory calculations. At first, in the case of 1,1,1-trinitrobutane, used as a reference molecule, two primary channels were highlighted among the five investigated ones: the breaking of the C-N bond and the HONO elimination. Then, the influence of various structural parameters was studied for these two reactions by changing the length of the carbon chain, adding substituents or double bonds along the carbon chain. If some slight changes in activation energies were observed for most of these features, no modification of the competition between the two investigated reactions was highlighted and the breaking of the C-N bond remained the favoured mechanism. At last, the reactions involving the trinitroalkyl fragments were highlighted to be more competitive than reactions involving nitro groups linked to aromatic cycles in two aromatic systems (4-(1,1,1-trinitrobutyl)-nitrobenzene and 2-(1,1,1-trinitrobutyl)-nitrobenzene). This showed that aromatic nitro compounds with trinitroalkyl derivatives decompose from their alkyl part and may be considered more likely as aliphatic than as aromatic regarding the initiation of their decomposition process.

  2. Non-Thermal Plasma Combined with Cordierite-Supported Mn and Fe Based Catalysts for the Decomposition of Diethylether

    Directory of Open Access Journals (Sweden)

    Quang Hung Trinh

    2015-04-01

    Full Text Available The removal of dilute diethylether (DEE, concentration: 150 ppm from an air stream (flow rate: 1.0 L min−1 using non-thermal plasma combined with different cordierite-supported catalysts, including Mn, Fe, and mixed Mn-Fe oxides, was investigated. The experimental results showed that the decomposition of DEE occurred in a one-stage reactor without the positive synergy of plasma and supported catalysts, by which ca. 96% of DEE was removed at a specific input energy (SIE of ca. 600 J L−1, except when the mixed Mn-Fe/cordierite was used. Among the catalysts that were examined, Mn-Fe/cordierite, the catalyst that was the most efficient at decomposing ozone was found to negatively affect the decomposition of DEE in the one-stage reactor. However, when it was utilized as a catalyst in the post-plasma stage of a two-part hybrid reactor, in which Mn/cordierite was directly exposed to the plasma, the reactor performance in terms of DEE decomposition efficiency was improved by more than 10% at low values of SIE compared to the efficiency that was achieved without Mn-Fe/cordierite. The ozone that was formed during the plasma stage and its subsequent catalytic dissociation during the post-plasma stage to produce atomic oxygen therefore played important roles in the removal of DEE.

  3. ESR studies on the thermal decomposition of trimethylamine oxide to formaldehyde and dimethylamine in jumbo squid (Dosidicus gigas) extract.

    Science.gov (United States)

    Zhu, Junli; Jia, Jia; Li, Xuepeng; Dong, Liangliang; Li, Jianrong

    2013-12-15

    The effects of ferrous iron, heating temperature and different additives on the decomposition of trimethylamine oxide (TMAO) to formaldehyde (FA) and dimethylamine (DMA) and generation of free radicals in jumbo squid (Dosidicus gigas) extract during heating were evaluated by electron spin resonance (ESR). The thermal decomposition of TMAO to TMA, DMA and FA and free radical signals was observed in squid extract, whereas no DMA, FA and free radical signals were detected in cod extract or in aqueous TMAO solution in vitro at high temperatures. Significant increase in levels of DMA, FA and radicals intensity were observed in squid extract and TMAO solution in the presence of ferrous iron with increasing temperature. Hydrogen peroxide stimulated the production of DMA, FA and ESR signals in squid extract, while citric acid, trisodium citrate, calcium chloride, tea polyphenols and resveratrol had the opposite effect. Similar ESR spectra of six peaks regarded as amminium radical were detected in the squid extract and TMAO-iron(II) solution, suggesting that the amminium radical was involved in the decomposition of TMAO. Copyright © 2013 Elsevier Ltd. All rights reserved.

  4. A theoretical study of the decomposition mechanisms in substituted o-nitrotoluenes.

    Science.gov (United States)

    Fayet, Guillaume; Joubert, Laurent; Rotureau, Patricia; Adamo, Carlo

    2009-12-03

    The pathways corresponding to the most energetically favorable decomposition reactions that can be envisaged for o-nitrotoluene (and 20 of its derivatives) have been studied, using density functional theory, in order to evaluate the influence of substituents' nature (nitro, methyl, amino, carboxylic acid, and hydroxyl) and position. The first mechanism consists of the direct dissociation (homolysis) of the carbon nitrogen bond (CH(3)C(6)H(4)NO(2) = CH(3)C(6)H(4) + NO(2)) whereas the second one is a more complex process initiated by C-H alpha attack and leading to the formation of anthranil and water (C(6)H(4)C(H)ON + H(2)O). For each compound, the initial step of this last channel is the rate limiting one, the Gibbs activation energy of all systems being very close, that is all in the 40-44 kcal/mol range. More important variations have been observed for the C-NO(2) homolysis Gibbs activation energies (46-60 kcal/mol). These variations have been related to electron donor-acceptor properties of substituents by considering significant correlations (R(2) > 0.9) with the Hammett parameters (sigma). Nevertheless, though the influence of substituents on the direct breaking of the C-NO(2) bond was important, the C-H alpha attack remained finally the major decomposition channel for the studied compounds. Our study underlines the complexity of the decomposition process in nitroaromatic compounds and casts some doubts on the characterization of the energetic properties of such molecules only on the basis of C-NO(2) homolysis.

  5. Kinetic modeling of thermal decomposition of zinc ferrite from neutral leach residues based on stochastic geometric model

    Energy Technology Data Exchange (ETDEWEB)

    Janković, Bojan, E-mail: bojanjan@ffh.bg.ac.rs [Faculty of Physical Chemistry, Department for Dynamics and Matter Structure, University of Belgrade, Studentski trg 12-16, P.O. Box 137, 11001 Belgrade (Serbia); Stopić, Srećko; Güven, Aybars; Friedrich, Bernd [IME Process Metallurgy and Metal Recycling, RWTH Aachen University, Aachen (Germany)

    2014-05-01

    The stochastic geometric model was applied to kinetic modeling the complex process of thermal decomposition of zinc ferrite from neutral leach residues, at different operating temperatures (600 °C, 750 °C, 950 °C and 1150 °C). Based on functional dependence of Avrami's constant (n) in a function of the effective activation energy (E{sub a}), it was found that at T>950 °C, the crystallization process takes place in autocatalytic stage, under the conditions where the rate of nucleation rapidly increases. It was established that the high nucleation rate can be attributed to formation of both Zn and Fe rich regions which provide a high number of heterogeneous nucleation sites. Based on the obtained final shape of the particles, it was found a strong presence of zinc, iron (present only in the form of Fe{sub 3}O{sub 4} (magnetite)), magnesium (in the form of Mg{sub 2}Si{sub 2}O{sub 6}), and also lead oxides. Thermodynamic analysis showed that the decomposition depends on the introduction of heat, and exerts a positive value of the Gibbs free energy of activation. Such a feature was expected since the ferrite system has been submitted to a forced decomposition and volatilization reactions. - Highlights: • Thermo-chemical investigations. • Autocatalytic stage of process, where the rate of nucleation rapidly increases. • Iron is present in the form of Fe{sub 3}O{sub 4} (magnetite). • The possibility of preparing of the nanosized magnetic particles. • Final product which underwent decomposition has the magnetic properties.

  6. Investigating the thermal decomposition of starch and cellulose in model systems and toasted bread using domino tandem mass spectrometry.

    Science.gov (United States)

    Golon, Agnieszka; González, Francisco Javier; Dávalos, Juan Z; Kuhnert, Nikolai

    2013-01-23

    Many dietary products containing polysaccharides, mostly starch and cellulose, are processed by thermal treatment. Similarly to the formation of caramel from mono- and disaccharides, the chemical structure of the carbohydrates is dramatically altered by heat treatment. This contribution investigates the products of thermal decomposition of pure starch and cellulose as model systems followed by an investigation of bread obtained at comparable conditions using a combination of modern mass spectrometry techniques. From both starch and cellulose, dehydrated oligomers of glucose and dehydrated glucose have been predominately observed, with oligomers of more than four glucose moieties dominating. Moreover, disproportionation and oligomers with up to six carbohydrates units are formed through unselective glycosidic bond breakage. MALDI-MS data confirm the presence of the majority of products in toasted bread.

  7. Scattering Mechanism Extraction by a Modified Cloude-Pottier Decomposition for Dual Polarization SAR

    Directory of Open Access Journals (Sweden)

    Kefeng Ji

    2015-06-01

    Full Text Available Dual polarization is a typical operational mode of polarimetric synthetic aperture radar (SAR. However, few studies have considered the scattering mechanism extraction of dual-polarization SARs. A modified Cloude-Pottier decomposition is proposed to investigate the performance of the scattering mechanism extraction of dual-polarization SARs. It is theoretically demonstrated that only HH-VV SAR can discriminate the three canonical scattering mechanisms from an isotropic surface, horizontal dipole, and isotropic dihedral. Various experiments are conducted using 21 scenes from real datasets acquired by AIRSAR, Convair-580 SAR, EMISAR, E-SAR, Pi-SAR, and RADARSAT-2. Division of the dual-polarization H-α plane is experimentally obtained. The lack of cross-polarization induces the diffusion of scattering mechanisms and their overlap in the HH-VV H-α plane. However, the performance of HH-VV SAR for extracting scattering mechanisms is acceptable. Thus, HH-VV SAR is a suitable alternative to full-polarization SAR in certain cases. Meanwhile, the extraction performance of the other two dual-polarization SARs is badly degraded due to the lack of co-polarization. Therefore, HH-HV and HV-VV SARs cannot effectively extract the scattering mechanisms in the H-α plane.

  8. Mechanical properties of thermal protection system materials.

    Energy Technology Data Exchange (ETDEWEB)

    Hardy, Robert Douglas; Bronowski, David R.; Lee, Moo Yul; Hofer, John H.

    2005-06-01

    An experimental study was conducted to measure the mechanical properties of the Thermal Protection System (TPS) materials used for the Space Shuttle. Three types of TPS materials (LI-900, LI-2200, and FRCI-12) were tested in 'in-plane' and 'out-of-plane' orientations. Four types of quasi-static mechanical tests (uniaxial tension, uniaxial compression, uniaxial strain, and shear) were performed under low (10{sup -4} to 10{sup -3}/s) and intermediate (1 to 10/s) strain rate conditions. In addition, split Hopkinson pressure bar tests were conducted to obtain the strength of the materials under a relatively higher strain rate ({approx}10{sup 2} to 10{sup 3}/s) condition. In general, TPS materials have higher strength and higher Young's modulus when tested in 'in-plane' than in 'through-the-thickness' orientation under compressive (unconfined and confined) and tensile stress conditions. In both stress conditions, the strength of the material increases as the strain rate increases. The rate of increase in LI-900 is relatively small compared to those for the other two TPS materials tested in this study. But, the Young's modulus appears to be insensitive to the different strain rates applied. The FRCI-12 material, designed to replace the heavier LI-2200, showed higher strengths under tensile and shear stress conditions. But, under a compressive stress condition, LI-2200 showed higher strength than FRCI-12. As far as the modulus is concerned, LI-2200 has higher Young's modulus both in compression and in tension. The shear modulus of FRCI-12 and LI-2200 fell in the same range.

  9. Mechanical, Hygric and Thermal Properties of Flue Gas Desulfurization Gypsum

    Directory of Open Access Journals (Sweden)

    P. Tesárek

    2004-01-01

    Full Text Available The reference measurements of basic mechanical, thermal and hygric parameters of hardened flue gas desulfurization gypsum are carried out. Moisture diffusivity, water vapor diffusion coefficient, thermal conductivity, volumetric heat capacity and linear thermal expansion coefficient are determined with the primary aim of comparison with data obtained for various types of modified gypsum in the future. 

  10. Multispectral linear array (MLA) focal plane mechanical and thermal design

    Science.gov (United States)

    Mitchell, A. S.; Kaminski, E. F.

    1982-01-01

    The mechanical and thermal design of an integrated focal plane subsystem of a Multispectral Linear Array (MLA) instrument is discussed in terms of focal-plane alignment, thermoelastic performance, and thermal requirements. The modular construction and thermal control of the focal plane array are discussed.

  11. Comparison of the thermal decomposition processes of several aminoalcohol-based ZnO inks with one containing ethanolamine

    Energy Technology Data Exchange (ETDEWEB)

    Gómez-Núñez, Alberto [University of Barcelona, Department of Electronics, Martí i Franquès 1, E08028-Barcelona (Spain); Roura, Pere [University of Girona, Department of Physics, Campus Montilivi, Edif. PII, E17071-Girona, Catalonia (Spain); López, Concepción [University of Barcelona, Department of Inorganic Chemistry, Martí i Franquès 1, E08028-Barcelona (Spain); Vilà, Anna, E-mail: avila@el.ub.edu [University of Barcelona, Department of Electronics, Martí i Franquès 1, E08028-Barcelona (Spain)

    2016-09-15

    Highlights: • Four alternatives to ethanolamine as stabilizer for the chemical synthesis of ZnO with zinc acetate dihydrate are proposed: aminopropanol, aminomethyl butanol, aminophenol and aminobenzyl alcohol. • Thermal decomposition processes described. Nitrogen cyclic compounds result. • Molecule flexibility helps decomposition, and in particular aliphatic aminoalcohols (quite flexible) decompose the precursor at lower temperatures than aromatic ones (more rigid). • Aminopropanol, aminomethyl butanol and aminobenzyl crystallize ZnO at a lower temperature than ethanolamine. • Nitrogen cyclic specimens have been identified and evolve in all cases (included ethanolamine) at temperatures up to 600 °C. - Abstract: Four inks for the production of ZnO semiconducting films have been prepared with zinc acetate dihydrate as precursor salt and one among the following aminoalcohols: aminopropanol (APr), aminomethyl butanol (AMB), aminophenol (APh) and aminobenzyl alcohol (AB) as stabilizing agent. Their thermal decomposition process has been analyzed in situ by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and evolved gas analysis (EGA), whereas the solid product has been analysed ex-situ by X-ray diffraction (XRD) and infrared spectroscopy (IR). Although, except for the APh ink, crystalline ZnO is already obtained at 300 °C, the films contain an organic residue that evolves at higher temperature in the form of a large variety of nitrogen-containing cyclic compounds. The results indicate that APr can be a better stabilizing agent than ethanolamine (EA). It gives larger ZnO crystal sizes with similar carbon content. However, a common drawback of all the amino stabilizers (EA included) is that nitrogen atoms have not been completely removed from the ZnO film at the highest temperature of our experiments (600 °C).

  12. Nickel Oxide (NiO nanoparticles prepared by solid-state thermal decomposition of Nickel (II schiff base precursor

    Directory of Open Access Journals (Sweden)

    Aliakbar Dehno Khalaji

    2015-06-01

    Full Text Available In this paper, plate-like NiO nanoparticles were prepared by one-pot solid-state thermal decomposition of nickel (II Schiff base complex as new precursor. First, the nickel (II Schiff base precursor was prepared by solid-state grinding using nickel (II nitrate hexahydrate, Ni(NO32∙6H2O, and the Schiff base ligand N,N′-bis-(salicylidene benzene-1,4-diamine for 30 min without using any solvent, catalyst, template or surfactant. It was characterized by Fourier Transform Infrared spectroscopy (FT-IR and elemental analysis (CHN. The resultant solid was subsequently annealed in the electrical furnace at 450 °C for 3 h in air atmosphere. Nanoparticles of NiO were produced and characterized by X-ray powder diffraction (XRD at 2θ degree 0-140°, FT-IR spectroscopy, scanning electron microscopy (SEM and transmission electron microscopy (TEM. The XRD and FT-IR results showed that the product is pure and has good crystallinity with cubic structure because no characteristic peaks of impurity were observed, while the SEM and TEM results showed that the obtained product is tiny, aggregated with plate-like shape, narrow size distribution with an average size between 10-40 nm. Results show that the solid state thermal decomposition method is simple, environmentally friendly, safe and suitable for preparation of NiO nanoparticles. This method can also be used to synthesize nanoparticles of other metal oxides.

  13. Reaction mechanism of ethylene glycol decomposition on Pt model catalysts: A density functional theory study

    Energy Technology Data Exchange (ETDEWEB)

    Lv, Cun-Qin [College of Chemistry and Environmental Engineering, Shanxi Datong University, Datong 037009, Shanxi Province (China); Department of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin 300071 (China); Yang, Bo; Pang, Xian-Yong [College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan, 030024 (China); Wang, Gui-Chang, E-mail: wangguichang@nankai.edu.cn [Department of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin 300071 (China)

    2016-12-30

    Highlights: • DFT calculations were performed to study the ethylene glycol decomposition on Pt. • The final products are CO and H{sub 2} on Pt(111), (100) and (211). • Ethylene glycol decomposition on Pt(111) undergoes via initial O−H bond scission and followed by C−H bond cleavage. • Ethylene glycol decomposition proceeds via initial O−H bond scission and followed by O−H bond cleavage on Pt(100)/(211). - Abstract: Understanding and controlling bond beak sequence is important in catalytic processes. The DFT-GGA method combined with slab model was performed to study the ethylene glycol decomposition on various Pt model catalysts such as close-packed Pt(111), stepped Pt(211) and a more open one, Pt(100). Calculation results show that the adsorption energies of ethylene glycol and other decomposition species depend on the coordination number of surface atom, that is, low coordination number correspond to high adsorption energy. Moreover, it was found that final products of ethylene glycol decomposition are CO and H{sub 2} on all model catalysts, but the reaction mechanism varies: On Pt(111), the first step is O−H bond scission, followed by C−H bond cleavage, namely C{sub 2}H{sub 6}O{sub 2} → HOCH{sub 2}CH{sub 2}O + H → HOCH{sub 2}CHO + 2H→ HOCH{sub 2}CO +3H → OCH{sub 2}CO + 4H → OCHCO + 5H → CO + HCO + 5H → 2CO + 6H→ 2CO + 3H{sub 2}; On Pt(211) and Pt(100), however, it is a second O−H bond cleavage that follows the initial O−H bond scission, that is, C{sub 2}H{sub 6}O{sub 2} → HOCH{sub 2}CH{sub 2}O + H → OCH{sub 2}CH{sub 2}O + 2H → OCHCH{sub 2}O + 3H → OCHCHO + 4H → 2HCO + 4H → 2CO + 6H → 2CO + 3H{sub 2}  on Pt(211), and C{sub 2}H{sub 6}O{sub 2} →HOCH{sub 2}CH{sub 2}O+ H → OCH{sub 2}CH{sub 2}O + 2H→OCHCH{sub 2}O+3H→OCCH{sub 2}O+4H→CO+H{sub 2}CO+4H→CO+HCO+5H→2CO+6H→2CO+3H{sub 2} on Pt(100) For the catalytic order of ethylene glycol to form H{sub 2}, it may be determined based on the rate

  14. Decomposition mechanism of melamine borate in pyrolytic and thermo-oxidative conditions

    Energy Technology Data Exchange (ETDEWEB)

    Hoffendahl, Carmen; Duquesne, Sophie; Fontaine, Gaëlle; Bourbigot, Serge, E-mail: serge.bourbigot@ensc-lille.fr

    2014-08-20

    Highlights: • Decomposition of melamine borate in pyrolytic and thermo-oxidative conditions was investigated. • With increasing temperature, orthoboric acid forms boron oxide releasing water. • Melamine decomposes evolving melamine, ammonia and other fragments. • Boron oxide is transformed into boron nitride and boron nitride-oxide structures through presence of ammonia. - Abstract: Decomposition mechanism of melamine borate (MB) in pyrolytic and thermo-oxidative conditions is investigated in the condensed and gas phases using solid state NMR ({sup 13}C and {sup 11}B), X-ray photoelectron spectroscopy (XPS), pyrolysis-gas chromatography–mass spectrometry (py-GCMS) and thermogravimetric analysis coupled with a Fourier transform infrared spectrometer (TGA–FTIR). It is evidenced that orthoboric acid dehydrates to metaboric and then to boron oxide. The melamine is partially sublimated. At the same time, melamine condensates, i.e., melem and melon are formed. Melon is only formed in thermo-oxidative conditions. At higher temperature, melem and melon decompose releasing ammonia which reacts with the boron oxide to form boron nitride (BN) and BNO structures.

  15. Representing Matrix Cracks Through Decomposition of the Deformation Gradient Tensor in Continuum Damage Mechanics Methods

    Science.gov (United States)

    Leone, Frank A., Jr.

    2015-01-01

    A method is presented to represent the large-deformation kinematics of intraply matrix cracks and delaminations in continuum damage mechanics (CDM) constitutive material models. The method involves the additive decomposition of the deformation gradient tensor into 'crack' and 'bulk material' components. The response of the intact bulk material is represented by a reduced deformation gradient tensor, and the opening of an embedded cohesive interface is represented by a normalized cohesive displacement-jump vector. The rotation of the embedded interface is tracked as the material deforms and as the crack opens. The distribution of the total local deformation between the bulk material and the cohesive interface components is determined by minimizing the difference between the cohesive stress and the bulk material stress projected onto the cohesive interface. The improvements to the accuracy of CDM models that incorporate the presented method over existing approaches are demonstrated for a single element subjected to simple shear deformation and for a finite element model of a unidirectional open-hole tension specimen. The material model is implemented as a VUMAT user subroutine for the Abaqus/Explicit finite element software. The presented deformation gradient decomposition method reduces the artificial load transfer across matrix cracks subjected to large shearing deformations, and avoids the spurious secondary failure modes that often occur in analyses based on conventional progressive damage models.

  16. Pressurizer with a mechanically attached surge nozzle thermal sleeve

    Science.gov (United States)

    Wepfer, Robert M

    2014-03-25

    A thermal sleeve is mechanically attached to the bore of a surge nozzle of a pressurizer for the primary circuit of a pressurized water reactor steam generating system. The thermal sleeve is attached with a series of keys and slots which maintain the thermal sleeve centered in the nozzle while permitting thermal growth and restricting flow between the sleeve and the interior wall of the nozzle.

  17. Synthesis, mechanical, thermal and chemical properties of ...

    Indian Academy of Sciences (India)

    Cardanol, an excellent monomer for polymer production, has been isolated from CNSL and allowed to react with formaldehyde in a particular mole ratio in the presence of glutaric acid catalyst to give ... Differential thermal analysis (DTA) and thermo-gravimetric analysis (TGA) were undertaken for thermal characterization.

  18. Thermal decomposition of energetic materials. 2. Deuterium isotope effects and isotopic scrambling in condensed-phase decomposition of octahydro-1,3,5,7-tetranitro- 1,3,5,7-tetrazocine. (Reannouncement with new availability information)

    Energy Technology Data Exchange (ETDEWEB)

    Behrens, R.; Bulusu, S.

    1991-12-31

    The products formed in the thermal decomposition of octahydro-1,3,5,7-tetranitro- 1,3,5,7-tetrazocine (HMX) have been traced by using mixtures of different isotopically labeled analogues of HMX. The fraction of isotropic scrambling and the extent of the deuterium kinetic isotope effect (DKIE) are reported for the different thermal decomposition products. Isotropic scrambling is not observed for the N-Nbond in N2O and the C-H bonds in CH2O. Only one of the C-N bonds in N-methylformamide (NMFA) undergoes isotropic scrambling. The lack of complete isotopic scrambling of the N-NO bond in 1-nitroso-3,5-7-trinitro- 1,3,5,7-tetrazocine (ONTNTA) is shown to imply that some HMX decomposition occurs in the lattice. The behavior of the DKIE in different mixtures of isotopic analogues of HMX suggests that water probably acts as a catalyst in the decomposition. The results demonstrate that decomposition of HMX in the condensed phase has several reaction branches.

  19. Molecular dynamics studies of the thermal decomposition of 2,3-diazabicyclo(2.2.1)hept-2-ene

    Science.gov (United States)

    Sorescu, Dan C.; Thompson, Donald L.; Raff, Lionel M.

    1995-05-01

    The reaction dynamics of the thermal gas-phase decomposition of 2,3-diazabicyclo (2.2.1)hept-2-ene-exo, exo-5,6-d2 have been investigated using classical trajectory methods on a semiempirical potential-energy surface. The global potential is written as a superposition of different reaction channel potentials containing bond stretching, bending and torsional terms, connected by parametrized switching functions. Reaction channels for stepwise and concerted cleavage of the two C-N bonds of the reactant have both been considered in construction of the potential. The geometries of 2,3-diazabicyclo(2.2.1)hept-2-ene, the diazenyl biradical and of the transition state corresponding to breaking of the remaining C-N bond of diazenyl biradical have been determined at the second order Möller-Plesset perturbation theory (MP2/6-31G*) and at Hartree-Fock (HF/6-31G*) levels, respectively. The bond dissociation energies have been estimated using the available thermochemical data and previously reported results for bicyclo(2.1.0)pentane [J. Chem. Phys. 101, 3729 (1994)]. The equilibrium geometries predicted by the semiempirical potential for reactants and products, the barrier height for thermal nitrogen extrusion from 2,3-diazabicyclo(2.2.1)hept-2-ene and the fundamental vibrational frequencies are in good to excellent agreement with the measured or ab initio calculated values. Using a projection method of the instantaneous Cartesian velocities onto the normal mode vectors and classical trajectory calculations, the dissociation dynamics of 2,3-diazabicyclo(2.2.1)hept-2-ene-exo, exo-5,6-d2 are investigated at several excitation energies in the range 60-175 kcal/mol. The results show the following: (1) The thermal reaction takes place with a preference for inversion of configuration in the reaction products, the exo-labeled bicyclo(2.1.0) pentane being the major product. The exo/endo ratio of bicyclo(2.1.0) pentane isomers is found to vary between 1.8-2.2 for the energy range

  20. Adomian Decomposition Method for a Nonlinear Heat Equation with Temperature Dependent Thermal Properties

    Directory of Open Access Journals (Sweden)

    Ashfaque H. Bokhari

    2009-01-01

    Full Text Available The solutions of nonlinear heat equation with temperature dependent diffusivity are investigated using the modified Adomian decomposition method. Analysis of the method and examples are given to show that the Adomian series solution gives an excellent approximation to the exact solution. This accuracy can be increased by increasing the number of terms in the series expansion. The Adomian solutions are presented in some situations of interest.

  1. A Continuum Damage Mechanics Model to Predict Kink-Band Propagation Using Deformation Gradient Tensor Decomposition

    Science.gov (United States)

    Bergan, Andrew C.; Leone, Frank A., Jr.

    2016-01-01

    A new model is proposed that represents the kinematics of kink-band formation and propagation within the framework of a mesoscale continuum damage mechanics (CDM) model. The model uses the recently proposed deformation gradient decomposition approach to represent a kink band as a displacement jump via a cohesive interface that is embedded in an elastic bulk material. The model is capable of representing the combination of matrix failure in the frame of a misaligned fiber and instability due to shear nonlinearity. In contrast to conventional linear or bilinear strain softening laws used in most mesoscale CDM models for longitudinal compression, the constitutive response of the proposed model includes features predicted by detailed micromechanical models. These features include: 1) the rotational kinematics of the kink band, 2) an instability when the peak load is reached, and 3) a nonzero plateau stress under large strains.

  2. Molecular Theory of Detonation Initiation: Insight from First Principles Modeling of the Decomposition Mechanisms of Organic Nitro Energetic Materials

    Directory of Open Access Journals (Sweden)

    Roman V. Tsyshevsky

    2016-02-01

    Full Text Available This review presents a concept, which assumes that thermal decomposition processes play a major role in defining the sensitivity of organic energetic materials to detonation initiation. As a science and engineering community we are still far away from having a comprehensive molecular detonation initiation theory in a widely agreed upon form. However, recent advances in experimental and theoretical methods allow for a constructive and rigorous approach to design and test the theory or at least some of its fundamental building blocks. In this review, we analyzed a set of select experimental and theoretical articles, which were augmented by our own first principles modeling and simulations, to reveal new trends in energetic materials and to refine known existing correlations between their structures, properties, and functions. Our consideration is intentionally limited to the processes of thermally stimulated chemical reactions at the earliest stage of decomposition of molecules and materials containing defects.

  3. Kinetics and the thermal decomposition of Sodium Alanate in the presence of MmNi4.5Al0.5 nanoparticles

    Science.gov (United States)

    Edla, Raju; Gangal, Aneesh C.; Manna, Joydev; Vashistha, Manvendra; Sharma, Pratibha

    2014-03-01

    Sodium Alanate (NaAlH4) is a promising hydrogen storage material due to its high hydrogen content (7.6 wt% of H2), and relatively moderate dehydrogenation and rehydrogenation temperatures. The addition of an appropriate catalyst to NaAlH4 results in a reversible release of 5.5 wt% H2 in a low temperature range of about 90 to 150 °C. Catalyst nano particles of MmNi4.5Al0.5 (henceforth referred to as Mm) to NaAlH4 were added by mechanical ball milling (BM) in mass ratios of 100:5, 100:10, and 100:20, respectively. Thermal decomposition studies were performed at various temperatures (90-150 °C) and a significant improvement in the dehydrogenation was observed after the addition of Mm to the NaAlH4. Un-doped ball milled NaAlH4 released 1.55 wt% of H2 at 150 °C in 60 min, and Mm added NaAlH4 released 3.10-3.25 wt% of H2 were released, respectively. Kinetics analysis was done by using model fit, model free fitting and the obtained activation energy values for both have shown good agreement and the possible decomposition mechanism in all samples by nucleation-growth-saturation mechanism. The improved thermodynamics and kinetics can be attributed to the uniform dispersion and catalytic effect of the Mm nanoparticles, and also to the effect of ball milling.

  4. Palladium-atom catalyzed formic acid decomposition and the switch of reaction mechanism with temperature.

    Science.gov (United States)

    He, Nan; Li, Zhen Hua

    2016-04-21

    Formic acid decomposition (FAD) reaction has been an innovative way for hydrogen energy. Noble metal catalysts, especially palladium-containing nanoparticles, supported or unsupported, perform well in this reaction. Herein, we considered the simplest model, wherein one Pd atom is used as the FAD catalyst. With high-level theoretical calculations of CCSD(T)/CBS quality, we investigated all possible FAD pathways. The results show that FAD catalyzed by one Pd atom follows a different mechanism compared with that catalyzed by surfaces or larger clusters. At the initial stage of the reaction, FAD follows a dehydration route and is quickly poisoned by CO due to the formation of very stable PdCO. PdCO then becomes the actual catalyst for FAD at temperatures approximately below 1050 K. Beyond 1050 K, there is a switch of catalyst from PdCO to Pd atom. The results also show that dehydration is always favoured over dehydrogenation on either the Pd-atom or PdCO catalyst. On the Pd-atom catalyst, neither dehydrogenation nor dehydration follows the formate mechanism. In contrast, on the PdCO catalyst, dehydrogenation follows the formate mechanism, whereas dehydration does not. We also systematically investigated the performance of 24 density functional theory methods. We found that the performance of the double hybrid mPW2PLYP functional is the best, followed by the B3LYP, B3PW91, N12SX, M11, and B2PLYP functionals.

  5. A vacuum ultraviolet photoionization study on the thermal decomposition of ammonium perchlorate

    Science.gov (United States)

    Góbi, Sándor; Zhao, Long; Xu, Bo; Ablikim, Utuq; Ahmed, Musahid; Kaiser, Ralf I.

    2018-01-01

    Pyrolysis products of ammonium perchlorate (NH4ClO4) at 483 K were monitored on line and in situ via single photon photoionization reflectron time-of-flight spectrometry (PI-ReTOF-MS) in the photon energy range of 9.00-17.50 eV. The photoionization efficiency curves (PIE) of the subliming product molecules were collected and allowed for detection of three class of products containing chlorine, nitrogen, and oxygen including atoms and free radicals. These results suggest a new insight into possible low-temperature decomposition pathways of NH4ClO4.

  6. Signatures in magnetites formed by (Ca,Mg,Fe)CO3 thermal decomposition: Terrestrial and extraterrestrial implications

    Science.gov (United States)

    Jimenez-Lopez, Concepcion; Rodriguez-Navarro, Carlos; Rodriguez-Navarro, Alejandro; Perez-Gonzalez, Teresa; Bazylinski, Dennis A.; Lauer, Howard V.; Romanek, Christopher S.

    2012-06-01

    It has never been demonstrated whether magnetite synthesized through the heat-dependent decomposition of carbonate precursors retains the chemical and structural features of the carbonates. In this study, synthetic (Ca,Mg,Fe)CO3 was thermally decomposed by heating from 25 to 700 °C under 1 atm CO2, and by in situ exposure under vacuum to the electron beam of a transmission electron microscope. In both cases, the decomposition of the carbonate was topotactic and resulted in porous pseudomorphs composed of oriented aggregates of magnetite nanocrystals. Both calcium and magnesium were incorporated into nanophase magnetite, forming (Ca,Mg)-magnetites and (Ca,Mg)-ferrites when these elements were present in the parent material, thus preserving the chemical signature of the precursor. These results show that magnetites synthesized in this way acquire a chemical and structural inheritance from their carbonate precursor that indicates how they were produced. These results are not only important in the determination of the origin of chemically-impure, oriented nanophase magnetite crystals in general, but they also provide important insights into the origin of the large, euhedral, chemically-pure, [111]-elongated magnetites found within Ca-, Mg- and Fe-rich carbonates of the Martian meteorite ALH84001. Based on our experimental results, the chemically-pure magnetites within ALH84001 cannot be genetically related to the Ca-, Mg- and Fe-rich carbonate matrix within which they are embedded, and an alternative explanation for their occurrence is warranted.

  7. Decomposition Characteristics of Toluene Vapor Using Titanium Dioxide Photocatalyst and Zeolite Thermally Sprayed on an Aluminum Fiber Filter.

    Science.gov (United States)

    Hori, Hajime; Hinoue, Mitsuo; Ishimatsu, Sumiyo; Fueta, Yukiko; Ishidao, Toru; Takabatake, Kaori; Yakiyama, Natsumi; Yamamoto, Kiyoshi

    Decomposition characteristics of toluene vapor by titanium dioxide photocatalyst and zeolite that are prepared by thermal spraying on an aluminum fiber filter (photocatalyst filter) were investigated. Toluene vapor was injected into a small chamber made of stainless steel, and an air cleaner equipped with the photocatalyst filter was operated. The vapor concentration in the chamber decreased exponentially. The decreasing rate of toluene vapor in the chamber depended on the initial toluene concentration, and the higher the initial vapor concentration was, the lower the decreasing rate was obtained. The decreasing rate was constant during each decomposition experiment, although the concentration decreased with time. To investigate the effect of zeolite on the reduction of the vapor concentration, we compared the decreasing rates of toluene vapor by photocatalyst filters with and without zeolite.The decreasing rate of toluene concentration using the filter without zeolite was larger than that with zeolite. The reason for this would be that photocatalyst decomposed toluene not only in air but also adsorbed in zeolite.

  8. Unveiling the structure and composition of titanium oxide nanotubes through ion exchange chemical reactions and thermal decomposition processes

    Directory of Open Access Journals (Sweden)

    Ferreira Odair P.

    2006-01-01

    Full Text Available In this paper we report the ion exchange reactions and the thermal decomposition of titanium oxide nanotubes, obtained by hydrothermal treatment of TiO2 and NaOH. Based on these results we propose a new composition for the as-prepared nanotubes as Na2Ti3O7.nH2O. Our results also suggest that nanotube walls have structure similar to those observed in the layer of the bulk Na2Ti3O7. Depending on how the washing process is performed on the nanotubes (water or acid solutions the Na+ content can be modified via the exchange reaction of Na+ by H+. Thus, a general chemical formula was also proposed: Na2-xHxTi3O7 .nH2O (0 < x < 2, x being dependent on the washing process.

  9. Monitoring thermally induced structural deformation and framework decomposition of ZIF-8 through in situ temperature dependent measurements.

    Science.gov (United States)

    Xu, Ben; Mei, Yingjie; Xiao, Zhenyu; Kang, Zixi; Wang, Rongming; Sun, Daofeng

    2017-10-18

    ZIF-8 is an easily synthesized porous material which is widely applied in gas storage/separation, catalysis, and nanoarchitecture fabrication. Thermally induced atomic displacements and the resultant framework deformation/collapse significantly influence the application of ZIF-8, and therefore, in situ temperature dependent FTIR spectroscopy was utilized to study the framework changes during heating in the oxidative environment. The results suggest that ZIF-8 undergoes three transition stages, which are the lattice expansion stage below 200 °C, the "reversible" structural deformation stage from 200 to 350 °C, and the decomposition/collapse stage over 350 °C. Our research indicates that the Zn-N bond breaks at a temperature of 350 °C in the oxidant environment, leading to a drastic deformation of the ZIF-8 structure.

  10. Determination of The Minimal Amount of Water for Effective Suppression of The Thermal Decomposition of Forest Combustible Materials

    Directory of Open Access Journals (Sweden)

    Zhdanova Alena О.

    2016-01-01

    Full Text Available Forest fires are big problem for whole the world community. The development of new effective methods is needed to increase the efficiency of the firefighting. We have investigated experimentally the suppression of thermal decomposition of different typical forest combustibles using water aerosol. Droplet sizes were 0.02-0.2mm; the concentration −3.8·10−5 m3 of water/m3, the flow rate −0.00035 l/s, flow velocity −2 m/s. Registration of the aerosol propagation and interaction with combustibles was done by high-speed video camera using Shadow Photography and Particle Tracking Velocimetry methods. The effective water volumes for fire suppression were determined together with corresponding suppression times. The obtained results could be used for improvement of the fire-fighting technologies.

  11. Investigation of the thermal decomposition of magnesium–sodium nitrate pyrotechnic composition (SR-524 and the effect of accelerated aging

    Directory of Open Access Journals (Sweden)

    Zaheer-ud-din Babar

    2017-03-01

    Full Text Available The aging behavior of the pyrotechnics is influenced by the storage atmosphere and more specifically on the temperature and humidity levels. The investigated composition SR 524 is a military pyrotechnic composition that is used as a tracer. The accelerated aging of the SR 524 composition has been carried out at a temperature of 70 °C and relative humidity of 70 percent. The results indicate that there is significant change in the thermal behavior, kinetic parameters and the morphology of the aged composition. The decomposition temperature and the activation energy were found to be lowered in the aged composition. The activation energy of the aged composition decreased nearly 57 percent. SEM micrographs of the aged composition revealed the development of micro cracks as a result of accelerated aging. XRD spectra of the aged composition showed the presence of magnesium hydroxide indicating the reaction between magnesium and water vapors present in the highly humid atmosphere.

  12. Economically attractive route for the preparation of high quality magnetic nanoparticles by the thermal decomposition of iron(III) acetylacetonate

    Science.gov (United States)

    Effenberger, Fernando B.; Couto, Ricardo A.; Kiyohara, Pedro K.; Machado, Giovanna; Masunaga, Sueli H.; Jardim, Renato F.; Rossi, Liane M.

    2017-03-01

    The thermal decomposition (TD) methods are among the most successful in obtaining magnetic nanoparticles with a high degree of control of size and narrow particle size distribution. Here we investigated the TD of iron(III) acetylacetonate in the presence of oleic acid, oleylamine, and a series of alcohols in order to disclose their role and also investigate economically attractive alternatives for the synthesis of iron oxide nanoparticles without compromising their size and shape control. We have found that some affordable and reasonably less priced alcohols, such as 1,2-octanediol and cyclohexanol, may replace the commonly used and expensive 1,2-hexadecanediol, providing an economically attractive route for the synthesis of high quality magnetic nanoparticles. The relative cost for the preparation of Fe3O4 NPs is reduced to only 21% and 9% of the original cost when using 1,2-octanediol and cyclohexanol, respectively.

  13. Thermal, mechanical and morphological properties of polypropylene/clay/wood flour nanocomposites

    Directory of Open Access Journals (Sweden)

    2008-02-01

    Full Text Available Nanocomposites with polypropylene/clay/wood flour were prepared by melt compounding. Thermal, mechanical and morphological properties were characterized. The addition of clay, compatibilizer and wood flour considerably improved the thermal stability (i.e., decomposition and melting temperatures of the hybrids. The tensile modulus and strength of most hybrids were highly increased with the increased loading of clay, MAPP and wood flour, compared to the hybrids without wood flour. The wide angle X-ray diffraction (WAXD patterns showed the increased d-spacing of clay layers, indicating enhanced compatibility between PP and clay with the addition of maleated polypropylene (MAPP. The transmission electron microscopy (TEM photomicrographs illustrated the intercalated and partially exfoliated structures of the hybrids with clay, MAPP and wood flour.

  14. Thermal, electrochemical and mechanical properties of shape

    African Journals Online (AJOL)

    T. Ahmad

    2017-05-01

    May 1, 2017 ... He also discussed the uses of superelastic NiTi powder for the resistance of SnPdAg solder against failure due to thermal stresses. European has been recently using NiTiNb plug for sealing high-pressure fuel passages in diesel engine injectors made of SMA actuators. This research is aimed to develop ...

  15. Sol–gel method to prepare graphene/Fe{sub 2}O{sub 3} aerogel and its catalytic application for the thermal decomposition of ammonium perchlorate

    Energy Technology Data Exchange (ETDEWEB)

    Lan, Yuanfei; Li, Xiaoyu; Li, Guoping; Luo, Yunjun, E-mail: yjluo@bit.edu.cn [Beijing Institute of Technology, School of Materials Science and Engineering (China)

    2015-10-15

    Graphene/Fe{sub 2}O{sub 3} (Gr/Fe{sub 2}O{sub 3}) aerogel was synthesized by a simple sol–gel method and supercritical carbon dioxide drying technique. In this study, the morphology and structure were characterized by scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and nitrogen sorption tests. The catalytic performance of the as-synthesized Gr/Fe{sub 2}O{sub 3} aerogel on the thermal decomposition of ammonium perchlorate (AP) was investigated by thermogravimetric and differential scanning calorimeter. The experimental results showed that Fe{sub 2}O{sub 3} with particle sizes in the nanometer range was anchored on the Gr sheets and Gr/Fe{sub 2}O{sub 3} aerogel exhibits promising catalytic effects for the thermal decomposition of AP. The decomposition temperature of AP was obviously decreased and the total heat release increased as well.

  16. Crystal structures, thermal decompositions and sensitivity properties of [Cu(ethylenediamine)2(nitroformate)2] and [Cd(ethylenediamine)3](nitroformate)2.

    Science.gov (United States)

    Yang, Li; Zhang, Jin; Zhang, Tonglai; Zhang, Jianguo; Cui, Yan

    2009-05-30

    Two new coordination compounds [Cu(ethylenediamine)(2)(nitroformate)(2)] and [Cd(ethylenediamine)(3)](nitroformate)(2) were synthesized and characterized through elemental analysis, IR and UV spectra. Their crystal structures were determined through X-ray single crystal diffraction. The first compound crystallizes in the triclinic space group P1; the second one crystallizes in the orthorhombic space group Pbca. For the first compound, central Cu(II) ion is hexa-coordinated with two ethylenediamine ligand molecules and two nitroformate anions to form the centrosymmetric octahedral structure. For the second one, central Cd(II) ion is hexa-coordinated with three ethylenediamine ligand molecules to form the slightly distorted octahedra. Through hydrogen bonds, molecules are linked together to form the three-dimensional packing diagrams. Thermal decomposition mechanisms of these two compounds were predicted through DSC, TG-DTG and FTIR analyses. In addition, the impact sensitivity, friction sensitivity and flame sensitivity were measured. All observed properties show that the first one has high energy, good thermal stability and moderate flame sensitivity.

  17. New insights on the thermal decomposition of lanthanide(III) and actinide(III) oxalates: from neodymium and cerium to plutonium

    OpenAIRE

    De Almeida, Lucie; Grandjean, Stéphane; Vigier, Nicolas; Patisson, Fabrice

    2012-01-01

    International audience; Lanthanides are often used as surrogates to study the properties of actinide compounds. Their behaviour is considered to be quite similar as they both possess f valence electrons and are close in size and chemical properties. This study examines the potential of using two lanthanides (neodymium and cerium) as surrogates for plutonium during the thermal decomposition of isomorphic oxalate compounds, in the trivalent oxidation state, into oxides. Thus, the thermal decomp...

  18. Thermal decomposition of energetic materials 85: Cryogels of nanoscale hydrazinium diperchlorate in resorcinol-formaldehyde

    Energy Technology Data Exchange (ETDEWEB)

    Tappan, Bryce C.; Brill, Thomas B. [Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716 (United States)

    2003-04-01

    The objective of this work was to try to desensitize an energetic material by using sol-gel processing and freeze drying to incorporate the energetic material into the fuel matrix on the nano (or at least submicron) particle size scale. Hydrazinium diperchlorate ([N{sub 2}H{sub 6}][ClO{sub 4}]{sub 2} or HP{sub 2}) and resorcinol-formaldehyde (RF) were chosen as the oxidizer and fuel, respectively. Solid loading up to 88% HP{sub 2} was achieved by using the sol gel-to-cryogel method. Various weight percentages of HP{sub 2} in RF were characterized by elemental analysis, scanning electron (SEM) and optical microscopy, T-jump/FTIR spectroscopy, DSC, and drop-weight impact. SEM indicated that 20-50 nm diameter HP{sub 2} plates aggregated into porous 400-800 nm size clusters. Below 80% HP{sub 2} the cryogels are less sensitive to impact than physical mixtures having the same ratios of HP{sub 2} and RF. The decomposition temperatures of the cryogels are higher than that of pure HP{sub 2}, which is consistent with their lower impact sensitivity. The heat of decomposition as measured at a low heating rate increases with increasing percentage of HP{sub 2}. The cryogels and physical mixtures release similar amounts of energy, but the cryogels exhibit mainly a single exotherm by DSC whereas the physical mixtures showed a two-step energy release. Flash pyrolysis revealed gaseous product ratios suggestive of more energy being released from the cryogels than the physical mixtures. Cryogels also burn faster by visual observation. (Abstract Copyright [2003], Wiley Periodicals, Inc.)

  19. Thermal Decomposition Reaction of cis-6-Phenyl-5,6-(2-phenylpropilydene-3,3-tetramethylene-1,2,4-trioxacyclohexane in Different Solvents

    Directory of Open Access Journals (Sweden)

    L. F. R. Cafferata

    2000-03-01

    Full Text Available The kinetics of the thermal decomposition reaction of cis-6-phenyl-5,6-(2-phenyl-propilydene-3,3-tetramethylene-1,2,4-trioxacyclohexane (I was investigated in the temperature range of 100-130°C in selected solvents of different physicochemical properties to evaluate a solvent effect on the reaction.

  20. Characterization of volatile organic compounds from human analogue decomposition using thermal desorption coupled to comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry.

    Science.gov (United States)

    Stadler, Sonja; Stefanuto, Pierre-Hugues; Brokl, Michał; Forbes, Shari L; Focant, Jean-François

    2013-01-15

    Complex processes of decomposition produce a variety of chemicals as soft tissues, and their component parts are broken down. Among others, these decomposition byproducts include volatile organic compounds (VOCs) responsible for the odor of decomposition. Human remains detection (HRD) canines utilize this odor signature to locate human remains during police investigations and recovery missions in the event of a mass disaster. Currently, it is unknown what compounds or combinations of compounds are recognized by the HRD canines. Furthermore, a comprehensive decomposition VOC profile remains elusive. This is likely due to difficulties associated with the nontarget analysis of complex samples. In this study, cadaveric VOCs were collected from the decomposition headspace of pig carcasses and were further analyzed using thermal desorption coupled to comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (TD-GC × GC-TOFMS). Along with an advanced data handling methodology, this approach allowed for enhanced characterization of these complex samples. The additional peak capacity of GC × GC, the spectral deconvolution algorithms applied to unskewed mass spectral data, and the use of a robust data mining strategy generated a characteristic profile of decomposition VOCs across the various stages of soft-tissue decomposition. The profile was comprised of numerous chemical families, particularly alcohols, carboxylic acids, aromatics, and sulfides. Characteristic compounds identified in this study, e.g., 1-butanol, 1-octen-3-ol, 2-and 3-methyl butanoic acid, hexanoic acid, octanal, indole, phenol, benzaldehyde, dimethyl disulfide, and trisulfide, are potential target compounds of decomposition odor. This approach will facilitate the comparison of complex odor profiles and produce a comprehensive VOC profile for decomposition.

  1. TRANSITION AND DECOMPOSITION TEMPERATURES OF CEMENT PHASES - A COLLECTION OF THERMAL ANALYSIS DATA

    Directory of Open Access Journals (Sweden)

    Nick C. Collier

    2016-10-01

    Full Text Available Thermal analysis techniques provide the cement chemist with valuable tools to qualify and quantify the products formed during the hydration of cementitious materials. These techniques are commonly used alongside complimentary techniques such as X-ray diffraction and electron microscopy/energy dispersive spectroscopy to confirm the composition of phases present and identify amorphous material unidentified by other techniques. The most common thermal analysis techniques used by cement chemists are thermogravimetry, differential thermal analysis and differential scanning calorimetry. In order to provide a useful reference tool to the cement chemist, this paper provides a brief summary of the temperatures at which phase changes occur in the most common cement hydrates in the range 0-800°C in order to aid phase identification.

  2. Effects of Thermal Treatment on the Dynamic Mechanical Properties of Coal Measures Sandstone

    Science.gov (United States)

    Li, Ming; Mao, Xianbiao; Cao, Lili; Pu, Hai; Mao, Rongrong; Lu, Aihong

    2016-09-01

    Many projects such as the underground gasification of coal seams and coal-bed methane mining (exploitation) widely involve the dynamic problems of coal measures sandstone achieved via thermal treatment. This study examines the dynamic mechanical properties of coal measures sandstone after thermal treatment by means of an MTS653 high-temperature furnace and Split Hopkinson pressure bar test system. Experimental results indicate that 500 °C is a transition point for the dynamic mechanical parameters of coal measures sandstone. The dynamic elastic modulus and peak strength increase linearly from 25 to 500 °C while the dynamic peak strain decreases linearly over the same temperature range. The dynamic elastic modulus and peak strength drop quickly from 500 to 800 °C, with a significant increase in the dynamic peak strain over the same temperature range. The rock mechanics are closely linked to material composition and mesoscopic structure. Analysis by X-ray diffraction and scanning electron microscopy indicate that the molecules inside the sandstone increase in density due to the thermal expansion of the material particles, which effectively improves the deformation resistance and carrying capacity of the sandstone and reduces the likelihood of axial deformation. With heat treatment that exceeds 500 °C, the dynamic mechanical properties rapidly weaken due to the decomposition of kaolinite; additionally, hot cracking of the mineral particles within the materials arises from coal sandstone internal porosity, and other defects gradually appear.

  3. Acyloxyl radical pair intermediate for the initial stage of the thermal decomposition of diacyl peroxide: a density functional study

    Science.gov (United States)

    Uchimaru, Tadafumi; Hara, Ryoma; Tanabe, Kazutoshi; Fujimori, Ken

    1997-03-01

    To examine the reaction mechanism for the thermal reorganization, or more specifically the oxygen scrambling, in diacyl peroxide, we have carried out a hybrid density functional study using formyl peroxide as a model compound. The B3LYP calculations suggest that the oxygen scrambling in diacyl peroxide is most likely to occur via a σ-acyloxyl radical pair species: the competitive pathways of the [3,3]- and [1,3]-sigmatropic shifts are highly improbable. Thus, the mechanism for the thermal oxygen scrambling in diacyl peroxide should be completely different from those for the carbon counterparts of diacyl peroxide (the Cope and Claisen rearrangement).

  4. Densely crosslinked polycarbosiloxanes .2. Thermal and mechanical properties

    NARCIS (Netherlands)

    Flipsen, T.A C; Derks, R.; van der Vegt, H.A.; Stenekes, R.; Pennings, A.J; Hadziioannou, G

    1997-01-01

    The thermal and mechanical properties of two densely crosslinked polycarbosiloxane systems were investigated in relation to the molecular structure. The networks were prepared from functional branched prepolymers and crosslinked via a hydrosilylation curing reaction. The prepolymers having only

  5. Synthesis and characterization of polyurethane/bentonite nanoclay based nanocomposites using different diisocyanates: relation between mechanical and thermal properties

    Science.gov (United States)

    Bocchio, Javier; Wittemberg, Víctor; Quagliano, Javier

    2017-05-01

    Polyurethanes (PUs) and polyurethane nanocomposites (PUNC) with bentonite nanoclay were prepared by the reaction of toluene-2,4-diisocyanate (TDI), dimeryl diisocyanate (DDI) and isophorone diisocyanate (IPDI) with two different polymers: hydroxyl terminated polybutadiene (HTPB) and polytetramethylene ether glycol (PTMEG), and the chains were further extended with 1,4-butanediol (1,4-BDO) to get final PUs and PUNCs. PUNCs were prepared by dispersing within the polymers a commercial and a synthesized bentonite nanoclay by mechanical dispersion. Mechanical properties showed that the addition of a small amount of nanoclay resulted in a significant increase in tensile strength and reduction in elongation at break (maximum increase of 2.3 and 5-times reduction, respectively, for a HTPB-TDI-BDO PUNCs). Thermal analysis revealed that the addition of nanoclays improved the thermal stability and increased decomposition temperature of PUNCs. We concluded that there is a positive correlation between mechanical and thermal properties as a result of nanoclay addition.

  6. Mechanical and Thermal Properties of Polypropylene Reinforced by Calcined and Uncalcined Zeolite

    Directory of Open Access Journals (Sweden)

    Nurdin Bukit

    2013-04-01

    Full Text Available This study was carried out to compare mechanical and thermal properties of polypropylene (PP reinforced with uncalcined and calcined zeolites. The PP samples were reinforced with zeolites at various quantities of 2, 4, and 6 (wt %. The comparison of the two types of zeolite was based  on mechanical properties, including tensile strength, elongation at break, and Young’s modulus, and thermal characteristics analyzed using DSC, and DTA/TGA technique. The results obtained clearly revealed that both zeolites were able to significantly increase tensile strength and Young’s modulus of the samples, with calcined zeolite was found to work better. Addition of calcined zeolite was found to result in increased fracture elongation of the samples reinforced with up to 4 wt% zeolite but decreased sharply for the sample reinforced with 6 wt% zeolite, while for the samples reinforced with uncalcined zeolite, no consistent trend was observed. Thermal analyses demonstrated that the samples reinforced with calcined zeolite are more resistant to thermal treatment than those reinforced with uncalcined zeolite, as indicated by their higher decomposition temperature. DSC analysis revealed that there  was no significant difference  of the melting points of the samples was observed, but the effect of the quantity of zeolite on enthalphy was quite evident, in which the enthalpies of the samples reinforced with calcined zeolites were relatively lower than those of the samples reinforced with uncalcined zeolites. 

  7. Leaf litter mixtures alter microbial community development: mechanisms for non-additive effects in litter decomposition.

    Directory of Open Access Journals (Sweden)

    Samantha K Chapman

    Full Text Available To what extent microbial community composition can explain variability in ecosystem processes remains an open question in ecology. Microbial decomposer communities can change during litter decomposition due to biotic interactions and shifting substrate availability. Though relative abundance of decomposers may change due to mixing leaf litter, linking these shifts to the non-additive patterns often recorded in mixed species litter decomposition rates has been elusive, and links community composition to ecosystem function. We extracted phospholipid fatty acids (PLFAs from single species and mixed species leaf litterbags after 10 and 27 months of decomposition in a mixed conifer forest. Total PLFA concentrations were 70% higher on litter mixtures than single litter types after 10 months, but were only 20% higher after 27 months. Similarly, fungal-to-bacterial ratios differed between mixed and single litter types after 10 months of decomposition, but equalized over time. Microbial community composition, as indicated by principal components analyses, differed due to both litter mixing and stage of litter decomposition. PLFA biomarkers a15∶0 and cy17∶0, which indicate gram-positive and gram-negative bacteria respectively, in particular drove these shifts. Total PLFA correlated significantly with single litter mass loss early in decomposition but not at later stages. We conclude that litter mixing alters microbial community development, which can contribute to synergisms in litter decomposition. These findings advance our understanding of how changing forest biodiversity can alter microbial communities and the ecosystem processes they mediate.

  8. Improved accuracy and precision in δ15 NAIR measurements of explosives, urea, and inorganic nitrates by elemental analyzer/isotope ratio mass spectrometry using thermal decomposition.

    Science.gov (United States)

    Lott, Michael J; Howa, John D; Chesson, Lesley A; Ehleringer, James R

    2015-08-15

    Elemental analyzer systems generate N(2) and CO(2) for elemental composition and isotope ratio measurements. As quantitative conversion of nitrogen in some materials (i.e., nitrate salts and nitro-organic compounds) is difficult, this study tests a recently published method - thermal decomposition without the addition of O(2) - for the analysis of these materials. Elemental analyzer/isotope ratio mass spectrometry (EA/IRMS) was used to compare the traditional combustion method (CM) and the thermal decomposition method (TDM), where additional O(2) is eliminated from the reaction. The comparisons used organic and inorganic materials with oxidized and/or reduced nitrogen and included ureas, nitrate salts, ammonium sulfate, nitro esters, and nitramines. Previous TDM applications were limited to nitrate salts and ammonium sulfate. The measurement precision and accuracy were compared to determine the effectiveness of converting materials containing different fractions of oxidized nitrogen into N(2). The δ(13) C(VPDB) values were not meaningfully different when measured via CM or TDM, allowing for the analysis of multiple elements in one sample. For materials containing oxidized nitrogen, (15) N measurements made using thermal decomposition were more precise than those made using combustion. The precision was similar between the methods for materials containing reduced nitrogen. The %N values were closer to theoretical when measured by TDM than by CM. The δ(15) N(AIR) values of purchased nitrate salts and ureas were nearer to the known values when analyzed using thermal decomposition than using combustion. The thermal decomposition method addresses insufficient recovery of nitrogen during elemental analysis in a variety of organic and inorganic materials. Its implementation requires relatively few changes to the elemental analyzer. Using TDM, it is possible to directly calibrate certain organic materials to international nitrate isotope reference materials without off

  9. Modeling of transport phenomena during gas hydrate decomposition by depressurization and/or thermal stimulation

    Science.gov (United States)

    Abendroth*, Sven; Klump, Jens; Thaler, Jan; Schicks, Judith M.

    2013-04-01

    In the context of the German joint project SUGAR (Submarine Gas Hydrate Reservoirs: exploration, extraction and transport) we conducted a series of experiments in the LArge Reservoir Simulator (LARS) at the German Research Centre of Geosciences Potsdam (Beeskow-Strauch et al., this volume). These experiments allow us to investigate the formation and dissociation of hydrates at large scale laboratory conditions. Processes inside LARS are modeled to study the effects of sediment properties as well as physical and chemical processes on parameters such as hydrate dissociation rate and methane production rate. The experimental results from LARS are used to provide details about processes inside the pressure vessel, validate the models through history matching, and feed back into the design of future experiments. In experiments in LARS the amount of methane produced from gas hydrates was much lower than expected. Previously published models predict a methane production rate higher than the observed in experiments and field studies (Uddin and Wright 2005; Uddin et al. 2010; Wright et al. 2011). The authors of the aforementioned studies point out that the current modeling approach overestimates the gas production rate when modeling gas production by depressurization. Uddin and Wright (2005) suggested that trapping of gas bubbles inside the porous medium is responsible for the reduced gas production rate. They point out that this behavior of multi-phase flow is not well explained by a "residual oil" model, but rather resembles a "foamy oil" model. Our study applies Uddin's (2010) "foamy oil" model and combines it with history matches of our experiments in LARS. First results indicate a better agreement between experimental and model results when using the "foamy oil" model instead of conventional models featuring gas flow in water. Further experiments with LARS, including hydrate dissociation by depressurization and thermal stimulation by in-situ combustion will be used to

  10. Methane-induced Activation Mechanism of Fused Ferric Oxide-Alumina Catalysts during Methane Decomposition

    KAUST Repository

    Reddy Enakonda, Linga

    2016-06-27

    Activation of Fe2O3-Al2O3 with CH4 (instead of H2) is a meaningful method to achieve catalytic methane decomposition (CMD). This reaction of CMD is more economic and simple against commercial methane steam reforming (MSR) as it produces COx-free H2. In this study, for the first time, structure changes of the catalyst were screened during CH4 reduction with time on stream. The aim was to optimize the pretreatment conditions through understanding the activation mechanism. Based on results from various characterization techniques, reduction of Fe2O3 by CH4 proceeds in three steps: Fe2O3→Fe3O4→FeO→Fe0. Once Fe0 is formed, it decomposes CH4 with formation of Fe3C, which is the crucial initiation step in the CMD process to initiate formation of multiwall carbon nanotubes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Influence of Chemical Treatment on Thermal Decomposition and Crystallite Size of Coir Fiber

    Science.gov (United States)

    Manjula, R.; Raju, N. V.; Chakradhar, R. P. S.; Kalkornsurapranee, Ekwipoo; Johns, Jobish

    2018-01-01

    Coir fibers were treated with sodium hydroxide (NaOH) and glutaraldehyde (GA). The influence of alkali and aldehyde treatment on thermal degradation and crystallinity of coir fiber was studied in detail. Thermogravimetric analysis and X-ray diffraction techniques were mainly used to characterize the coir samples. Activation energy of degradation was calculated from Broido and Horowitz-Metzger equations. NaOH-treated samples showed an increase in thermal stability. Removal of impurities such as waxy and fatty acid residues from the coir fiber by reacting with strong base solution improved the stability of fiber. Crosslinking of cellulose with GA in the fiber enhanced the stability of the material. Scanning electron microscopy was employed to analyze the change in surface morphology upon chemical treatment. Improvement in the properties suggests that NaOH and GA can be effectively used to modify coir fiber with excellent stability.

  12. Thermal Decomposition of 1,5-Dinitrobiuret (DNB): Direct Dynamics Trajectory Simulations and Statistical Modeling

    Science.gov (United States)

    2011-05-03

    gaseous products were identified using mass spectrometry and Fourier transform infrared spectroscopy.1,4 DSC analysis revealed that thermal...apply, because the molecular transformations are too complex. A useful approach to treating such system is quasi-classical, direct dynamics...A.; Li, G.; Lim, K.; Lu, D.; Peslherbe, G. H.; Song, K.; Swamy, K. N.; Vande Linde, S. R.; Varandas, A.; Wang, H.; Wolf, R. J. VENUS99: A general

  13. Decomposition of tar in gas from updraft gasifier by thermal cracking

    DEFF Research Database (Denmark)

    Brandt, Peder; Henriksen, Ulrik Birk

    2000-01-01

    Continuing earlier work with tar reduction by partial oxidation of pyrolysis gas [1] thermal cracking has been evaluated as a gas cleaning process. The work has been focusing on cleaning gas from updraft gasifiers, and the long term purpose is to develop a tar cleaning unit based on thermal...... cracking. An experimental set-up has been built, in which a flow of contaminated gas can be heated up to 1290°C in a reactor made of pure Al2O3. Four measurements were made. Three with gas from a pyrolysis unit simulating updraft gasifier, and one with gas from an updraft gasifier. Cracking temperatures...... was 1200, 1250 and 1290°C, and the residence time at this temperature was 0.5 second. The measurements show that at the selected residence time of 0.5 second, the gas flow in a thermal tar cracking unit has to be heated to at least 1250°C to achieve sufficient tar cleaning. At 1290°C, a tar content as low...

  14. Magnetic changes accompanying the thermal decomposition of nontronite /in air/ and its relevance to Martian mineralogy

    Science.gov (United States)

    Moskowitz, B. M.; Hargraves, R. B.

    1982-11-01

    It is found that the thermal treatment of nontronite in air, for long periods at 700 C or short periods at 900 C, results in the destruction of the nontronite structure, a distinct reddening in color, and a large increase in magnetic susceptibility and saturation magnetization. Measurements and calculations of the magnetic properties suggest that the magnetism is due to the presence of ultrafine particles of alpha or gamma Fe2O3. The highly magnetic thermally treated nontronite is amorphous to X-rays consistent with an ultrafine grain size. Prolonged heating results in the growth of alpha Fe2O3, while reflectivity spectra of a sample heated for 1 hr at 900 C indicate the presence of an opaque, magnetite-like phase in addition to alpha Fe2O3. It is found that the thermally treated nontronite has chemical, color, and magnetic properties similar to those found by Viking on Mars. It is concluded that these results indicate an origin for the fine grained Martian surface material by repeated impacts into an Fe-rich smectite-charged regolith (Weldon et al., 1980).

  15. Thermal Decomposition of Methyl Acetate (CH_3COOCH_3) in a Flash-Pyrolysis Micro-Reactor

    Science.gov (United States)

    Porterfield, Jessica P.; Bross, David H.; Ruscic, Branko; Thorpe, James H.; Nguyen, Thanh Lam; Baraban, Joshua H.; Stanton, John F.; Daily, John W.; Ellison, Barney

    2017-06-01

    The thermal decomposition of methyl acetate (CH_3COOCH_3) has been studied in a set of flash pyrolysis micro-reactors. Samples were diluted to (0.06 - 0.13%) in carrier gases (He, Ar) and subjected to temperatures of 300 - 1600 K at roughly 20 Torr. After residence times of approximately 25 - 150 μseconds, the unimolecular pyrolysis products were detected by vacuum ultraviolet photoionization mass spectrometry at 10.487 eV (118.2 nm). Complementary product identification was provided by matrix isolation infrared spectroscopy. Decomposition began at 1000 K with the observation of (CH_2=C=O, CH_3OH), products of a four centered rearrangement with a Δ_{rxn}H_{298} = 39.1 ± 0.2 kcal mol^{-1}. As the micro-reactor was heated to 1300 K, a mixture of (CH_2=C=O, CH_3OH, CH_3, CH_2=O, H, CO, CO_2) appeared. A new novel pathway is calculated in which both methyl groups leave behind CO_2 simultaneously, Δ_{rxn}H_{298} = 74.5 ± 0.4 kcal mol^{-1}. This pathway is in contrast to step-wise loss of methyl radical, which can go in two ways: Δ_{rxn}H_{298} (CH_3COOCH_3 → CH_3 + COOCH_3) = 95.4 ± 0.4 kcal mol^{-1}, Δ_{rxn}H_{298} (CH_3COOCH_3 → CH_3COO + CH_3) = 88.0 ± 0.3 kcal mol^{-1}.

  16. Monodisperse Iron Oxide Nanoparticles by Thermal Decomposition: Elucidating Particle Formation by Second-Resolved in Situ Small-Angle X-ray Scattering

    Science.gov (United States)

    2017-01-01

    The synthesis of iron oxide nanoparticles (NPs) by thermal decomposition of iron precursors using oleic acid as surfactant has evolved to a state-of-the-art method to produce monodisperse, spherical NPs. The principles behind such monodisperse syntheses are well-known: the key is a separation between burst nucleation and growth phase, whereas the size of the population is set by the precursor-to-surfactant ratio. Here we follow the thermal decomposition of iron pentacarbonyl in the presence of oleic acid via in situ X-ray scattering. This method allows reaction kinetics and precursor states to be followed with high time resolution and statistical significance. Our investigation demonstrates that the final particle size is directly related to a phase of inorganic cluster formation that takes place between precursor decomposition and particle nucleation. The size and concentration of clusters were shown to be dependent on precursor-to-surfactant ratio and heating rate, which in turn led to differences in the onset of nucleation and concentration of nuclei after the burst nucleation phase. This first direct observation of prenucleation formation of inorganic and micellar structures in iron oxide nanoparticle synthesis by thermal decomposition likely has implications for synthesis of other NPs by similar routes. PMID:28572705

  17. Investigation of thermal decomposition as the kinetic process that causes the loss of crystalline structure in sucrose using a chemical analysis approach (part II).

    Science.gov (United States)

    Lee, Joo Won; Thomas, Leonard C; Jerrell, John; Feng, Hao; Cadwallader, Keith R; Schmidt, Shelly J

    2011-01-26

    High performance liquid chromatography (HPLC) on a calcium form cation exchange column with refractive index and photodiode array detection was used to investigate thermal decomposition as the cause of the loss of crystalline structure in sucrose. Crystalline sucrose structure was removed using a standard differential scanning calorimetry (SDSC) method (fast heating method) and a quasi-isothermal modulated differential scanning calorimetry (MDSC) method (slow heating method). In the fast heating method, initial decomposition components, glucose (0.365%) and 5-HMF (0.003%), were found in the sucrose sample coincident with the onset temperature of the first endothermic peak. In the slow heating method, glucose (0.411%) and 5-HMF (0.003%) were found in the sucrose sample coincident with the holding time (50 min) at which the reversing heat capacity began to increase. In both methods, even before the crystalline structure in sucrose was completely removed, unidentified thermal decomposition components were formed. These results prove not only that the loss of crystalline structure in sucrose is caused by thermal decomposition, but also that it is achieved via a time-temperature combination process. This knowledge is important for quality assurance purposes and for developing new sugar based food and pharmaceutical products. In addition, this research provides new insights into the caramelization process, showing that caramelization can occur under low temperature (significantly below the literature reported melting temperature), albeit longer time, conditions.

  18. Adsorption and photocatalytic decomposition of roxarsone by TiO₂ and its mechanism.

    Science.gov (United States)

    Lu, Donglei; Ji, Feng; Wang, Feng; Yuan, Shoujun; Hu, Zhen-Hu; Chen, Tianhu

    2014-01-01

    Roxarsone (3-nitro-4-hydroxyphenylarsonic acid) has been widely used as organic arsenic additive in animal industry. In this study, the adsorption of roxarsone on TiO₂ under dark conditions, the photocatalytic decomposition of roxarsone under UV/TiO₂, and the possible photocatalytic pathway were investigated. At the initial concentration of 5-35 mg/L, the adsorption of roxarsone fitted well with the pseudo-second-order kinetics. The isotherms analysis showed that the Langmuir model was better than the Freundlich and Dubinin–Radushkevich models for describing the adsorption process. After 7 h of photocatalytic decomposition, a complete disappearance of roxarsone was achieved. The pH value has a significant effect on both adsorption and photocatalytic decomposition of roxarsone. The results of high-performance liquid chromatography-hydride generation-atomic fluorescence spectrometry (HPLC-HG-AFS) and gas chromatography-mass spectrometry (GC/MS) analyses proved the cleavage of the As-C bond during the photocatalytic decomposition process by TiO2 and the intermediates of the decomposition. Based on the results, a possible photocatalytic decomposition pathway was proposed.

  19. In situ thermally reduced graphene oxide/epoxy composites: thermal and mechanical properties

    National Research Council Canada - National Science Library

    Olowojoba, Ganiu B; Eslava, Salvador; Gutierrez, Eduardo S; Kinloch, Anthony J; Mattevi, Cecilia; Rocha, Victoria G; Taylor, Ambrose C

    2016-01-01

    Graphene has excellent mechanical, thermal, optical and electrical properties and this has made it a prime target for use as a filler material in the development of multifunctional polymeric composites...

  20. INFLUENCE OF VARIOUS FACTORS ON THE THERMAL DECOMPOSITION OF ALKALINE-REDUCING SUBSTANCES

    Directory of Open Access Journals (Sweden)

    V. A. Golybin

    2014-01-01

    Full Text Available Summary. According to the modern technology of sugar production normative expansion reducing substances in the cleaning diffusion juice, should be held in the main liming controlled temperature with an excess of lime alkalinity, followed by removal of the decay products have appeared due to the adsorption of calcium carbonate in the processing of juice carbon dioxide. Test data show the growth rate of thermochemical quantities of sucrose decay with increasing temperature, with the greatest degree in the experiments with a small share of reducing substances in solutions. With increase in the proportion of reducing substances to 0,3 %, the rate is reduced to about twice, with a 80 ° C and found to decrease its rate of growth . Main liming process preceded progressive preliming , not only where the epimerization faster but less stable , and the decomposition of fructose in the composition of the reducing substances to produce reactive products influencing the alkalinity of the solution and the surface state of microparticles of calcium hydroxide . The presence on the surface OH-groups and the appearance of tumors in the working environment, having in their structures group (= CO, (= O, (- СОН contributes to the appearance of induced hydrogen bonds and partial reduction of the specific surface of the mass transfer between the solid particles and the components of the solution. Carboxyl group reduce the level of active alkalinity, which as a result of blocking is limited, which reduces the pH of the environment and the decay constant reducing substances. When heated to about 85 °C decomposed 20% of the reducing substances, and chromaticity increased by 83,1 %, taking into account the heating and hot main liming chromaticity increased by 116,9 %. That is, the more reducing substances remain in solution after the first stage of the main liming, the stronger chroma increases upon subsequent heating and hot workability.

  1. Effect of the substitutional groups on the electrochemistry, kinetic of thermal decomposition and kinetic of substitution of some uranyl Schiff base complexes

    Energy Technology Data Exchange (ETDEWEB)

    Asadi, Zahra; Nasrollahi, Rahele; Ranjkeshshorkaei, Mohammad; Firuzabadi, Fahimeh Dehghani [Shiraz Univ. (Iran, Islamic Republic of). Chemistry Dept.; Dusek, Michal; Fejfarova, Karla [ASCR, Prague (Czech Republic). Inst. of Physics

    2016-05-15

    Uranyl(VI) complexes, [UO{sub 2}(X-saloph)(solvent)], where saloph denotes N,N{sup '}-bis(salicylidene)-1,2-phenylenediamine and X = NO{sub 2}, Cl, Me, H; were synthesized and characterized by 61H NMR, IR, UV-Vis spectroscopy, thermal gravimetry (TG), cyclic voltammetry, elemental analysis (C.H.N) and X-ray crystallography. X-ray crystallography of [UO{sub 2}(4-nitro-saloph)(DMF)] revealed coordination of the uranyl by the tetradentate Schiff base ligand and one solvent molecule, resulting in seven-coordinated uranium. The complex of [UO{sub 2}(4-nitro-saloph)(DMF)] was also synthesized in nano form. Transmission electron microscopy image showed nano-particles with sizes between 30 and 35 nm. The TG method and analysis of Coats-Redfern plots revealed that the kinetics of thermal decomposition of the complexes is of the first-order in all stages. The kinetics and mechanism of the exchange reaction of the coordinated solvent with tributylphosphine was investigated by spectrophotometric method. The second-order rate constants at four temperatures and the activation parameters showed an associative mechanism for all corresponding complexes with the following trend: 4-Nitro > 4-Cl > H > 4-Me. It was concluded that the steric and electronic properties of the complexes were important for the reaction rate. For analysis of anticancer properties of uranyl Schiff base complexes, cell culture and MTT assay was carried out. These results showed a reduction of jurkat cell line concentration across the complexes.

  2. Analysis of the decomposition gases from α and β-Cd(BH4)2 synthesized by temperature controlled mechanical milling

    DEFF Research Database (Denmark)

    Blanchard, Didier; Zatti, Matteo; Vegge, Tejs

    2013-01-01

    We present a comprehensive study on the controlled phase synthesis and thermal decomposition of Cd(BH2)4, a material for solid state hydrogen storage obtained via the metathesis reaction of LiBH4 with CdCl2. By adjusting the stochiometry of the reactants and controlling the mechanical milling vial...... temperature, we have isolated the tetragonal (P42mn) low temperature phase and the cubic (View the MathML source) high temperature phase of the cadmium borohydride. Cd(BH2)4 has a low thermodynamic stability and decomposes with fast kinetic at 348 K, when heated at 1 K min−1 against a backpressure of 1 bar H2...

  3. Thermal, electrochemical and mechanical properties of shape ...

    African Journals Online (AJOL)

    ... resemblance with structure of casted shape memory alloy obtained from the vacuum induction process. The Vickers hardness test was also performed. Quenched microstructure with improved hardness than pre-quenched structure was observed. Keywords: Shape Memory Alloy, Microstructure, Mechanical Properties ...

  4. Synthesis, mechanical, thermal and chemical properties of ...

    Indian Academy of Sciences (India)

    Unknown

    Department of Chemistry, Manonmaniam Sundaranar University, Abishekapatti, Tirunelveli 627 012, India. MS received 28 August 2003; ... thanes were characterized with respect to their resistance to chemical reagents and mechanical properties such as tensile strength, ..... Recent advances (ed.) I S. Bhardwajj (New ...

  5. Thermalization and its mechanism for generic isolated quantum systems.

    Science.gov (United States)

    Rigol, Marcos; Dunjko, Vanja; Olshanii, Maxim

    2008-04-17

    An understanding of the temporal evolution of isolated many-body quantum systems has long been elusive. Recently, meaningful experimental studies of the problem have become possible, stimulating theoretical interest. In generic isolated systems, non-equilibrium dynamics is expected to result in thermalization: a relaxation to states in which the values of macroscopic quantities are stationary, universal with respect to widely differing initial conditions, and predictable using statistical mechanics. However, it is not obvious what feature of many-body quantum mechanics makes quantum thermalization possible in a sense analogous to that in which dynamical chaos makes classical thermalization possible. For example, dynamical chaos itself cannot occur in an isolated quantum system, in which the time evolution is linear and the spectrum is discrete. Some recent studies even suggest that statistical mechanics may give incorrect predictions for the outcomes of relaxation in such systems. Here we demonstrate that a generic isolated quantum many-body system does relax to a state well described by the standard statistical-mechanical prescription. Moreover, we show that time evolution itself plays a merely auxiliary role in relaxation, and that thermalization instead happens at the level of individual eigenstates, as first proposed by Deutsch and Srednicki. A striking consequence of this eigenstate-thermalization scenario, confirmed for our system, is that knowledge of a single many-body eigenstate is sufficient to compute thermal averages-any eigenstate in the microcanonical energy window will do, because they all give the same result.

  6. A computational domain decomposition approach for solving coupled flow-structure-thermal interaction problems

    Directory of Open Access Journals (Sweden)

    Eugenio Aulisa

    2009-04-01

    Full Text Available Solving complex coupled processes involving fluid-structure-thermal interactions is a challenging problem in computational sciences and engineering. Currently there exist numerous public-domain and commercial codes available in the area of Computational Fluid Dynamics (CFD, Computational Structural Dynamics (CSD and Computational Thermodynamics (CTD. Different groups specializing in modelling individual process such as CSD, CFD, CTD often come together to solve a complex coupled application. Direct numerical simulation of the non-linear equations for even the most simplified fluid-structure-thermal interaction (FSTI model depends on the convergence of iterative solvers which in turn rely heavily on the properties of the coupled system. The purpose of this paper is to introduce a flexible multilevel algorithm with finite elements that can be used to study a coupled FSTI. The method relies on decomposing the complex global domain, into several local sub-domains, solving smaller problems over these sub-domains and then gluing back the local solution in an efficient and accurate fashion to yield the global solution. Our numerical results suggest that the proposed solution methodology is robust and reliable.

  7. Thermal expansion and decomposition of jarosite: a high-temperature neutron diffraction study

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Hongwu [Los Alamos National Laboratory; Zhao, Yusheng [Los Alamos National Laboratory; Vogel, Sven C [Los Alamos National Laboratory; Hickmott, Donald D [Los Alamos National Laboratory; Daemen, Luke L [Los Alamos National Laboratory; Hartl, Monika A [Los Alamos National Laboratory

    2009-01-01

    The structure of deuterated jarosite, KFe{sub 3}(SO{sub 4}){sub 2}(OD){sub 6}, was investigated using time-of-flight neutron diffraction up to its dehydroxylation temperature. Rietveld analysis reveals that with increasing temperature, its c dimension expands at a rate {approx}10 times greater than that for a. This anisotropy of thermal expansion is due to rapid increase in the thickness of the (001) sheet of [Fe(O,OH){sub 6}] octahedra and [SO{sub 4}] tetrahedra with increasing temperature. Fitting of the measured cell volumes yields a coefficient of thermal expansion, a = a{sub 0} + a{sub 1} T, where a{sub 0} = 1.01 x 10{sup -4} K{sup -1} and a{sub 1} = -1.15 x 10{sup -7} K{sup -2}. On heating, the hydrogen bonds, O1{hor_ellipsis}D-O3, through which the (001) octahedral-tetrahedral sheets are held together, become weakened, as reflected by an increase in the D{hor_ellipsis}O1 distance and a concomitant decrease in the O3-D distance with increasing temperature. On further heating to 575 K, jarosite starts to decompose into nanocrystalline yavapaiite and hematite (as well as water vapor), a direct result of the breaking of the hydrogen bonds that hold the jarosite structure together.

  8. Numerical Investigation of AdBlue Droplet Evaporation and Thermal Decomposition in the Context of NOx-SCR Using a Multi-Component Evaporation Model

    Directory of Open Access Journals (Sweden)

    Kaushal Nishad

    2018-01-01

    Full Text Available To cope with the progressive tightening of the emission regulations, gasoline and diesel engines will continuously require highly improved exhaust after-treatment systems. In the case of diesel engines, the selective catalytic reduction (SCR appears as one of the widely adopted technologies to reduce NOx (nitrogen oxides emissions. Thereby, with the help of available heat from exhaust gas, the injected urea–water solution (UWS turns inside the exhaust port immediately into gaseous ammonia (NH3 by evaporation of mixture and thermal decomposition of urea. The reaction and conversion efficiency mostly depend upon the evaporation and subsequent mixing of the NH3 into the exhaust gas, which in turn depends upon the engine loading conditions. Up to now, the aggregation of urea after evaporation of water and during the thermal decomposition of urea is not clearly understood. Hence, various scenarios for the urea depletion in the gaseous phase that can be envisaged have to be appraised under SCR operating conditions relying on an appropriate evaporation description. The objective of the present paper is therefore fourfold. First, a reliable multi-component evaporation model that includes a proper binary diffusion coefficient is developed for the first time in the Euler–Lagrangian CFD (computational fluid dynamics framework to account properly for the distinct evaporation regimes of adBlue droplets under various operating conditions. Second, this model is extended for thermal decomposition of urea in the gaseous phase, where, depending on how the heat of thermal decomposition of urea is provided, different scenarios are considered. Third, since the evaporation model at and around the droplet surface is based on a gas film approach, how the material properties are evaluated in the film influences the process results is reported, also for the first time. Finally, the impact of various ambient temperatures on the adBlue droplet depletion characteristics

  9. Research on the thermal decomposition of Mongolian Baganuur lignite and Naryn sukhait bituminous coal

    Directory of Open Access Journals (Sweden)

    A. Ariunaa

    2016-03-01

    Full Text Available The technical characteristics, elemental composition of the organic and mineral matters, ash melting behaviors and carbonization and gasification reactivities of coals from Baganuur and Naryn sukhait deposits were investigated. The results of proximate and ultimate analysis confirmed that the coal from Baganuur deposit can be graded as a low rank lignite B2 mark coal and Naryn sukhait coal is a bituminous G mark one. The carbonization and gasification experiments were performed using TGA apparatus and fixed bed quartz reactor. The data obtained with two experimental reactors showed that Baganuur lignite had lower thermal stability and much higher CO2 gasification reactivity at 950°C as compared to those for Naryn sukhait bituminous coal.Mongolian Journal of Chemistry 16 (42, 2015, 22-29

  10. Pure CuCr2O4 nanoparticles: Synthesis, characterization and their morphological and size effects on the catalytic thermal decomposition of ammonium perchlorate

    Science.gov (United States)

    Hosseini, Seyed Ghorban; Abazari, Reza; Gavi, Azam

    2014-11-01

    In the present paper a pure phase of the copper chromite spinel nanoparticles (CuCr2O4 SNPs) were synthesized via the sol-gel route using citric acid as a complexing agent. Then, the CuCr2O4 SNPs has been characterized by field emission scanning electron microscope (FE-SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD). In the next step, with the addition of Cu-Cr-O nanoparticles (NPs), the effects of different parameters such as Cu-Cr-O particle size and the Cu/Cr molar ratios on the thermal behavior of Cu-Cr-O NPs + AP (ammonium perchlorate) mixtures were investigated. As such, the catalytic effect of the Cu-Cr-O NPs for thermal decomposition of AP was evaluated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). TGA/DSC results showed that the samples with different morphologies exhibited different catalytic activity in different stages of thermal decomposition of AP. Also, in the presence of Cu-Cr-O nanocatalysts, all of the exothermic peaks of AP shifted to a lower temperature, indicating the thermal decomposition of AP was enhanced. Moreover, the heat released (ΔH) in the presence of Cu-Cr-O nanocatalysts was increased to 1490 J g-1.

  11. Multifunctional Thermal Structures Using Cellular Contact-Aided Complaint Mechanisms

    Science.gov (United States)

    2016-10-31

    structure. Based on a finite element formulation and Solid Isotropic Material with Penalization (SIMP) interpolation for material properties...scheme for seeking specific values of the design variables. The objective function was the global mechanical / thermal compliance of the structure. A...Distribution approved for public release. 23 4.3.5 Topology optimization algorithm This section considers the minimization of the “thermal compliance

  12. Theoretical studies on thermal degradation reaction mechanism of model compound of bisphenol A polycarbonate.

    Science.gov (United States)

    Huang, Jinbao; He, Chao; Li, Xinsheng; Pan, Guiying; Tong, Hong

    2018-01-01

    Density functional theory methods (DFT) M062X have been used to investigate the thermal degradation processes of model compound of bisphenol A polycarbonate (MPC) and to identify the optimal reaction paths in the thermal decomposition of bisphenol A polycarbonate (PC). The bond dissociation energies of main bonds in MPC were calculated, and it is found that the weakest bond in MPC is the single bond between the methylic carbon and carbon atom and the second weakest bond in MPC is the single bond between oxygen atom and the carbonyl carbon. On the basis of computational results of kinetic parameters, a mechanism is proposed where the hydrolysis (or alcoholysis) reaction is the main degradation pathways for the formation of the evolved products, and the homolytic cleavage and rearrangement reactions are the competitive reaction pathways in the thermal degradation of PC. The proposed mechanism is consistent with experimental observations of CO2, bisphenol A and 1,1-bis(4-hydroxyphenyl)-ethane as the main degradation products, together with a small amount of CO, alkyl phenol and diphenyl carbonate. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. Improving the Model Fidelity for the Mechanical Response in a Thermal Cookoff of HMX

    Science.gov (United States)

    Nichols, Albert

    2011-06-01

    Understanding the response of energetic materials to adverse thermal environments is necessary to have confidence in the safety those systems. In the past few years we have been improving our thermal-mechanical-chemical modeling of HMX-VitonA based systems. Time to event predictions are very good, to within a degree of the experimental result. However, the chemical network/reaction rates are under constrained, and many networks can achieve the same level of accuracy. Recently, we have significantly improved the mechanical response modeling by the inclusion of porosity and surface tension in the solid species in the reaction network. We discuss the addition of the reversible sublimation/vaporization reactions to the reaction network. This reaction provides a non-reactive pathway yielding mass loss in the lower temperature region in TGA experiments. This implies that a lower decomposition rate can achieve the same overall level of mass loss, thus reducing the gas pressurization in the models of experiments like the Scaled Thermal Explosion eXperiemt. This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. This work was partially funded by the Joint DoD/DOE Munitions Technology Development Program.

  14. HEAVY AND THERMAL OIL RECOVERY PRODUCTION MECHANISMS

    Energy Technology Data Exchange (ETDEWEB)

    Anthony R. Kovscek; Louis M. Castanier

    2002-09-30

    The Stanford University Petroleum Research Institute (SUPRI-A) conducts a broad spectrum of research intended to help improve the recovery efficiency from difficult to produce reservoirs including heavy oil and fractured low permeability systems. Our scope of work is relevant across near-, mid-, and long-term time frames. The primary functions of the group are to conduct direction-setting research, transfer research results to industry, and educate and train students for careers in industry. Presently, research in SUPRI-A is divided into 5 main project areas. These projects and their goals include: (1) Multiphase flow and rock properties--to develop better understanding of the physics of displacement in porous media through experiment and theory. This category includes work on imbibition, flow in fractured media, and the effect of temperature on relative permeability and capillary pressure. (2) Hot fluid injection--to improve the application of nonconventional wells for enhanced oil recovery and elucidate the mechanisms of steamdrive in low permeability, fractured porous media. (3) Mechanisms of primary heavy oil recovery--to develop a mechanistic understanding of so-called ''foamy oil'' and its associated physical chemistry. (4) In-situ combustion--to evaluate the effect of different reservoir parameters on the insitu combustion process. (5) Reservoir definition--to develop and improve techniques for evaluating formation properties from production information. What follows is a report on activities for the past year. Significant progress was made in all areas.

  15. High temperature shock tube and theoretical studies on the thermal decomposition of dimethyl carbonate and its bimolecular reactions with H and D-atoms.

    Science.gov (United States)

    Peukert, S L; Sivaramakrishnan, R; Michael, J V

    2013-05-09

    The shock tube technique was used to study the high temperature thermal decomposition of dimethyl carbonate, CH3OC(O)OCH3 (DMC). The formation of H-atoms was measured behind reflected shock waves by using atomic resonance absorption spectrometry (ARAS). The experiments span a T-range of 1053-1157 K at pressures ∼0.5 atm. The H-atom profiles were simulated using a detailed chemical kinetic mechanism for DMC thermal decomposition. Simulations indicate that the formation of H-atoms is sensitive to the rate constants for the energetically lowest-lying bond fission channel, CH3OC(O)OCH3 → CH3 + CH3OC(O)O [A], where H-atoms form instantaneously at high temperatures from the sequence of radical β-scissions, CH3OC(O)O → CH3O + CO2 → H + CH2O + CO2. A master equation analysis was performed using CCSD(T)/cc-pv∞z//M06-2X/cc-pvtz energetics and molecular properties for all thermal decomposition processes in DMC. The theoretical predictions were found to be in good agreement with the present experimentally derived rate constants for the bond fission channel (A). The theoretically derived rate constants for this important bond-fission process in DMC can be represented by a modified Arrhenius expression at 0.5 atm over the T-range 1000-2000 K as, kA(T) = 6.85 × 10(98)T (-24.239) exp(-65250 K/T) s(-1). The H-atom temporal profiles at long times show only minor sensitivity to the abstraction reaction, H + CH3OC(O)OCH3 → H2 + CH3OC(O)OCH2 [B]. However, H + DMC is an important fuel destruction reaction at high temperatures. Consequently, measurements of D-atom profiles using D-ARAS allowed unambiguous rate constant measurements for the deuterated analog of reaction B, D + CH3OC(O)OCH3 → HD + CH3OC(O)OCH2 [C]. Reaction C is a surrogate for H + DMC since the theoretically predicted kinetic isotope effect at high temperatures (1000 - 2000K) is close to unity, kC ≈ 1.2 kB. TST calculations employing CCSD(T)/cc-pv∞z//M06-2X/cc-pvtz energetics and molecular properties

  16. The thermal decomposition of the benzyl radical in a heated micro-reactor. II. Pyrolysis of the tropyl radical

    Energy Technology Data Exchange (ETDEWEB)

    Buckingham, Grant T. [Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215, USA; National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden Colorado 80401, USA; Porterfield, Jessica P. [Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215, USA; Kostko, Oleg [Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA; Troy, Tyler P. [Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA; Ahmed, Musahid [Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA; Robichaud, David J. [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden Colorado 80401, USA; Nimlos, Mark R. [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden Colorado 80401, USA; Daily, John W. [Department of Mechanical Engineering, Center for Combustion and Environmental Research, University of Colorado, Boulder, Colorado 80309-0427, USA; Ellison, G. Barney [Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215, USA

    2016-07-05

    Cycloheptatrienyl (tropyl) radical, C7H7, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. The pyrolysis products resulting from C7H7 were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 us. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C7H7 are only acetylene and cyclopentadienyl radicals. Tropyl radicals do not isomerize to benzyl radicals at reactor temperatures up to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C7H7) radicals but rather only benzyl (C6H5CH2). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C6H5CH2, C6H5CD2, C6D5CH2, and C6H5 13CH2. Analysis of the temperature dependence for the pyrolysis of the isotopic species (C6H5CD2, C6D5CH2, and C6H5 13CH2) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).

  17. Photocatalytic degradation of methyl orange using ZnO nanopowders synthesized via thermal decomposition of oxalate precursor method

    Science.gov (United States)

    Kaur, Japinder; Bansal, S.; Singhal, Sonal

    2013-05-01

    ZnO nanoparticles were synthesized by thermal decomposition of oxalate precursor method. The nanopowders were characterized using powder X-ray diffraction technique and scanning electron microscopy and sample was found to have hexagonal wurtzite structure of ZnO. Average crystallite size of ZnO was found to be ∼27 nm. The photocatalytic activity of ZnO was evaluated by using methyl orange (MO) as probe molecule. It was inferred from control experiments that presence of both ZnO and UV light is necessary for photodegradation. From photocatalytic experiment it was observed that MO is completely degraded in 80 min when the amount of catalyst is 1 g/L and initial concentration of MO is 0.03 mM. The effect of dye concentration, catalyst loading and solution pH on photodegradation rate was also investigated. It was found that optimal conditions for photodegradation of MO are 1 g/L catalyst at a solution pH 9. Photodegradation of MO was found to follow pseudo-first order kinetics. Langmuir-Hinshelwood model was also used to describe the photodegradation process.

  18. Preparation of magnetic Ni-P amorphous alloy microspheres and their catalytic performance towards thermal decomposition of ammonium perchlorate

    Science.gov (United States)

    Deng, Yi; Yang, Yuanyi; Ge, Liya; Yang, Weizhong; Xie, Kenan

    2017-12-01

    In this work, a series of amorphous Ni-P alloys with diverse microspheric structures and magnetic properties were successfully prepared through a facile aqueous solution reduction using sodium hypophosphite as reducing agent with the assistance of polyvinylpyrrolidone (PVP). Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and laser particle size analysis were used to investigate the structure of Ni-P alloy particles, which demonstrated that the as-prepared alloys possessed spherical morphologies and tunable compositions. We investigated the effects of the synthesis conditions including reaction temperature, initial Ni2+ concentration, pH value, and surfactant type on the morphologies and chemical constitutes of Ni-P alloy particles. Compared with other microsphere counterparts (ferromagnetism), the spherical Ni-P alloy powders with diameter of about 500 nm exhibited apparent paramagnetism. In addition, the catalytic performance of the products on the thermal decomposition of ammonium perchlorate (AP) was further investigated via thermogravimetric analysis (TG) and differential scanning calorimetry (DSC). These Ni-P noncrystalline alloy particles with different magnetic properties and good catalytic activities would broaden the technological and industrial applications of Ni-P alloys in petrochemical reaction, soft magnetic devices, and burning rate catalysts.

  19. Photocatalytical Properties and Theoretical Analysis of N, Cd-Codoped TiO2 Synthesized by Thermal Decomposition Method

    Directory of Open Access Journals (Sweden)

    Hongtao Gao

    2012-01-01

    Full Text Available N, Cd-codoped TiO2 have been synthesized by thermal decomposition method. The products were characterized by X-ray diffraction (XRD, scanning electron microscope (SEM, UV-visible diffuse reflectance spectra (DRS, X-ray photoelectron spectroscopy (XPS, and Brunauer-Emmett-Teller (BET specific surface area analysis, respectively. The products represented good performance in photocatalytic degradation of methyl orange. The effect of the incorporation of N and Cd on electronic structure and optical properties of TiO2 was studied by first-principle calculations on the basis of density functional theory (DFT. The impurity states, introduced by N 2p or Cd 5d, lied between the valence band and the conduction band. Due to dopants, the band gap of N, Cd-codoped TiO2 became narrow. The electronic transition from the valence band to conduction band became easy, which could account for the observed photocatalytic performance of N, Cd-codoped TiO2. The theoretical analysis might provide a probable reference for the experimentally element-doped TiO2 synthesis.

  20. Pyrolysis of aseptic packages (tetrapak) in a laboratory screw type reactor and secondary thermal/catalytic tar decomposition.

    Science.gov (United States)

    Haydary, J; Susa, D; Dudáš, J

    2013-05-01

    Pyrolysis of aseptic packages (tetrapak cartons) in a laboratory apparatus using a flow screw type reactor and a secondary catalytic reactor for tar cracking was studied. The pyrolysis experiments were realized at temperatures ranging from 650 °C to 850 °C aimed at maximizing of the amount of the gas product and reducing its tar content. Distribution of tetrapak into the product yields at different conditions was obtained. The presence of H2, CO, CH4, CO2 and light hydrocarbons, HCx, in the gas product was observed. The Aluminum foil was easily separated from the solid product. The rest part of char was characterized by proximate and elemental analysis and calorimetric measurements. The total organic carbon in the tar product was estimated by elemental analysis of tars. Two types of catalysts (dolomite and red clay marked AFRC) were used for catalytic thermal tar decomposition. Three series of experiments (without catalyst in a secondary cracking reactor, with dolomite and with AFRC) at temperatures of 650, 700, 750, 800 and 850 °C were carried out. Both types of catalysts have significantly affected the content of tars and other components in pyrolytic gases. The effect of catalyst on the tetrapack distribution into the product yield on the composition of gas and on the total organic carbon in the tar product is presented in this work. Copyright © 2013 Elsevier Ltd. All rights reserved.

  1. Experimental and modeling study of the thermal decomposition of C3-C5 ethyl esters behind reflected shock waves.

    Science.gov (United States)

    Ren, Wei; Spearrin, R Mitchell; Davidson, David F; Hanson, Ronald K

    2014-03-13

    The thermal decomposition of three ethyl esters, ethyl formate (C3H6O2), ethyl acetate (C4H8O2), and ethyl propanoate (C5H10O2), was studied behind reflected shock waves using laser absorption to measure concentration time-histories of H2O, CO2, and CO. Experimental conditions covered temperatures of 1301-1636 K, pressures of 1.48-1.72 atm, and reactant concentrations of 2000 ppm in argon. Recently developed mid-infrared laser diagnostics for H2O (2.5 μm), CO2 (4.3 μm), and CO (4.6 μm) provide orders-of-magnitude greater detectivity compared to previous near-infrared absorption sensors. The experimental results have highlighted significant differences among these three ethyl esters: negligible CO2 production during ethyl formate pyrolysis, quite slow CO formation rate during ethyl acetate pyrolysis, and nearly equal formation rate of H2O, CO2, and CO during ethyl propanoate pyrolysis. Detailed kinetic modeling was performed to understand the destruction pathways of these three ethyl esters with different alkyl chain lengths. Rate of production and sensitivity analyses were also carried out to interpret the experimental results and to identify the key reactions affecting experimental results.

  2. Activity of nanosized titania synthesized from thermal decomposition of titanium (IV n-butoxide for the photocatalytic degradation of diuron

    Directory of Open Access Journals (Sweden)

    Jitlada Klongdee, Wansiri Petchkroh, Kosin Phuempoonsathaporn, Piyasan Praserthdam, Alisa S. Vangnai and Varong Pavarajarn

    2005-01-01

    Full Text Available Nanoparticles of anatase titania were synthesized by the thermal decomposition of titanium (IV n-butoxide in 1,4-butanediol. The powder obtained was characterized by various characterization techniques, such as XRD, BET, SEM and TEM, to confirm that it was a collection of single crystal anatase with particle size smaller than 15 nm. The synthesized titania was employed as catalyst for the photodegradation of diuron, a herbicide belonging to the phenylurea family, which has been considered as a biologically active pollutant in soil and water. Although diuron is chemically stable, degradation of diuron by photocatalyzed oxidation was found possible. The conversions achieved by titania prepared were in the range of 70–80% within 6 h of reaction, using standard UV lamps, while over 99% conversion was achieved under solar irradiation. The photocatalytic activity was compared with that of the Japanese Reference Catalyst (JRC-TIO-1 titania from the Catalysis Society of Japan. The synthesized titania exhibited higher rate and efficiency in diuron degradation than reference catalyst. The results from the investigations by controlling various reaction parameters, such as oxygen dissolved in the solution, diuron concentration, as well as light source, suggested that the enhanced photocatalytic activity was the result from higher crystallinity of the synthesized titania.

  3. Novel Recovery of Nano-Structured Ceria (CeO2 from Ce(III-Benzoxazine Dimer Complexes via Thermal Decomposition

    Directory of Open Access Journals (Sweden)

    Nattamon Koonsaeng

    2011-07-01

    Full Text Available N,N-bis(2-hydroxybenzylalkylamines, benzoxazine dimers, are the major product produced from benzoxazine monomers on mono-functional phenol by the one  step ring opening reaction. Due to the metal responsive property of benzoxazine dimers, in this present work, N,N-bis(5-methyl-2-hydroxybenzylmethylamine (MMD, N,N-bis (5-ethyl-2-hydroxybenzylmethylamine (EMD, and N,N-bis(5-methoxy-2-hydroxybenzyl methyl amine (MeMD, are considered as novel ligands for rare earth metal ion, such as cerium(III ion. The complex formed when the clear and colorless solutions of cerium nitrate and benzoxazine dimers were mixed, results in a brown colored solution. The metal-ligand ratios determined by the molar ratio and the Job’s methods were found to be in a ratio of 1:6. To clarify the evidence of the complex formation mechanism, the interactions among protons in benzoxazine dimers both prior to and after the formation of complexes were determined by means of 1H-NMR, 2D-NMR and a computational simulation. The single phase ceria (CeO2 was successfully prepared by thermal decomposition of the Ce(III-benzoxazine dimer complexes at 600 °C for 2 h, was then characterized using XRD. In addition, the ceria powder investigated by TEM is spherical with an average diameter of 20 nm.

  4. Mechanism of metal-independent decomposition of organic hydroperoxides and formation of alkoxyl radicals by halogenated quinones

    Science.gov (United States)

    Zhu, Ben-Zhan; Zhao, Hong-Tao; Kalyanaraman, Balaraman; Liu, Jun; Shan, Guo-Qiang; Du, Yu-Guo; Frei, Balz

    2007-01-01

    The metal-independent decomposition of organic hydroperoxides and the formation of organic alkoxyl radicals in the absence or presence of halogenated quinones were studied with electron spin resonance (ESR) and the spin-trapping agent 5,5-dimethyl-1-pyrroline N-oxide (DMPO). We found that 2,5-dichloro-1,4-benzoquinone (DCBQ) markedly enhanced the decomposition of tert-butylhydroperoxide (t-BuOOH), leading to the formation of the DMPO adducts with t-butoxyl radicals (t-BuO•) and methyl radicals (•CH3). The formation of DMPO/t-BuO• and DMPO/•CH3 was dose-dependent with respect to both DCBQ and t-BuOOH and was not affected by iron- or copper-specific metal chelators. Comparison of the data obtained with DCBQ and t-BuOOH with those obtained in a parallel study with ferrous iron and t-BuOOH strongly suggested that t-BuO• was produced by DCBQ and t-BuOOH through a metal-independent mechanism. Other halogenated quinones were also found to enhance the decomposition of t-BuOOH and other organic hydroperoxides such as cumene hydroperoxide, leading to the formation of the respective organic alkoxyl radicals in a metal-independent manner. Based on these data, we propose a mechanism for DCBQ-mediated t-BuOOH decomposition and formation of t-BuO•: a nucleophilic attack of t-BuOOH on DCBQ, forming a chloro-t-butylperoxyl-1,4-benzoquinone intermediate, which decomposes homolytically to produce t-BuO•. This represents a mechanism of organic alkoxyl radical formation not requiring the involvement of redox-active transition metal ions. PMID:17360415

  5. Thermal Decomposition of Calcium Perchlorate/Iron-Mineral Mixtures: Implications of the Evolved Oxygen from the Rocknest Eolian Deposit in Gale Crater, Mars

    Science.gov (United States)

    Bruck, A. M.; Sutter, B.; Ming, D. W.; Mahaffy, P.

    2014-01-01

    A major oxygen release between 300 and 500 C was detected by the Mars Curiosity Rover Sample Analysis at Mars (SAM) instrument at the Rocknest eolian deposit. Thermal decomposition of perchlorate (ClO4-) salts in the Rocknest samples are a possible explanation for this evolved oxygen release. Releative to Na-, K-, Mg-, and Fe-perchlorate, the thermal decomposition of Ca-perchlorate in laboratory experiments released O2 in the temperature range (400-500degC) closest to the O2 release temperatures observed for the Rocknest material. Furthermore, calcium perchlorate could have been the source of Cl in the chlorinated-hydrocarbons species that were detected by SAM. Different components in the Martian soil could affect the decomposition temperature of calcium per-chlorate or another oxychlorine species. This interaction of the two components in the soil could result in O2 release temperatures consistent with those detected by SAM in the Rocknest materials. The decomposition temperatures of various alkali metal perchlorates are known to decrease in the presence of a catalyst. The objective of this work is to investigate catalytic interactions on calcium perchlorate from various iron-bearing minerals known to be present in the Rocknest material

  6. Deposition of defected graphene on (001) Si substrates by thermal decomposition of acetone

    Science.gov (United States)

    Milenov, T. I.; Avramova, I.; Valcheva, E.; Avdeev, G. V.; Rusev, S.; Kolev, S.; Balchev, I.; Petrov, I.; Pishinkov, D.; Popov, V. N.

    2017-11-01

    We present results on the deposition and characterization of defected graphene by the chemical vapor deposition (CVD) method. The source of carbon/carbon-containing radicals is thermally decomposed acetone (C2H6CO) in Ar main gas flow. The deposition takes place on (001) Si substrates at about 1150-1160 °C. We established by Raman spectroscopy the presence of single- to few- layered defected graphene deposited on two types of interlayers that possess different surface morphology and consisted of mixed sp2 and sp3 hybridized carbon. The study of interlayers by XPS, XRD, GIXRD and SEM identifies different phase composition: i) a diamond-like carbon dominated film consisting some residual SiC, SiO2 etc.; ii) a sp2- dominated film consisting small quantities of C60/C70 fullerenes and residual Si-O-, Cdbnd O etc. species. The polarized Raman studies confirm the presence of many single-layered defected graphene areas that are larger than few microns in size on the predominantly amorphous carbon interlayers.

  7. Rapid hydrogen gas generation using reactive thermal decomposition of uranium hydride.

    Energy Technology Data Exchange (ETDEWEB)

    Kanouff, Michael P.; Van Blarigan, Peter; Robinson, David B.; Shugard, Andrew D.; Gharagozloo, Patricia E.; Buffleben, George M.; James, Scott Carlton; Mills, Bernice E.

    2011-09-01

    Oxygen gas injection has been studied as one method for rapidly generating hydrogen gas from a uranium hydride storage system. Small scale reactors, 2.9 g UH{sub 3}, were used to study the process experimentally. Complimentary numerical simulations were used to better characterize and understand the strongly coupled chemical and thermal transport processes controlling hydrogen gas liberation. The results indicate that UH{sub 3} and O{sub 2} are sufficiently reactive to enable a well designed system to release gram quantities of hydrogen in {approx} 2 seconds over a broad temperature range. The major system-design challenge appears to be heat management. In addition to the oxidation tests, H/D isotope exchange experiments were performed. The rate limiting step in the overall gas-to-particle exchange process was found to be hydrogen diffusion in the {approx}0.5 {mu}m hydride particles. The experiments generated a set of high quality experimental data; from which effective intra-particle diffusion coefficients can be inferred.

  8. Dependence of Glass Mechanical Properties on Thermal and Pressure History

    DEFF Research Database (Denmark)

    Smedskjær, Morten Mattrup; Bauchy, Mathieu

    Predicting the properties of new glasses prior to manufacturing is a topic attracting great industrial and scientific interest. Mechanical properties are currently of particular interest given the increasing demand for stronger, thinner, and more flexible glasses in recent years. However, as a non......-equilibrium material, the structure and properties of glass depend not only on its composition, but also on its thermal and pressure histories. Here we review our recent findings regarding the thermal and pressure history dependence of indentation-derived mechanical properties of oxide glasses....

  9. Mechanics and thermal management of stretchable inorganic electronics

    Science.gov (United States)

    Song, Jizhou; Feng, Xue; Huang, Yonggang

    2016-01-01

    Stretchable electronics enables lots of novel applications ranging from wearable electronics, curvilinear electronics to bio-integrated therapeutic devices that are not possible through conventional electronics that is rigid and flat in nature. One effective strategy to realize stretchable electronics exploits the design of inorganic semiconductor material in a stretchable format on an elastomeric substrate. In this review, we summarize the advances in mechanics and thermal management of stretchable electronics based on inorganic semiconductor materials. The mechanics and thermal models are very helpful in understanding the underlying physics associated with these systems, and they also provide design guidelines for the development of stretchable inorganic electronics. PMID:27547485

  10. The ammonium nitrate and its mechanism of decomposition in the gas phase: a theoretical study and a DFT benchmark.

    Science.gov (United States)

    Cagnina, Stefania; Rotureau, Patricia; Fayet, Guillaume; Adamo, Carlo

    2013-07-14

    The decomposition mechanism of ammonium nitrate in the gas phase was investigated and fully characterized by means of CBS-QB3 calculations. Five reaction channels were identified, leading to the formation of products (N2, H2O, O2, OH, HNO, NO3) found in the experimental works. The identified mechanism well underlines the origin of the chemical hazard of ammonium nitrate which is related to the exothermicity of the lowest decomposition channels. Furthermore, the high barrier to overcome in the rate determining step well explained the fact that the reaction is not usually spontaneous and requires a significant external stimulus for its onset. An accurate DFT benchmark study was then conducted to determine the most suitable exchange-correlation functional to accurately describe the reaction profile both in terms of structures and thermochemistry. This evaluation supports the use of the M06-2X functional as the best option for the study of ammonium nitrate decomposition and related reactions. Indeed, this level of theory provided the lowest deviations with respect to CBS-QB3 reference values, outperforming functionals especially developed for reaction kinetics.

  11. Major mechanisms contributing to the macrofauna-mediated slow down of litter decomposition

    Czech Academy of Sciences Publication Activity Database

    Frouz, Jan; Špaldoňová, A.; Lhotáková, Z.; Cajthaml, T.

    2015-01-01

    Roč. 91, December (2015), s. 23-31 ISSN 0038-0717 Grant - others:GA ČR(CZ) GAP504/12/1288 Program:GA Institutional support: RVO:60077344 Keywords : alkalinization * Bibio * CN ratio * litter decomposition * mineralization * pyrolysis Subject RIV: DF - Soil Science Impact factor: 4.152, year: 2015

  12. In situ thermally reduced graphene oxide/epoxy composites: thermal and mechanical properties

    Science.gov (United States)

    Olowojoba, Ganiu B.; Eslava, Salvador; Gutierrez, Eduardo S.; Kinloch, Anthony J.; Mattevi, Cecilia; Rocha, Victoria G.; Taylor, Ambrose C.

    2016-10-01

    Graphene has excellent mechanical, thermal, optical and electrical properties and this has made it a prime target for use as a filler material in the development of multifunctional polymeric composites. However, several challenges need to be overcome to take full advantage of the aforementioned properties of graphene. These include achieving good dispersion and interfacial properties between the graphene filler and the polymeric matrix. In the present work, we report the thermal and mechanical properties of reduced graphene oxide/epoxy composites prepared via a facile, scalable and commercially viable method. Electron micrographs of the composites demonstrate that the reduced graphene oxide (rGO) is well dispersed throughout the composite. Although no improvements in glass transition temperature, tensile strength and thermal stability in air of the composites were observed, good improvements in thermal conductivity (about 36 %), tensile and storage moduli (more than 13 %) were recorded with the addition of 2 wt% of rGO.

  13. In situ thermally reduced graphene oxide/epoxy composites: thermal and mechanical properties

    Directory of Open Access Journals (Sweden)

    Ganiu B. Olowojoba

    2016-01-01

    Full Text Available Abstract Graphene has excellent mechanical, thermal, optical and electrical properties and this has made it a prime target for use as a filler material in the development of multifunctional polymeric composites. However, several challenges need to be overcome to take full advantage of the aforementioned properties of graphene. These include achieving good dispersion and interfacial properties between the graphene filler and the polymeric matrix. In the present work, we report the thermal and mechanical properties of reduced graphene oxide/epoxy composites prepared via a facile, scalable and commercially viable method. Electron micrographs of the composites demonstrate that the reduced graphene oxide (rGO is well dispersed throughout the composite. Although no improvements in glass transition temperature, tensile strength and thermal stability in air of the composites were observed, good improvements in thermal conductivity (about 36 %, tensile and storage moduli (more than 13 % were recorded with the addition of 2 wt% of rGO.

  14. Facile, mild and fast thermal-decomposition reduction of graphene oxide in air and its application in high-performance lithium batteries.

    Science.gov (United States)

    Wang, Zhong-li; Xu, Dan; Huang, Yun; Wu, Zhong; Wang, Li-min; Zhang, Xin-bo

    2012-01-25

    We firstly propose a facile, mild and effective thermal-decomposition strategy to prepare high-quality graphene at a low temperature of 300 °C in only 5 min under an ambient atmosphere. Applying the advantage of this strategy that provides an oxidizing atmosphere, pure V(2)O(5)/graphene composite is successfully synthesized and exerts excellent lithium storage properties. This journal is © The Royal Society of Chemistry 2012

  15. Correlation between ionic radii of metals and thermal decomposition of supramolecular structure of azodye complexes

    Science.gov (United States)

    El-Sonbati, A. Z.; Diab, M. A.; El-Bindary, A. A.; Eldesoky, A. M.; Morgan, Sh. M.

    2015-01-01

    An interesting azodye heterocyclic ligand of copper(II), cobalt(II), nickel(II) and uranyl(II) complexes have been synthesized by the reaction of metal salts with 5-(2,3-dimethyl-1-phenylpyrazol-5-one azo)-2-thioxo-4-thiazolidinone (HL) yields 1:1 and 1:2 (M:L) complexes depending on the reaction conditions. The elemental analysis, magnetic moments, spectral (UV-Vis, IR, 1H and 13C NMR and ESR) and thermal studies were used to characterize the isolated complexes. The molecular structures of the ligand tautomers are optimized theoretically and the quantum chemical parameters are calculated. The IR spectra showed that the ligand (HL) act as monobasic tridentate/neutral bidentate through the (sbnd Ndbnd N), enolic (Csbnd O)- and/or oxygen keto moiety groups forming a five/six-membered structures. According to intramolecular hydrogen bond leads to increasing of the complexes stability. The molar conductivities show that all the complexes are non-electrolytes. The ESR spectra indicate that the free electron is in dxy orbital. The calculated bonding parameter indicates that in-plane σ-bonding is more covalent than in-plane π-bonding. The coordination geometry is five/six-coordinated trigonal bipyramidal for complex (1) and octahedral for complexes (2-6). The value of covalency factor β12 and orbital reduction factor K accounts for the covalent nature of the complexes. The activation thermodynamic parameters are calculated using Coats-Redfern and Horowitz-Metzger methods. The synthesized ligand (HL) and its Cu(II) complexes (1, 2 and 4) are screened for their biological activity against bacterial and fungal species. The ligand (HL) showed antimicrobial activities against Escherichia coli. The ligand (HL) and its Cu(II) complexes (2 and 4) have very high antifungal activity against Penicillium italicum. The inhibitive action of ligand (HL), against the corrosion of C-steel in 2 M HCl solution has been investigated using potentiodynamic polarization and electrochemical

  16. Thermal Stability, Combustion Behavior, and Mechanical Property in a Flame-Retardant Polypropylene System

    Directory of Open Access Journals (Sweden)

    Lili Wang

    2017-01-01

    Full Text Available In order to comprehensively improve the strength, toughness, flame retardancy, smoke suppression, and thermal stability of polypropylene (PP, layered double hydroxide (LDH Ni0.2Mg2.8Al–LDH was synthesized by a coprecipitation method coupled with the microwave-hydrothermal treatment. The X-ray diffraction (XRD, morphology, mechanical, thermal, and fire properties for PP composites containing 1 wt %–20 wt % Ni0.2Mg2.8Al–LDH were investigated. The cone calorimeter tests confirm that the peak heat release rate (pk–HRR of PP–20%LDH was decreased to 500 kW/m2 from the 1057 kW/m2 of PP. The pk–HRR, average mass loss rate (AMLR and effective heat of combustion (EHC analysis indicates that the condensed phase fire retardant mechanism of Ni0.2Mg2.8Al–LDH in the composites. The production rate and mean release yield of CO for composites gradually decrease as Ni0.2Mg2.8Al–LDH increases in the PP matrix. Thermal analysis indicates that the decomposition temperature for PP–5%LDH and PP–10%LDH is 34 °C higher than that of the pure PP. The mechanical tests reveal that the tensile strength of PP–1%LDH is 7.9 MPa higher than that of the pure PP. Furthermore, the elongation at break of PP–10%LDH is 361% higher than PP. In this work, the synthetic LDH Ni0.2Mg2.8Al–LDH can be used as a flame retardant, smoke suppressant, thermal stabilizer, reinforcing, and toughening agent of PP products.

  17. TG-MS analysis and kinetic study for thermal decomposition of six representative components of municipal solid waste under steam atmosphere.

    Science.gov (United States)

    Zhang, Jinzhi; Chen, Tianju; Wu, Jingli; Wu, Jinhu

    2015-09-01

    Thermal decomposition of six representative components of municipal solid waste (MSW, including lignin, printing paper, cotton, rubber, polyvinyl chloride (PVC) and cabbage) was investigated by thermogravimetric-mass spectroscopy (TG-MS) under steam atmosphere. Compared with TG and derivative thermogravimetric (DTG) curves under N2 atmosphere, thermal decomposition of MSW components under steam atmosphere was divided into pyrolysis and gasification stages. In the pyrolysis stage, the shapes of TG and DTG curves under steam atmosphere were almost the same with those under N2 atmosphere. In the gasification stage, the presence of steam led to a greater mass loss because of the steam partial oxidation of char residue. The evolution profiles of H2, CH4, CO and CO2 were well consistent with DTG curves in terms of appearance of peaks and relevant stages in the whole temperature range, and the steam partial oxidation of char residue promoted the generation of more gas products in high temperature range. The multi-Gaussian distributed activation energy model (DAEM) was proved plausible to describe thermal decomposition behaviours of MSW components under steam atmosphere. Copyright © 2015 Elsevier Ltd. All rights reserved.

  18. Influence of thermal-decomposition temperatures on structures and properties of V2O5 as cathode materials for lithium ion battery

    Directory of Open Access Journals (Sweden)

    Yu Chen

    2015-02-01

    Full Text Available Submicron spherical V2O5 particles with a uniform size and a lower crystallinity were successfully synthesized by a chemical precipitation-thermal decomposition technique using the commercial V2O5 powders as starting material. The crystal structure and grain morphology of samples were characterized by X-ray diffraction (XRD and scanning electron microscopy (SEM, respectively. Electrochemical testing such as discharge–charge cycling (CD and cyclic voltammetry (CV were employed in evaluating their electrochemical properties as cathode materials for lithium ion battery. Results reveal that the crystallinity and crystalline size of V2O5 particles increased when the thermal-decomposition temperature increased from 400 °C to 500 °C, and their adhesiveness was also synchronously increased. This indicate that the thermal-decomposition temperature palyed a significant influence on electrochemical properties of V2O5 cathodes. The V2O5 sample obtained at 400 °C delivered not only a high initial discharge capacity of 330 mA h g−1 and also the good cycle stability during 50 cycles due to its higher values of α in crystal structure and better dispersity in grain morphology.

  19. Enhanced mechanical, thermal, and electric properties of graphene aerogels via supercritical ethanol drying and high-temperature thermal reduction

    OpenAIRE

    Yehong Cheng; Shanbao Zhou; Ping Hu; Guangdong Zhao; Yongxia Li; Xinghong Zhang; Wenbo Han

    2017-01-01

    Graphene aerogels with high surface areas, ultra-low densities and thermal conductivities have been prepared to exploit their wide applications from pollution adsorption to energy storage, supercapacitor, and thermal insulation. However, the low mechanical properties, poor thermal stability and electric conductivity restrict these aerogels? applications. In this paper, we prepared mechanically strong graphene aerogels with large BET surface areas, low thermal conductivities, high thermal stab...

  20. Chemical, thermal and mechanical stabilities of metal-organic frameworks

    Science.gov (United States)

    Howarth, Ashlee J.; Liu, Yangyang; Li, Peng; Li, Zhanyong; Wang, Timothy C.; Hupp, Joseph T.; Farha, Omar K.

    2016-03-01

    The construction of thousands of well-defined, porous, metal-organic framework (MOF) structures, spanning a broad range of topologies and an even broader range of pore sizes and chemical functionalities, has fuelled the exploration of many applications. Accompanying this applied focus has been a recognition of the need to engender MOFs with mechanical, thermal and/or chemical stability. Chemical stability in acidic, basic and neutral aqueous solutions is important. Advances over recent years have made it possible to design MOFs that possess different combinations of mechanical, thermal and chemical stability. Here, we review these advances and the associated design principles and synthesis strategies. We focus on how these advances may render MOFs effective as heterogeneous catalysts, both in chemically harsh condensed phases and in thermally challenging conditions relevant to gas-phase reactions. Finally, we briefly discuss future directions of study for the production of highly stable MOFs.

  1. Effect of high thermal expansion glass infiltration on mechanical ...

    Indian Academy of Sciences (India)

    Administrator

    Abstract. This work studies the effect on the mechanical properties of alumina-10 wt% zirconia (3 mol% yttria stabilized) composite by infiltrating glass of a higher thermal expansion (soda lime glass) on the surface at high temperature. The glass improved the strength of composite at room temperature as well as at high.

  2. Preparation and studies of some thermal, mechanical and optical ...

    Indian Academy of Sciences (India)

    Unknown

    Preparation and studies of some thermal, mechanical and optical properties of xAl2O3(1 – x)NaPO3 glass system. K V SHAH, V SUDARSAN†, M GOSWAMI, A SARKAR, S MANIKANDAN,. RAKESH KUMAR, B I SHARMA, V K SHRIKHANDE and G P KOTHIYAL*. Technical Physics and Prototype Engineering Division, ...

  3. Statistical mechanics of thermal denaturation of DNA oligomers

    Indian Academy of Sciences (India)

    Statistical mechanics of thermal denaturation of DNA oligomers. NAVIN SINGH and YASHWANT SINGH. Department of Physics, Banaras Hindu University, Varanasi 221 005, India. Email: ysingh@bhu.ac.in. Abstract. Double stranded DNA chain is known to have non-trivial elasticity. We study the effect of this elasticity on ...

  4. Thermal and mechanical modelling of convergent plate margins

    NARCIS (Netherlands)

    van den Beukel, P.J.

    1990-01-01

    In this thesis, the thermal and mechanical structure of convergent plate margins will be investigated by means of numerical modelling. In addition, we will discuss the implications of modelling results for geological processes such as metamorphism or the break-up of a plate at a convergent plate

  5. Thermal degradation mechanism of addition-cure liquid silicone rubber with urea-containing silane

    Energy Technology Data Exchange (ETDEWEB)

    Fang, Weizhen; Zeng, Xingrong, E-mail: psxrzeng@gmail.com; Lai, Xuejun; Li, Hongqiang; Chen, Wanjuan; Zhang, Yajun

    2015-04-10

    Highlights: • The urea-containing silane was incorporated into addition-cure liquid silicone rubber (ALSR) via hydrosilylation reaction. • The thermal stability of the ALSR was improved by DEUPAS both in nitrogen and air • The TG–FTIR of evolved gases during degradation was performed. • The possible degradation mechanism of the ALSR samples was proposed. - Abstract: The reactive urea-containing silane, (γ-diethylureidopropyl) allyloxyethoxysilane (DEUPAS), was synthesized by the trans-etherification reaction. The chemical structure was characterized by Fourier transform infrared spectrometry (FTIR) and {sup 1}H nuclear magnetic resonance spectrometry ({sup 1}H NMR). Subsequently, DEUPAS was incorporated into addition-cure liquid silicone rubber (ALSR) via hydrosilylation reaction. The thermal stability of the ALSR samples was investigated by thermogravimetry (TG) and thermogravimetry–Fourier transform infrared spectrometry (TG–FTIR). When DEUPAS was incorporated, the temperature of 10% weight loss and 20% weight loss under air atmosphere were respectively increased by 31 °C and 60 °C compared with those of the ALSR without DEUPAS. Meanwhile, the residual weight at 800 °C increased from 33.5% to 58.7%. It was found that the striking enhancement in thermal stability of the ALSR samples was likely attributed to the decomposition of the urea groups to isocyanic acid, which reacted with hydroxyl groups to inhibit the unzipping depolymerization.

  6. A mechanism of Pennsylvania anthracite graphitization involving carbide formation and decomposition

    Science.gov (United States)

    Pappano, Peter Jarod

    Four Pennsylvania anthracites were selected for this research based on presumed geological differences, in terms of mineral matter type and content, as well as amount of fixed carbon content. The LCNN, UAE, Joddo, and Summit anthracites were all heat-treated to the same temperatures for the same period of time, based on heating rate and soak time at maximum temperature. The heat-treatment temperatures were 2000, 2200, 2500, and 2640°C with a soak time of one hour. After heat-treatment it was found that all the anthracites graphitized, as evidenced by the presence of a weak (112) X-ray diffraction peak, but that the Summit anthracite achieved the highest degree of graphitization, in terms of d-spacing closest to 3.354 A and largest crystallite dimensions. It was also determined that a non graphite phase was present in the 2200°C heat-treated anthracites, and that this non-graphite phase must be a reaction product, or carbide, formed from the carbon of the anthracite and metallic elements of the minerals. The carbide phase was no longer present in the 2500°C heat-treated anthracites, meaning that the carbide must have decomposed. The possibility that this carbide formation and decomposition was involved in promoting graphitization was examined by demineralizing the Summit anthracite and adding the minerals rutile, quartz, iron oxide, and calcite back into this demineralized sample, as well as to the least graphitizing Joddo anthracite. These four minerals were selected because of computer controlled scanning electron microscopy (CCSEM) data, plasma emission data, and literature on industrial production of carbides and carbon electrode additives. The result of this demineralization and re-mineralization was that the Jeddo sample with added minerals achieved a higher degree of graphitization than the raw Jeddo anthracite, and that the demineralized Summit anthracite could no longer be considered a gaphitizing carbon because the (112) peak was absent from the 2600

  7. Terahertz time domain spectroscopy of amorphous and crystalline aluminum oxide nanostructures synthesized by thermal decomposition of AACH

    Energy Technology Data Exchange (ETDEWEB)

    Mehboob, Shoaib, E-mail: smehboob@pieas.edu.pk [National Center for Nanotechnology, Department of Metallurgy and Materials Engineering, Pakistan Institute of Engineering and Applied Sciences (PIEAS), Nilore 45650, Islamabad (Pakistan); Mehmood, Mazhar [National Center for Nanotechnology, Department of Metallurgy and Materials Engineering, Pakistan Institute of Engineering and Applied Sciences (PIEAS), Nilore 45650, Islamabad (Pakistan); Ahmed, Mushtaq [National Institute of Lasers and Optronics (NILOP), Nilore 45650, Islamabad (Pakistan); Ahmad, Jamil; Tanvir, Muhammad Tauseef [National Center for Nanotechnology, Department of Metallurgy and Materials Engineering, Pakistan Institute of Engineering and Applied Sciences (PIEAS), Nilore 45650, Islamabad (Pakistan); Ahmad, Izhar [National Institute of Lasers and Optronics (NILOP), Nilore 45650, Islamabad (Pakistan); Hassan, Syed Mujtaba ul [National Center for Nanotechnology, Department of Metallurgy and Materials Engineering, Pakistan Institute of Engineering and Applied Sciences (PIEAS), Nilore 45650, Islamabad (Pakistan)

    2017-04-15

    The objective of this work is to study the changes in optical and dielectric properties with the transformation of aluminum ammonium carbonate hydroxide (AACH) to α-alumina, using terahertz time domain spectroscopy (THz-TDS). The nanostructured AACH was synthesized by hydrothermal treatment of the raw chemicals at 140 °C for 12 h. This AACH was then calcined at different temperatures. The AACH was decomposed to amorphous phase at 400 °C and transformed to δ* + α-alumina at 1000 °C. Finally, the crystalline α-alumina was achieved at 1200 °C. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy were employed to identify the phases formed after calcination. The morphology of samples was studied using scanning electron microscopy (SEM), which revealed that the AACH sample had rod-like morphology which was retained in the calcined samples. THz-TDS measurements showed that AACH had lowest refractive index in the frequency range of measurements. The refractive index at 0.1 THZ increased from 2.41 for AACH to 2.58 for the amorphous phase and to 2.87 for the crystalline α-alumina. The real part of complex permittivity increased with the calcination temperature. Further, the absorption coefficient was highest for AACH, which reduced with calcination temperature. The amorphous phase had higher absorption coefficient than the crystalline alumina. - Highlights: • Aluminum oxide nanostructures were obtained by thermal decomposition of AACH. • Crystalline phases of aluminum oxide have higher refractive index than that of amorphous phase. • The removal of heavier ionic species led to the lower absorption of THz radiations.

  8. Molecular mechanism of metal-independent decomposition of organic hydroperoxides by halogenated quinoid carcinogens and the potential biological implications.

    Science.gov (United States)

    Huang, Chun-Hua; Ren, Fu-Rong; Shan, Guo-Qiang; Qin, Hao; Mao, Li; Zhu, Ben-Zhan

    2015-05-18

    Halogenated quinones (XQ) are a class of carcinogenic intermediates and newly identified chlorination disinfection byproducts in drinking water. Organic hydroperoxides (ROOH) can be produced both by free radical reactions and enzymatic oxidation of polyunsaturated fatty acids. ROOH have been shown to decompose to alkoxyl radicals via catalysis by transition metal ions, which may initiate lipid peroxidation or transform further to the reactive aldehydes. However, it is not clear whether XQ react with ROOH in a similar manner to generate alkoxyl radicals metal-independently. By complementary applications of ESR spin-trapping, HPLC/high resolution mass spectrometric and other analytical methods, we found that 2,5-dichloro-1,4-benzoquinone (DCBQ) could significantly enhance the decomposition of a model ROOH tert-butylhydroperoxide, resulting in the formation of t-butoxyl radicals independent of transition metals. On the basis of the above findings, we detected and identified, for the first time, an unprecedented C-centered quinone ketoxy radical. Then, we extended our study to the more physiologically relevant endogenous ROOH 13-hydroperoxy-9,11-octadecadienoic acid and found that DCBQ could also markedly enhance its decomposition to generate the reactive lipid alkyl radicals and the genotoxic 4-hydroxy-2-nonenal (HNE). Similar results were observed with other XQ. In summary, these findings demonstrated that XQ can facilitate ROOH decomposition to produce reactive alkoxyl, quinone ketoxy, lipid alkyl radicals, and genotoxic HNE via a novel metal-independent mechanism, which may explain partly their potential genotoxicity and carcinogenicity.

  9. On the semigroup decomposition of the time evolution of quantum mechanical resonances

    CERN Document Server

    Strauss, Y

    2005-01-01

    A way of utilizing Lax-Phillips type semigroups for the description of the time evolution of resonances for scattering problems involving Hamiltonians with a semibounded spectrum was recently introduced by Y. Strauss. In the proposed framework the evolution is decomposed into a background term and an exponentially decaying resonance term evolving according to a semigroup law given by a Lax-Phillips type semigroup; this is called the semigroup decomposition. However, the proposed framework assumes that the S-matrix in the energy representation is the boundary value on the positive real axis of a bounded analytic function in the upper half-plane. This condition puts strong restrictions on possible applications of this formalism. In this paper it is shown that there is a simple way of weakening the assumptions on the S-matrix analyticity while still obtaining the semigroup decomposition of the evolution of a resonance.

  10. [Mechanism of cyanide and thiocyanate decomposition by an association of Pseudomonas putida and Pseudomonas stutzeri strains].

    Science.gov (United States)

    Grigor'eva, N V; Kondrat'eva, T F; Krasil'nikova, E N; Karavaĭko, G I

    2006-01-01

    The intermediate and terminal products of cyanide and thiocyanate decomposition by individual strains of the genus Pseudomonas, P. putida strain 21 and P. stutzeri strain 18, and by their association were analyzed. The activity of the enzymes of nitrogen and sulfur metabolism in these strains was compared with that of the collection strains P. putida VKM B-2187T and P. stutzeri VKM B-975T. Upon the introduction of CN- and SCN- into cell suspensions of strains 18 and 21 in phosphate buffer (pH 8.8), the production of NH4+ was observed. Due to the high rate of their utilization, NH3, NH4+, and CNO- were absent from the culture liquids of P. putida strain 21 and P. stutzeri strain 18 grown with CN- or SCN-. Both Pseudomonas strains decomposed SCN- via cyanate production. The cyanase activity was 0.75 micromol/(min mg protein) for P. putida strain 21 and 1.26 micromol/(min mg protein) for P. stutzeri strain 18. The cyanase activity was present in the cells grown with SCN- but absent in cells grown with NH4+. Strain 21 of P. putida was a more active CN- decomposer than strain 18 of P. stutzeri. Ammonium and CO2 were the terminal nitrogen and carbon products of CN- and SCN- decomposition. The terminal sulfur products of SCN- decomposition by P. stutzeri strain 18 and P. putida strain 21 were thiosulfate and tetrathionate, respectively. The strains utilized the toxic compounds in the anabolism only, as sources of nitrogen (CN- and SCN-) and sulfur (SCN-). The pathway of thiocyanate decomposition by the association of bacteria of the genus Pseudomonas is proposed based on the results obtained.

  11. Elucidating the decomposition mechanism of energetic materials with geminal dinitro groups using 2-bromo-2-nitropropane photodissociation.

    Science.gov (United States)

    Booth, Ryan S; Lam, Chow-Shing; Brynteson, Matthew D; Wang, Lei; Butler, Laurie J

    2013-10-03

    These experiments photolytically generate two key intermediates in the decomposition mechanisms of energetic materials with nitro substituents, 2-nitropropene, and 2-nitro-2-propyl radicals. These intermediates are produced at high internal energies and access a number of competing unimolecular dissociation channels investigated herein. We use a combination of crossed laser-molecular beam scattering and velocity map imaging to study the photodissociation of 2-bromo-2-nitropropane at 193 nm and the subsequent unimolecular dissociation of the intermediates above. Our results demonstrate that 2-bromo-2-nitropropane has four primary photodissociation pathways: C-Br bond fission yielding the 2-nitro-2-propyl radical, HBr elimination yielding 2-nitropropene, C-N bond fission yielding the 2-bromo-2-propyl radical, and HONO elimination yielding 2-bromopropene. The photofragments are formed with significant internal energy and undergo many secondary dissociation events, including the exothermic dissociation of 2-nitro-2-propyl radicals to NO + acetone. Calculations at the G4//B3LYP/6-311++g(3df,2p) level show that the presence of a radical at a nitroalkyl center changes the mechanism for and substantially lowers the barrier to NO loss. This mechanism involves an intermediate with a three-center ring rather than the intermediate formed during the traditional nitro-nitrite isomerization. The observed dissociation pathways of the 2-nitro-2-propyl radical and 2-nitropropene help elucidate the decomposition mechanism of larger energetic materials with geminal dinitro groups.

  12. Theoretical study of the decomposition mechanism of environmentally friendly insulating medium C3F7CN in the presence of H2O in a discharge

    Science.gov (United States)

    Zhang, Xiaoxing; Li, Yi; Xiao, Song; Tian, Shuangshuang; Deng, Zaitao; Tang, Ju

    2017-08-01

    C3F7CN has been the focus of the alternative gas research field over the past two years because of its excellent insulation properties and environmental characteristics. Experimental studies on its insulation performance have made many achievements. However, few studies on the formation mechanism of the decomposition components exist. A discussion of the decomposition characteristics of insulating media will provide guidance for scientific experimental research and the work that must be completed before further engineering application. In this study, the decomposition mechanism of C3F7CN in the presence of trace H2O under discharge was calculated based on the density functional theory and transition state theory. The reaction heat, Gibbs free energy, and activation energy of different decomposition pathways were investigated. The ionization parameters and toxicity of C3F7CN and various decomposition products were analyzed from the molecular structure perspective. The formation mechanism of the C3F7CN discharge decomposition components and the influence of trace water were evaluated. This paper confirms that C3F7CN has excellent decomposition characteristics, which provide theoretical support for later experiments and related engineering applications. However, the existence of trace water has a negative impact on C3F7CN’s insulation performance. Thus, strict trace water content standards should be developed to ensure dielectric insulation and the safety of maintenance personnel.

  13. Active sites and mechanisms for H2O2 decomposition over Pd catalysts

    Science.gov (United States)

    Plauck, Anthony; Stangland, Eric E.; Dumesic, James A.; Mavrikakis, Manos

    2016-01-01

    A combination of periodic, self-consistent density functional theory (DFT-GGA-PW91) calculations, reaction kinetics experiments on a SiO2-supported Pd catalyst, and mean-field microkinetic modeling are used to probe key aspects of H2O2 decomposition on Pd in the absence of cofeeding H2. We conclude that both Pd(111) and OH-partially covered Pd(100) surfaces represent the nature of the active site for H2O2 decomposition on the supported Pd catalyst reasonably well. Furthermore, all reaction flux in the closed catalytic cycle is predicted to flow through an O–O bond scission step in either H2O2 or OOH, followed by rapid H-transfer steps to produce the H2O and O2 products. The barrier for O–O bond scission is sensitive to Pd surface structure and is concluded to be the central parameter governing H2O2 decomposition activity. PMID:27006504

  14. Thermal-Mechanical Optimization of Folded Core Sandwich Panels for Thermal Protection Systems of Space Vehicles

    Directory of Open Access Journals (Sweden)

    Chen Zhou

    2017-01-01

    Full Text Available The integrated thermal protection system (ITPS is a complicated system that addresses both mechanical and thermal considerations. An M-pattern folded core sandwich panel packed with low-density insulation material provides inherently low mass for a potential ITPS panel. Herein, we identify the most influential geometric parameters and establish a viable, computationally efficient optimization procedure. Variables considered for optimization are geometric dimensions of the ITPS, while temperature and deflection are taken as constraints. A one-dimensional (1D thermal model based on a modified form of the rule of mixtures was established, while a three-dimensional (3D model was adopted for linear static analyses. Parametric models were generated to facilitate a design of experiment (DOE study, and approximate models using radial basis functions were obtained to carry out the optimization process. Sensitivity studies were first conducted to investigate the effect of geometric parameters on the ITPS responses. Then optimizations were performed for both thermal and thermal-mechanical constraints. The results show that the simplified 1D thermal model is able to predict temperature through the ITPS thickness satisfactorily. The combined optimization strategy evidently improves the computational efficiency of the design process showing it can be used for initial design of folded core ITPS.

  15. Thermal decomposition of Ln(C2H5CO2)3·H2O (Ln = Ho, Er, Tm and Yb)

    DEFF Research Database (Denmark)

    Grivel, Jean-Claude

    2012-01-01

    The thermal decomposition of Ho(III), Er(III), Tm(III) and Yb(III) propionate monohydrates in argon was studied by means of thermogravimetry (TG), differential thermal analysis (DTA), IR-spectroscopy and X-ray diffraction (XRD). Dehydration takes place around 90 °C. It is followed...... by the decomposition of the anhydrous propionates to Ln2O2CO3 (Ln = Ho, Er, Tm or Yb) with the evolution of CO2 and 3-pentanone (C2H5COC2H5) between 300 and 400 °C. The further decomposition of Ln2O2CO3 to the respective sesquioxides Ln2O3 is characterized by an intermediate plateau extending from approximately 500......–700 °C in the TG traces. This stage corresponds to an overall composition of Ln2O2.5(CO3)0.5 but is more probably a mixture of Ln2O2CO3 and Ln2O3. The stability of this intermediate state decreases for the lighter rare-earth (RE) compounds studied. Full conversion to Ln2O3 is achieved at about 1,100 °C...

  16. Channel microstructure and thermal insulation mechanism of sepiolite mineral nanofibers.

    Science.gov (United States)

    Wang, Fei; Liang, Jinsheng; Tang, Qingguo; Chen, Cong; Chen, Yalei

    2014-05-01

    The longitudinal and cross sectional TEM images of sepiolite mineral nanofibers were prepared by cutting in the direction parallel and perpendicular to nanofibers, and the channel microstructure of sepiolite nanofibers was studied. The thermal insulation mechanism of sepiolite nanofibers was analyzed according to the diagrammatic sketch obtained from the above experimental method. The results showed that many discontinuously connected bending shape channels with about 23-26 nm in diameter existed in the center region of nanofibers, and many discontinuously connected irregular micropores and mesopores with the size of about 1-9 nm existed on the wall of nanofibers. The main reasons for the formation of channel microstructure in sepiolite nanofibers were their minerogenetic conditions and the interaction between acid and high-speed airflow in the process of nanofibers preparation, and bubbles in the hydrotherm played a significant role in the microstructure formation. The thermal insulation performance of sepiolite nanofibers could be attributed to obstructive and infrared radiative thermal insulation.

  17. Nanoporous Carbon Monoliths with Tunable Thermal Insulation and Mechanical Properties.

    Science.gov (United States)

    Wang, Xiaopeng; Chen, Fenghua; Luo, Zhenhua; Li, Hao; Zhao, Tong

    2016-01-01

    In this work, nanoscale porous carbon monoliths, with excellent compressive strength and thermal insulation, were obtained with a simple method of carbonizing cured phenol-formaldehyde resin/poly(methyl methacrylate) blends. Apparent density, pore size and morphology of the carbon monoliths were tailored by changing the composition, curing process and carbonization temperature. The continuous nanopores played a key role in enhancing mechanical and thermal performance of the carbon materials. When PMMA concentration was 25%, apparent density and thermal conductivity of the nanoporous carbonaceous monoliths were obtained as low as 1.07 g · cm⁻³ and 0.42 W/(m · K), decreasing by 29.4% and 35.4% than that of carbonaceous monoliths obtained from pure PF; while compressive strength of the nanoporous carbonaceous monoliths was as high as 34 MPa, which was improved over five times than that of pure PF carbon monoliths.

  18. Enhanced mechanical, thermal, and electric properties of graphene aerogels via supercritical ethanol drying and high-temperature thermal reduction.

    Science.gov (United States)

    Cheng, Yehong; Zhou, Shanbao; Hu, Ping; Zhao, Guangdong; Li, Yongxia; Zhang, Xinghong; Han, Wenbo

    2017-05-03

    Graphene aerogels with high surface areas, ultra-low densities and thermal conductivities have been prepared to exploit their wide applications from pollution adsorption to energy storage, supercapacitor, and thermal insulation. However, the low mechanical properties, poor thermal stability and electric conductivity restrict these aerogels' applications. In this paper, we prepared mechanically strong graphene aerogels with large BET surface areas, low thermal conductivities, high thermal stability and electric conductivities via hydrothermal reduction and supercritical ethanol drying. Annealing at 1500 °C resulted in slightly increased thermal conductivity and further improvement in mechanical properties, oxidation temperature and electric conductivity of the graphene aerogel. The large BET surface areas, together with strong mechanical properties, low thermal conductivities, high thermal stability and electrical conductivities made these graphene aerogels feasible candidates for use in a number of fields covering from batteries to sensors, electrodes, lightweight conductor and insulation materials.

  19. Majorana Demonstrator Bolted Joint Mechanical and Thermal Analysis

    Energy Technology Data Exchange (ETDEWEB)

    Aguayo Navarrete, Estanislao; Reid, Douglas J.; Fast, James E.

    2012-06-01

    The MAJORANA DEMONSTRATOR is designed to probe for neutrinoless double-beta decay, an extremely rare process with a half-life in the order of 1026 years. The experiment uses an ultra-low background, high-purity germanium detector array. The germanium crystals are both the source and the detector in this experiment. Operating these crystals as ionizing radiation detectors requires having them under cryogenic conditions (below 90 K). A liquid nitrogen thermosyphon is used to extract the heat from the detectors. The detector channels are arranged in strings and thermally coupled to the thermosyphon through a cold plate. The cold plate is joined to the thermosyphon by a bolted joint. This circular plate is housed inside the cryostat can. This document provides a detailed study of the bolted joint that connects the cold plate and the thermosyphon. An analysis of the mechanical and thermal properties of this bolted joint is presented. The force applied to the joint is derived from the torque applied to each one of the six bolts that form the joint. The thermal conductivity of the joint is measured as a function of applied force. The required heat conductivity for a successful experiment is the combination of the thermal conductivity of the detector string and this joint. The thermal behavior of the joint is experimentally implemented and analyzed in this study.

  20. Thermal decomposition of heavy rare-earth butanoates, Ln(C3H7CO2)3 (Ln = Er, Tm, Yb and Lu) in argon

    DEFF Research Database (Denmark)

    Grivel, Jean-Claude; Yue, Zhao; Tang, Xiao

    2016-01-01

    was observed in all four compounds, but its course depends on the rare-earth element. Decomposition to sesquioxides proceeds via the formation of dioxymonocarbonates (Ln2O2CO3) and release of 4-heptanone (C3H7COC3H7) as well as carbon dioxide (CO2) without evidence for an intermediate oxobutanoate stage...... of Ln2O2CO3 and Ln2O3. The stability of this intermediate state seems to decrease with the mass of the rare-earth elements. Complete conversion to Ln2O3 is reached at about 1100 °C. The overall thermal decomposition behaviour of the title compounds is different from previous reports for other rare-earth...

  1. Mechanical and thermal properties of the Czech marbles

    Science.gov (United States)

    Čáchová, Monika; Koňáková, Dana; Vejmelková, Eva; Keppert, Martin; Černý, Robert

    2016-06-01

    The paper is dealing with selected parameters of four marbles with respect to their utilization as building materials. Stones from four function quarries in the Czech Republic were chosen and scopes of physical properties were determined. Basic physical, mechanical and thermal properties belong among studied characteristics. Bulk density of studied marbles is in average 2750 kg/m3, matrix density 2770 kg/m3, open porosity 0.7%. Pore structure show similar distributions. Mechanical properties show more differences; however minimal value of compressive strength was 66.5 MPa, while maximum was 174 MPa. Thermal conductivity of studied marbles was about 2.955 W/mK. Last measured characteristic was specific heat capacity; its average value was 609 J/kgK.

  2. Thermal and mechanical properties of PVDF/PANI blends

    Directory of Open Access Journals (Sweden)

    Luiz Francisco Malmonge

    2010-12-01

    Full Text Available Poly(vinylidene fluoride/polyaniline blends of different composition were synthesized by chemical polymerization of aniline in a mixture of Poly(vinylidene fluoride and N,N-dimethylformamide and their thermal and mechanical behavior was investigated as a function of the polyaniline doping level and the composition using thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis and tensile tests techniques. The results showed the blend obtained presents a good thermal stability with low weight loss up to 300 ºC, assigned to water and solvents evaporation. The glass transition and melting point is not affected by the PANI content in the blend, showing that polymers are no miscible. The films produced present a good sustainability; however the presence of the conducting polymer in the blend increases the tensile strength and the Young modulus, while diminishes the elongation at break, as compared to pure PVDF.

  3. Thermal/Mechanical Measurement and Modeling of Bicycle Disc Brakes

    Directory of Open Access Journals (Sweden)

    Ioan Feier

    2018-02-01

    Full Text Available Brake induced heating has become more difficult to control as bicycle component mass has been reduced. High-power braking with insufficient cooling or thermal capacitance can create excessive temperatures, boiling brake fluid, performance degradation, and damage. To better understand component heating, a disc braking dynamometer has been constructed with a motor driven disc, hydraulic braking, and a miniature wind tunnel. Disc temperatures are studied for various braking scenarios using infrared techniques and thermocouples. A transient, numerical, MATLAB, lumped parameter thermal/mechanical model is created to predict the impact of key design parameters on braking performance and to understand the heat loss mechanisms from the brake system components. Computational fluid dynamics (CFD simulations are used to estimate the disc surface convective cooling coefficients for the model. The final model provides transient temperature predictions based on bicycle velocity and braking power, and successfully matches dynamometer experimental data.

  4. Response of mechanical properties of glasses to their chemical, thermal and mechanical histories

    DEFF Research Database (Denmark)

    Yue, Yuanzheng

    of glass fibers are dependent on the thermal history (measured as fictive temperature), tension, chemical composition and redox state. However, the fictive temperature affects the hardness of bulk glass in a complicated manner, i.e., the effect does not exhibit a clear regularity in the range......Mechanical properties are a key factor to be considered when designing new glass compositions, optimizing glass processing parameters and defining the glass application fields. However, mechanical properties of glasses are complex values since they are influenced by many factors such as structure......, surface, thermal history or excess entropy of the final glass state. Here I review recent progresses in understanding of the responses of mechanical properties of oxide glasses to the compositional variation, thermal history and mechanical deformation. The tensile strength, elastic modulus and hardness...

  5. Bismuth sulphides prepared by thermal and hydrothermal decomposition of a single source precursor: the effect of reaction parameters on morphology, microstructure and catalytic activity.

    Science.gov (United States)

    Siqueira, Guilherme Oliveira; de Oliveira Porto, Arilza; Viana, Marcelo Machado; da Silva, Herculano Vieira; de Souza, Yara Gonçalves; da Silva, Hugo Wallison Alves; de Lima, Geraldo Magela; Matencio, Tulio

    2013-10-14

    Bismuth sulphides were prepared by thermal and hydrothermal decomposition of a precursor, bismuth tris-diethyldithiocarbamate, at different temperatures and times. The obtained results showed that the thermal decomposition of the precursor in a tube furnace was not very appropriate to control particle size and morphology. XRD results showed that at 310 °C the precursor was not fully decomposed but at 500 °C besides the orthorhombic bismuth sulphide, the metallic bismuth also started to be formed. At the highest temperature 1D crystals were formed with an apparent mean crystal size of 138 nm. However, hydrothermal decomposition was shown to be a very suitable method to control particle size and morphology just by varying some parameters such as temperature and time. For 6 hours reaction time, as temperature increased, the apparent mean crystal size decreased. The particle morphology was also very affected by this parameter, at 180 °C only 1D particles (nanorods) with lengths varying from 25 to 4700 nm were formed but at 200 °C not only 1D particles but also 2D particles were (nanosheets) obtained. Bismuth sulphide particles obtained at 180 °C and 24 hours reaction time were shown to be formed mostly by 2D particles compared to those obtained at 6 hours. It was clearly seen that the increase in reaction time and temperature led to the formation of bi-dimensional particles. The presence of 1D crystals in the samples obtained by hydrothermal decomposition at 180 °C/6 h and 180 °C/24 h is responsible for their high catalytic efficiency towards methylene blue dye degradation.

  6. A demodulating approach based on local mean decomposition and its applications in mechanical fault diagnosis

    Science.gov (United States)

    Chen, Baojia; He, Zhengjia; Chen, Xuefeng; Cao, Hongrui; Cai, Gaigai; Zi, Yanyang

    2011-05-01

    Since machinery fault vibration signals are usually multicomponent modulation signals, how to decompose complex signals into a set of mono-components whose instantaneous frequency (IF) has physical sense has become a key issue. Local mean decomposition (LMD) is a new kind of time-frequency analysis approach which can decompose a signal adaptively into a set of product function (PF) components. In this paper, a modulation feature extraction method-based LMD is proposed. The envelope of a PF is the instantaneous amplitude (IA) and the derivative of the unwrapped phase of a purely flat frequency demodulated (FM) signal is the IF. The computed IF and IA are displayed together in the form of time-frequency representation (TFR). Modulation features can be extracted from the spectrum analysis of the IA and IF. In order to make the IF have physical meaning, the phase-unwrapping algorithm and IF processing method of extrema are presented in detail along with a simulation FM signal example. Besides, the dependence of the LMD method on the signal-to-noise ratio (SNR) is also investigated by analyzing synthetic signals which are added with Gaussian noise. As a result, the recommended critical SNRs for PF decomposition and IF extraction are given according to the practical application. Successful fault diagnosis on a rolling bearing and gear of locomotive bogies shows that LMD has better identification capacity for modulation signal processing and is very suitable for failure detection in rotating machinery.

  7. Computationally efficient thermal-mechanical modelling of selective laser melting

    Science.gov (United States)

    Yang, Yabin; Ayas, Can

    2017-10-01

    The Selective laser melting (SLM) is a powder based additive manufacturing (AM) method to produce high density metal parts with complex topology. However, part distortions and accompanying residual stresses deteriorates the mechanical reliability of SLM products. Modelling of the SLM process is anticipated to be instrumental for understanding and predicting the development of residual stress field during the build process. However, SLM process modelling requires determination of the heat transients within the part being built which is coupled to a mechanical boundary value problem to calculate displacement and residual stress fields. Thermal models associated with SLM are typically complex and computationally demanding. In this paper, we present a simple semi-analytical thermal-mechanical model, developed for SLM that represents the effect of laser scanning vectors with line heat sources. The temperature field within the part being build is attained by superposition of temperature field associated with line heat sources in a semi-infinite medium and a complimentary temperature field which accounts for the actual boundary conditions. An analytical solution of a line heat source in a semi-infinite medium is first described followed by the numerical procedure used for finding the complimentary temperature field. This analytical description of the line heat sources is able to capture the steep temperature gradients in the vicinity of the laser spot which is typically tens of micrometers. In turn, semi-analytical thermal model allows for having a relatively coarse discretisation of the complimentary temperature field. The temperature history determined is used to calculate the thermal strain induced on the SLM part. Finally, a mechanical model governed by elastic-plastic constitutive rule having isotropic hardening is used to predict the residual stresses.

  8. 4D Printing with Mechanically Robust, Thermally Actuating Hydrogels.

    Science.gov (United States)

    Bakarich, Shannon E; Gorkin, Robert; in het Panhuis, Marc; Spinks, Geoffrey M

    2015-06-01

    A smart valve is created by 4D printing of hydrogels that are both mechanically robust and thermally actuating. The printed hydrogels are made up of an interpenetrating network of alginate and poly(N-isopropylacrylamide). 4D structures are created by printing the "dynamic" hydrogel ink alongside other static materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Thermal decomposition of specifically phosphorylated D-glucoses and their role in the control of the Maillard reaction.

    Science.gov (United States)

    Yaylayan, Varoujan A; Machiels, David; Istasse, Louis

    2003-05-21

    One of the main shortcomings of the information available on the Maillard reaction is the lack of knowledge to control the different pathways, especially when it is desired to direct the reaction away from the formation of carcinogenic and other toxic substances to more aroma and color generation. The use of specifically phosphorylated sugars may impart some elements of control over the aroma profile generated by the Maillard reaction. Thermal decomposition of 1- and 6-phosphorylated glucoses was studied in the presence and absence of ammonia and selected amino acids through pyrolysis/gas chromatography/mass spectrometry using nonpolar PLOT and medium polar DB-1 columns. The analysis of the data has indicated that glucose-1-phosphate relative to glucose undergoes more extensive phosphate-catalyzed ring opening followed by formation of sugar-derived reactive intermediates as was indicated by a 9-fold increase in the amount of trimethylpyrazine and a 5-fold increase in the amount of 2,3-dimethylpyrazine, when pyrolyzed in the presence of glycine. In addition, glucose-1-phosphate alone generated a 6-fold excess of acetol as compared to glucose. On the other hand, glucose-6-phosphate enhanced retro-aldol reactions initiated from a C-6 hydroxyl group and increased the subsequent formation of furfural and 4-cyclopentene-1,3-dione. Furthermore, it also stabilized 1- and 3-deoxyglucosone intermediates and enhanced the formation of six carbon atom-containing Maillard products derived directly from them through elimination reactions such as 1,6-dimethyl-2,4-dihydroxy-3-(2H)-furanone (acetylformoin), 2-acetylpyrrole, 5-methylfurfural, 5-hydroxymethylfurfural, and 4-hydroxy-2,5-dimethyl-3-(2H)-furanone (Furaneol), due to the enhanced leaving group ability of the phosphate moiety at the C-6 carbon. However, Maillard products generated through the nucleophilic action of the C-6 hydroxyl group such as 2-acetylfuran and 2,3-dihydro-3,5-dihydroxy-4H-pyran-4-one were retarded, due

  10. Mechanical property degradation and microstructural evolution of cast austenitic stainless steels under short-term thermal aging

    Energy Technology Data Exchange (ETDEWEB)

    Lach, Timothy G.; Byun, Thak Sang; Leonard, Keith J.

    2017-12-01

    Mechanical testing and microstructural characterization were performed on short-term thermally aged cast austenitic stainless steels (CASS) to understand the severity and mechanisms of thermal-aging degradation experienced during extended operation of light water reactor (LWR) coolant systems. Four CASS materials – CF3, CF3M, CF8, and CF8M – were thermally aged for 1500 hours at 290 °C, 330 °C, 360 °C, and 400 °C. All four alloys experienced insignificant change in strength and ductility properties but a significant reduction in absorbed impact energy. The primary microstructural and compositional changes during thermal aging were spinodal decomposition of the δ-ferrite into α/ α`, precipitation of G-phase in the δ-ferrite, segregation of solute to the austenite/ ferrite interphase boundary, and growth of M23C6 carbides on the austenite/ferrite interphase boundary. These changes were shown to be highly dependent on chemical composition, particularly the concentration of C and Mo, and aging temperature. A comprehensive model is being developed to correlate the microstructural evolution with mechanical behavior and simulation for predictive evaluations of LWR coolant system components.

  11. Synthesis of SiO{sub x}@CdS core–shell nanoparticles by simple thermal decomposition approach and studies on their optical properties

    Energy Technology Data Exchange (ETDEWEB)

    Kandula, Syam; Jeevanandam, P., E-mail: jeevafcy@iitr.ac.in

    2014-12-05

    Highlights: • SiO{sub x}@CdS nanoparticles have been synthesized by a novel thermal decomposition approach. • The method is easy and there is no need for surface functionalization of silica core. • SiO{sub x}@CdS nanoparticles show different optical properties compared to pure CdS. - Abstract: SiO{sub x}@CdS core–shell nanoparticles have been synthesized by a simple thermal decomposition approach. The synthesis involves two steps. In the first step, SiO{sub x} spheres were synthesized using StÖber’s process. Then, cadmium sulfide nanoparticles were deposited on the SiO{sub x} spheres by the thermal decomposition of cadmium acetate and thiourea in ethylene glycol at 180 °C. Electron microscopy results show uniform deposition of cadmium sulfide nanoparticles on the surface of SiO{sub x} spheres. Electron diffraction patterns confirm crystalline nature of the cadmium sulfide nanoparticles on silica and high resolution transmission electron microscopy images clearly show the lattice fringes due to cubic cadmium sulfide. Diffuse reflectance spectroscopy results show blue shift of band gap absorption of SiO{sub x}@CdS core–shell nanoparticles with respect to bulk cadmium sulfide and this is attributed to quantum size effect. Photoluminescence results show enhancement in intensity of band edge emission and weaker emission due to surface defects in SiO{sub x}@CdS core–shell nanoparticles compared to pure cadmium sulfide nanoparticles.

  12. Computational study of decomposition mechanisms and thermodynamic properties of molecular-type cracking patterns for the highly energetic molecule GZT.

    Science.gov (United States)

    Cheng, Sou-Ro; Cheng, Ken-Fa; Liu, Min-Hsien; Hong, Yaw-Shun; Chen, Cheng

    2013-09-01

    This study uses the Gaussian 03 program and density functional theory B3LYP with three basis set methods-[B3LYP/6-311+G(d,p), B3LYP/6-31+G(2d,p), and B3LYP/6-31G(d,p)]-to model the highly energetic ionic compound diguanidinium 5,5'-azotetrazolate (GZT) to research its decomposition mechanisms and thermodynamic properties. Molecular-type cracking patterns are proposed, which were initiated by heterocyclic ring opening, sequential cracking of the two five-membered rings of GZT, and simultaneous release of N2 molecules; whereas proton transfer, bond-breaking, and atomic rearrangements were performed subsequently. Finally, 15 reaction paths and five transition states were obtained. All possible decomposition species and transition states, including intermediates and products, were identified, and their corresponding enthalpy and Gibbs free energy values were obtained. The results revealed that (1) the maximum activation energy required is 187.8 kJ mol(-1), and the enthalpy change (ΔH) and Gibbs free-energy change (ΔG) of the net reaction are -525.1 kJ mol(-1) and -935.6 kJ mol(-1), respectively; (2) GZT can release large amounts of energy, the main contribution being from the disintegration of the 5,5'-azotetrazolate anion (ZT(2-)) skeleton (ΔH = -598.3 kJ mol(-1)); and (3) the final products contained major amounts of N2 gas, but remaining gas molecules such as HCN and NH3 were obtained, which are in agreement with experimental results. The detailed decomposition simulation results demonstrated the feasibility of this method to calculate the energies of the thermodynamic reactions for the highly energetic GZT and predict the most feasible pathways and the final products.

  13. Hemp Thermal Insulation Concrete with Alternative Binders, Analysis of their Thermal and Mechanical Properties

    Science.gov (United States)

    Sinka, M.; Sahmenko, G.; Korjakins, A.; Radina, L.; Bajare, D.

    2015-11-01

    One of the main challenges that construction industry faces today is how to address the demands for more sustainable, environmentally friendly and carbon neutral construction materials and building upkeep processes. One of the answers to these demands is lime-hemp concrete (LHC) building materials - carbon negative materials that have sufficient thermal insulation capabilities to be used as thermal insulation materials for new as well as for existing buildings. But one problem needs to be overcome before these materials can be used on a large scale - current manufacturing technology allows these materials to be used only as self-bearing thermal insulation material with large labour intensity in the manufacturing process. In order to lower the labour intensity and allow the material to be used in wider applications, a LHC block and board production is necessary, which in turn calls for the binders different from the classically used ones, as they show insufficient mechanical strength for this new use. The particular study focuses on alternative binders produced using gypsum-cement compositions ensuring they are usable in outdoor applications together with hemp shives. Physical, mechanical, thermal and water absorption properties of hemp concrete with various binders are addressed in the current study.

  14. Visible light induced degradation of methyl orange using β-Ag0.333V2O5 nanorod catalysts by facile thermal decomposition method

    Directory of Open Access Journals (Sweden)

    R. Saravanan

    2015-09-01

    Full Text Available One dimensional nanorods of β-Ag0.333V2O5 have been synthesized by facile thermal decomposition method without using any additives. The prepared sample was characterized by different physical and chemical techniques such as XRD, FE-SEM, TEM, DRS and XPS. The photocatalytic activity of β-Ag0.333V2O5 catalyst was investigated by studying the degradation of methyl orange (MO in aqueous medium under visible light exposure. The result shows β-Ag0.333V2O5 exhibits outstanding photocatalytic activity under visible light illumination.

  15. Thermal decomposition of RE(C2H5CO2)3·H2O (RE = Dy, Tb, Gd, Eu and Sm)

    DEFF Research Database (Denmark)

    Grivel, Jean-Claude

    2014-01-01

    The thermal decomposition of Dy(III), Tb(III), Gd(III), Eu(III), and Sm(III) propionate monohydrates was studied in argon by means of simultaneous differential thermal analysis and thermogravimetry, infrared-spectroscopy, X-ray diffraction, and optical microscopy. After dehydration, which takes p...

  16. Acetylated rice starches films with different levels of amylose: Mechanical, water vapor barrier, thermal, and biodegradability properties.

    Science.gov (United States)

    Colussi, Rosana; Pinto, Vânia Zanella; El Halal, Shanise Lisie Mello; Biduski, Bárbara; Prietto, Luciana; Castilhos, Danilo Dufech; Zavareze, Elessandra da Rosa; Dias, Alvaro Renato Guerra

    2017-04-15

    Biodegradable films from native or acetylated starches with different amylose levels were prepared. The films were characterized according to the mechanical, water vapor barrier, thermal, and biodegradability properties. The films from acetylated high amylose starches had higher moisture content and water solubility than the native high amylose starch film. However, the acetylation did not affect acid solubility of the films, regardless of the amylose content. Films made from high and medium amylose rice starches were obtained; however low amylose rice starches, whether native or acetylated, did not form films with desirable characteristics. The acetylation decreased the tensile strength and increased the elongation of the films. The acetylated starch-based films had a lower decomposition temperature and higher thermal stability than native starch films. Acetylated starches films exhibited more rapid degradation as compared with the native starches films. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Downstream evolution of unconfined vortices: mechanical and thermal aspects

    Science.gov (United States)

    Pérez-Saborid, M.; Herrada, M. A.; Gómez-Barea, A.; Barrero, A.

    2002-11-01

    We present a numerical study of the downstream evolution (mechanical and thermal) of vortex-jet cores whose velocity and temperature fields far from the axis match a family of inviscid and non-conducting vortices. The far-velocity field is rotational, except for a particular case which corresponds to the well-known Long's vortex. The evolution of the vortex core depends on both the conditions at a certain upstream station, characterized by the dimensionless value of the velocity at the axis, and a dimensionless swirling parameter L defined as the ratio of the values of the azimuthal and axial velocities outside the vortex core. This numerical study, based on the quasi-cylindrical approximation (QC) of the Navier Stokes equations, determines the conditions under which the vortex evolution proceeds smoothly, eventually reaching an asymptotic self-similar behaviour as described in the literature (Fernández-Feria, Fernández de la Mora & Barrero 1995; Herrada, Pérez-Saborid & Barrero 1999), or breaks in a non-slender solution (vortex breakdown). In particular, the critical value L = Lb(a) beyond which vortex breakdown occurs downstream is a function of a dimensionless parameter a characterizing the axial momentum of the vortex jet at an initial upstream station. It is found numerically that for very large values of a this vortex breakdown criterion tends to an asymptote which is precisely the value L = L* predicted by the self-similar analysis, and beyond which a self-similar structure of the vortex core does not exist. In addition, the computation of the total temperature field provides useful information on the physical mechanisms responsible for the thermal separation phenomenon observed in Ranque Hilsch tubes and other swirling jet devices. In particular, the mechanical work of viscous forces which gives rise to an intense loss of kinetic energy during the initial stages of the evolution has been identified as the physical mechanism responsible for thermal

  18. Decomposition mechanisms and kinetics of novel energetic molecules BNFF-1 and ANFF-1: quantum-chemical modeling.

    Science.gov (United States)

    Tsyshevsky, Roman V; Kuklja, Maija M

    2013-07-18

    Decomposition mechanisms, activation barriers, Arrhenius parameters, and reaction kinetics of the novel explosive compounds, 3,4-bis(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole (BNFF-1), and 3-(4-amino-1,2,5-oxadiazol-3-yl)-4-(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole (ANFF-1) were explored by means of density functional theory with a range of functionals combined with variational transition state theory. BNFF-1 and ANFF-1 were recently suggested to be good candidates for insensitive high energy density materials. Our modeling reveals that the decomposition initiation in both BNFF-1 and ANFF-1 molecules is triggered by ring cleavage reactions while the further process is defined by a competition between two major pathways, the fast C-NO₂ homolysis and slow nitro-nitrite isomerization releasing NO. We discuss insights on design of new energetic materials with targeted properties gained from our modeling.

  19. Decomposition Mechanisms and Kinetics of Novel Energetic Molecules BNFF-1 and ANFF-1: Quantum-Chemical Modeling

    Directory of Open Access Journals (Sweden)

    Maija M. Kuklja

    2013-07-01

    Full Text Available Decomposition mechanisms, activation barriers, Arrhenius parameters, and reaction kinetics of the novel explosive compounds, 3,4-bis(4-nitro-1,2,5-oxadiazol-3-yl-1,2,5-oxadiazole (BNFF-1, and 3-(4-amino-1,2,5-oxadiazol-3-yl-4-(4-nitro-1,2,5-oxadiazol-3-yl-1,2,5-oxadiazole (ANFF-1 were explored by means of density functional theory with a range of functionals combined with variational transition state theory. BNFF-1 and ANFF-1 were recently suggested to be good candidates for insensitive high energy density materials. Our modeling reveals that the decomposition initiation in both BNFF-1 and ANFF-1 molecules is triggered by ring cleavage reactions while the further process is defined by a competition between two major pathways, the fast C-NO2 homolysis and slow nitro-nitrite isomerization releasing NO. We discuss insights on design of new energetic materials with targeted properties gained from our modeling.

  20. Dissociative mechanism for irreversible thermal denaturation of oligomeric proteins.

    Science.gov (United States)

    Chebotareva, Natalia A; Roman, Svetlana G; Kurganov, Boris I

    2016-12-01

    Protein stability is a fundamental characteristic essential for understanding conformational transformations of the proteins in the cell. When using protein preparations in biotechnology and biomedicine, the problem of protein stability is of great importance. The kinetics of denaturation of oligomeric proteins may have characteristic properties determined by the quaternary structure. The kinetic schemes of denaturation can include the multiple stages of conformational transitions in the protein oligomer and stages of reversible dissociation of the oligomer. In this case, the shape of the kinetic curve of denaturation or the shape of the melting curve registered by differential scanning calorimetry can vary with varying the protein concentration. The experimental data illustrating dissociative mechanism for irreversible thermal denaturation of oligomeric proteins have been summarized in the present review. The use of test systems based on thermal aggregation of oligomeric proteins for screening of agents possessing anti-aggregation activity is discussed.

  1. Highly thermally conductive and mechanically strong graphene fibers.

    Science.gov (United States)

    Xin, Guoqing; Yao, Tiankai; Sun, Hongtao; Scott, Spencer Michael; Shao, Dali; Wang, Gongkai; Lian, Jie

    2015-09-04

    Graphene, a single layer of carbon atoms bonded in a hexagonal lattice, is the thinnest, strongest, and stiffest known material and an excellent conductor of heat and electricity. However, these superior properties have yet to be realized for graphene-derived macroscopic structures such as graphene fibers. We report the fabrication of graphene fibers with high thermal and electrical conductivity and enhanced mechanical strength. The inner fiber structure consists of large-sized graphene sheets forming a highly ordered arrangement intercalated with small-sized graphene sheets filling the space and microvoids. The graphene fibers exhibit a submicrometer crystallite domain size through high-temperature treatment, achieving an enhanced thermal conductivity up to 1290 watts per meter per kelvin. The tensile strength of the graphene fiber reaches 1080 megapascals. Copyright © 2015, American Association for the Advancement of Science.

  2. Mechanical and Thermal Characterization of Ultrasonic Additive Manufacturing

    Science.gov (United States)

    Foster, Daniel R.

    Additive manufacturing is an emerging production technology used to create net shaped 3-D objects from a digital model. Ultrasonic Additive Manufacturing (UAM) is a relatively new type of additive manufacturing that uses ultrasonic energy to sequentially bond layers of metal foils at temperatures much lower than the melting temperature of the material. Constructing metal structures without melting allows UAM to have distinct advantages over beam based additive manufacturing and other traditional manufacturing processes. This is because solidification defects can be avoided, structures can be composed of dissimilar material and secondary materials (both metallic and non-metallic) can be successfully embedded into the metal matrix. These advantages allow UAM to have tremendous potential to create metal matrix composite structures that cannot be built using any other manufacturing technique. Although UAM has tremendous engineering potential, the effect of interfacial bonding defects on the mechanical and thermal properties have not be characterized. Incomplete interfacial bonding at the laminar surfaces due to insufficient welding energy can result in interfacial voids. Voids create discontinuities in the structure which change the mechanical and thermal properties of the component, resulting in a structure that has different properties than the monolithic material used to create it. In-situ thermal experiments and thermal modeling demonstrates that voids at partially bonded interfaces significantly affected heat generation and thermal conductivity in. UAM parts during consolidation as well as in the final components. Using ultrasonic testing, elastic properties of UAM structures were found to be significantly reduced due to the presence of voids, with the reduction being the most severe in the transverse (foil staking) direction. Elastic constants in all three material directions decreased linearly with a reduction in the interfacial bonded area. The linear trend

  3. Thin-film methods for examining the decomposition chemistry of explosives

    Energy Technology Data Exchange (ETDEWEB)

    Erickson, K.L.; Trott, W.M.; Renlund, A.M.

    1993-11-01

    Experimental techniques using thin-film samples and infrared spectroscopy have been developed to examine thermally-induced condensed-phase decomposition chemistry of explosives. Experiments with nitrocellulose (NC) and 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) were done to examine the effects of confining the decomposition proucts so that intimate contact was maintained with the remaining explosive during isothermal decomposition at temperatures below those of the respective DTA exotherms. The NC experiments showed that substantial NC decomposition occurred at 150C and confinement of the decomposition products influenced the decomposition reactions. Some of the mechanisms and reaction rates with confined samples compared favorably with published mechanisms and rates from unconfined samples, while other mechanisms and reaction rates differed. The TATB experiments showed that significant TATB degradation occurred at temperatures as low as 210C, and substantial degradation occurred within 24 hours at 250C which is about 80C below the temperature of the DTA exotherm for TATB.

  4. Facile fabrication of Fe{sub 3}O{sub 4} and Co{sub 3}O{sub 4} microspheres and their influence on the thermal decomposition of ammonium perchlorate

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yifu, E-mail: yfzhang@dlut.edu.cn; Meng, Changgong

    2016-07-25

    Fe{sub 3}O{sub 4} and Co{sub 3}O{sub 4} microspheres were successfully synthesized by the hydrothermal decomposition of iron oxalate and cobalt oxalate solution. The composition and morphology of synthesized powders were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. The catalytic properties of the as-obtained Fe{sub 3}O{sub 4} and Co{sub 3}O{sub 4} microspheres on the thermal decomposition of ammonium perchlorate (AP) were evaluated by thermo-gravimetric analysis and differential thermal analysis (TGA/DTA) methods. The thermal decomposition temperatures of AP in the presence of 1, 2, 4 and 8 wt% of Fe{sub 3}O{sub 4} microspheres were respectively decreased by 58, 80, 102 and 129 °C (lowered to 398, 376, 354 and 327 °C). And the thermal decomposition temperatures of AP in the presence of 1, 2, 4 and 8 wt% of Co{sub 3}O{sub 4} microspheres were respectively decreased by 55, 74, 112 and 131 °C (lowered to 401, 382, 344 and 325 °C). The analysis of the thermal gravimetric analyzer couplet with infrared spectroscopy (TG-IR) test reveal that the additives can accelerate the thermal decomposition of AP via the high-temperature decomposition. All the results suggest the as-prepared Fe{sub 3}O{sub 4} and Co{sub 3}O{sub 4} microspheres have highly catalytic properties on the thermal decomposition of AP, which can be used as the promising additives in the future. - Graphical abstract: Real-time FTIR spectra to reveal the thermal decomposition process of AP. - Highlights: • Highly uniform Fe{sub 3}O{sub 4} and Co{sub 3}O{sub 4} microspheres were successfully synthesized. • The T{sub c} of AP with 1, 2, 4 and 8 wt% of Fe{sub 3}O{sub 4} microspheres was decreased by 58, 80, 102 and 129 °C. • The T{sub c} of AP with 1, 2, 4 and 8 wt% of Co{sub 3}O{sub 4} microspheres was decreased by 55, 74, 112 and 131 °C. • The thermal decomposition process of AP was detected by TG-IR.

  5. Thermalization and its mechanism for generic quantum isolated systems

    Science.gov (United States)

    Olshanii, Maxim; Dunjko, Vanja; Rigol, Marcos

    2008-05-01

    Time dynamics of isolated many-body quantum systems has long been an elusive subject, perhaps most urgently needed in the foundations of quantum statistical mechanics. In generic systems, one expects the nonequilibrium dynamics to lead to thermalization: a relaxation to states where the values of macroscopic quantities are stationary, universal with respect to widely differing initial conditions, and predictable through the time-tested recipe of statistical mechanics. The relaxation mechanism is not obvious, however; dynamical chaos cannot play the key role as it does in classical systems since quantum evolution is linear. Here we demonstrateootnotetextM. Rigol, V. Dunjko, and M. Olshanii, to appear in Nature (2008), using the results of an ab initio numerical experiment with 5 hard-core bosons moving in a 5x5 lattice, that in quantum systems thermalization happens not in course of time evolution but instead at the level of individual eigenstates, as first proposed by DeutschootnotetextJ. M. Deutsch, Phys.Rev. A 43, 2046 (1991) and SrednickiootnotetextM. Srednicki, Phys. Rev. E 50, 888 (1994).

  6. The mechanical and thermal setup of the GLORIA spectrometer

    Science.gov (United States)

    Piesch, C.; Sartorius, C.; Friedl-Vallon, F.; Gulde, T.; Heger, S.; Kretschmer, E.; Maucher, G.; Nordmeyer, H.; Barthel, J.; Ebersoldt, A.; Graf, F.; Hase, F.; Kleinert, A.; Neubert, T.; Schillings, H. J.

    2015-04-01

    The novel airborne Gimballed Limb Observer for Radiance Imaging of the Atmosphere (GLORIA) measures infrared emission of atmospheric trace constituents. GLORIA comprises a cooled imaging Fourier transform spectrometer, which is operated in unpressurized aircraft compartments at ambient temperature. The whole spectrometer is pointed by the gimbal towards the atmospheric target. In order to reach the required sensitivity for atmospheric emission measurements, the spectrometer optics needs to operate at a temperature below 220 K. A lightweight and compact design is mandatory due to limited space and high agility requirements. The cooled optical system needs to withstand high pressure and temperature gradients, humidity, and vibrations. A new cooling system based on carbon dioxide and liquid nitrogen combined with high-performance insulation has been developed to meet the mechanical, thermal, and logistical demands. The challenging mechanical and spatial requirements lead to the development of a novel rigid linear slide design in order to achieve the large optical path difference for high spectral resolution. This paper describes the mechanical and thermal setup of GLORIA and presents the performance results on two different research aircrafts.

  7. Mechanical and Thermal Properties of Praseodymium Monopnictides: AN Ultrasonic Study

    Science.gov (United States)

    Bhalla, Vyoma; Kumar, Raj; Tripathy, Chinmayee; Singh, Devraj

    2013-09-01

    We have computed ultrasonic attenuation, acoustic coupling constants and ultrasonic velocities of praseodymium monopnictides PrX(X: N, P, As, Sb and Bi) along the , , in the temperature range 100-500 K using higher order elastic constants. The higher order elastic constants are evaluated using Coulomb and Born-Mayer potential with two basic parameters viz. nearest-neighbor distance and hardness parameter in the temperature range of 0-500 K. Several other mechanical and thermal parameters like bulk modulus, shear modulus, Young's modulus, Poisson ratio, anisotropic ratio, tetragonal moduli, Breazeale's nonlinearity parameter and Debye temperature are also calculated. In the present study, the fracture/toughness (B/G) ratio is less than 1.75 which implies that PrX compounds are brittle in nature at room temperature. The chosen material fulfilled Born criterion of mechanical stability. We also found the deviation of Cauchy's relation at higher temperatures. PrN is most stable material as it has highest valued higher order elastic constants as well as the ultrasonic velocity. Further, the lattice thermal conductivity using modified approach of Slack and Berman is determined at room temperature. The ultrasonic attenuation due to phonon-phonon interaction and thermoelastic relaxation mechanisms have been computed using modified Mason's approach. The results with other well-known physical properties are useful for industrial applications.

  8. Volatilization and Thermal Decomposition Mechanisms of Room-Temperature Ionic Liquids (PRE-PRINT)

    Science.gov (United States)

    2017-03-07

    Date: 20 Nov 2008. 14. ABSTRACT Recent interest in room temperature ionic liquids (RTILs) was based initially on the replacement of volatile...indicated that volatilization of these species occurs as a single ion pair. Recent ALS studies on the photoionization of other 1- alkyl-3...methylimidazolium based RTILs, show these systems can be more complex, with possible dissociative photoionization occurring at even the lowest detectable reservoir

  9. Thermal Decomposition Mechanisms of Alkylimidazolium Ionic Liquids with CN-containing Anions

    Science.gov (United States)

    2014-11-01

    S. P., Heintz, A., Corfield, J.-A., Deyko, A., Lovelock, K. R. J., Licence , P. and Jones, R. G. Journal of Physical Chemistry B, 2008, 112, 11734...Jones, R. G., Licence , P., Lovelock, K. R. J., Satterly, C. J. and Villar-Garcia, I. J. Phys. Chem. Chem. Phys., 2007, 9, 982-990. (45) Holloczki

  10. Thermal decomposition and reconstruction of CaFe-layered double hydroxide studied by X-ray diffractometry and 57Fe Mössbauer spectroscopy

    Science.gov (United States)

    Bugris, Valéria; Ádok-Sipiczki, Mónika; Anitics, Tamás; Kuzmann, Ernő; Homonnay, Zoltán; Kukovecz, Ákos; Kónya, Zoltán; Sipos, Pál; Pálinkó, István

    2015-06-01

    In spite of numerous investigations on the various processes of the thermal decomposition and rehydration of layered double hydroxides (LDHs) by a variety sophisticated experimental means, many details are still unexplored and some contradictions are still unresolved. In this work, our efforts were focussed on clarifying the composition, structure and properties of thermally decomposed metaphases originating from CaFe-LDH, heat treated in the 373-973 K temperature range. The structure reconstruction ability of mixed metal oxide phases obtained after heat treatments was also investigated, mainly concentrating on the changes in the microenvironment of Fe(III), in the presence of controlled amount of water vapour (i.e., at different relative humidities). All samples were characterised by X-ray diffractometry, and the iron-containing phases were studied by 57Fe Mössbauer spectroscopy.

  11. Bulk Nanolaminated Nickel: Preparation, Microstructure, Mechanical Property, and Thermal Stability

    Science.gov (United States)

    Liu, Fan; Yuan, Hao; Goel, Sunkulp; Liu, Ying; Wang, Jing Tao

    2018-02-01

    A bulk nanolaminated (NL) structure with distinctive fractions of low- and high-angle grain boundaries ( f LAGBs and f HAGBs) is produced in pure nickel, through a two-step process of primary grain refinement by equal-channel angular pressing (ECAP), followed by a secondary geometrical refinement via liquid nitrogen rolling (LNR). The lamellar boundary spacings of 2N and 4N nickel are refined to 40 and 70 nm, respectively, and the yield strength of the NL structure in 2N nickel reaches 1.5 GPa. The impacts of the deformation path, material purity, grain boundary (GB) misorientation, and energy on the microstructure, refinement ability, mechanical strength, and thermal stability are investigated to understand the inherent governing mechanisms. GB migration is the main restoration mechanism limiting the refinement of an NL structure in 4N nickel, while in 2N nickel, shear banding occurs and mediates one-fifth of the total true normal rolling strain at the mesoscale, restricting further refinement. Three typical structures [ultrafine grained (UFG), NL with low f LAGBs, and NL with high f LAGBs] obtained through three different combinations of ECAP and LNR were studied by isochronal annealing for 1 hour at temperatures ranging from 433 K to 973 K (160 °C to 700 °C). Higher thermal stability in the NL structure with high f LAGBs is shown by a 50 K (50 °C) delay in the initiation temperature of recrystallization. Based on calculations and analyses of the stored energies of deformed structures from strain distribution, as characterized by kernel average misorientation (KAM), and from GB misorientations, higher thermal stability is attributed to high f LAGBs in this type of NL structure. This is confirmed by a slower change in the microstructure, as revealed by characterizing its annealing kinetics using KAM maps.

  12. Bulk Nanolaminated Nickel: Preparation, Microstructure, Mechanical Property, and Thermal Stability

    Science.gov (United States)

    Liu, Fan; Yuan, Hao; Goel, Sunkulp; Liu, Ying; Wang, Jing Tao

    2017-11-01

    A bulk nanolaminated (NL) structure with distinctive fractions of low- and high-angle grain boundaries (f LAGBs and f HAGBs) is produced in pure nickel, through a two-step process of primary grain refinement by equal-channel angular pressing (ECAP), followed by a secondary geometrical refinement via liquid nitrogen rolling (LNR). The lamellar boundary spacings of 2N and 4N nickel are refined to 40 and 70 nm, respectively, and the yield strength of the NL structure in 2N nickel reaches 1.5 GPa. The impacts of the deformation path, material purity, grain boundary (GB) misorientation, and energy on the microstructure, refinement ability, mechanical strength, and thermal stability are investigated to understand the inherent governing mechanisms. GB migration is the main restoration mechanism limiting the refinement of an NL structure in 4N nickel, while in 2N nickel, shear banding occurs and mediates one-fifth of the total true normal rolling strain at the mesoscale, restricting further refinement. Three typical structures [ultrafine grained (UFG), NL with low f LAGBs, and NL with high f LAGBs] obtained through three different combinations of ECAP and LNR were studied by isochronal annealing for 1 hour at temperatures ranging from 433 K to 973 K (160 °C to 700 °C). Higher thermal stability in the NL structure with high f LAGBs is shown by a 50 K (50 °C) delay in the initiation temperature of recrystallization. Based on calculations and analyses of the stored energies of deformed structures from strain distribution, as characterized by kernel average misorientation (KAM), and from GB misorientations, higher thermal stability is attributed to high f LAGBs in this type of NL structure. This is confirmed by a slower change in the microstructure, as revealed by characterizing its annealing kinetics using KAM maps.

  13. Dynamic mechanical thermal analysis of hypromellose 2910 free films.

    Science.gov (United States)

    Cespi, Marco; Bonacucina, Giulia; Mencarelli, Giovanna; Casettari, Luca; Palmieri, Giovanni Filippo

    2011-10-01

    It is common practice to coat oral solid dosage forms with polymeric materials for controlled release purposes or for practical and aesthetic reasons. Good knowledge of thermo-mechanical film properties or their variation as a function of polymer grade, type and amount of additives or preparation method is of prime importance in developing solid dosage forms. This work focused on the dynamic mechanical thermal characteristics of free films of hypromellose 2910 (also known as HPMC), prepared using three grades of this polymer from two different manufacturers, in order to assess whether polymer chain length or origin affects the mechanical or thermo-mechanical properties of the final films. Hypromellose free films were obtained by casting their aqueous solutions prepared at a specific concentrations in order to obtain the same viscosity for each. The films were stored at room temperature until dried and then examined using a dynamic mechanical analyser. The results of the frequency scans showed no significant differences in the mechanical moduli E' and E″ of the different samples when analysed at room temperature; however, the grade of the polymer affected material transitions during the heating process. Glass transition temperature, apparent activation energy and fragility parameters depended on polymer chain length, while the material brand showed little impact on film performance. Copyright © 2011 Elsevier B.V. All rights reserved.

  14. Thermal Degradation, Mechanical Properties and Morphology of Wheat Straw Flour Filled Recycled Thermoplastic Composites.

    Science.gov (United States)

    Mengeloglu, Fatih; Karakus, Kadir

    2008-01-24

    Thermal behaviors of wheat straw flour (WF) filled thermoplastic compositeswere measured applying the thermogravimetric analysis and differential scanningcalorimetry. Morphology and mechanical properties were also studied using scanningelectron microscope and universal testing machine, respectively. Presence of WF inthermoplastic matrix reduced the degradation temperature of the composites. One for WFand one for thermoplastics, two main decomposition peaks were observed. Morphologicalstudy showed that addition of coupling agent improved the compatibility between WFs andthermoplastic. WFs were embedded into the thermoplastic matrix indicating improvedadhesion. However, the bonding was not perfect because some debonding can also be seenon the interface of WFs and thermoplastic matrix. In the case of mechanical properties ofWF filled recycled thermoplastic, HDPE and PP based composites provided similar tensileand flexural properties. The addition of coupling agents improved the properties ofthermoplastic composites. MAPE coupling agents performed better in HDPE while MAPPcoupling agents were superior in PP based composites. The composites produced with thecombination of 50-percent mixture of recycled HDPE and PP performed similar with theuse of both coupling agents. All produced composites provided flexural properties requiredby the ASTM standard for polyolefin-based plastic lumber decking boards.

  15. Thermal Degradation, Mechanical Properties and Morphology of Wheat Straw Flour Filled Recycled Thermoplastic Composites

    Directory of Open Access Journals (Sweden)

    Kadir Karakus

    2008-01-01

    Full Text Available Thermal behaviors of wheat straw flour (WF filled thermoplastic compositeswere measured applying the thermogravimetric analysis and differential scanningcalorimetry. Morphology and mechanical properties were also studied using scanningelectron microscope and universal testing machine, respectively. Presence of WF inthermoplastic matrix reduced the degradation temperature of the composites. One for WFand one for thermoplastics, two main decomposition peaks were observed. Morphologicalstudy showed that addition of coupling agent improved the compatibility between WFs andthermoplastic. WFs were embedded into the thermoplastic matrix indicating improvedadhesion. However, the bonding was not perfect because some debonding can also be seenon the interface of WFs and thermoplastic matrix. In the case of mechanical properties ofWF filled recycled thermoplastic, HDPE and PP based composites provided similar tensileand flexural properties. The addition of coupling agents improved the properties ofthermoplastic composites. MAPE coupling agents performed better in HDPE while MAPPcoupling agents were superior in PP based composites. The composites produced with thecombination of 50-percent mixture of recycled HDPE and PP performed similar with theuse of both coupling agents. All produced composites provided flexural properties requiredby the ASTM standard for polyolefin-based plastic lumber decking boards.

  16. A mechanical-thermal noise analysis of a nonlinear microgyroscope

    Science.gov (United States)

    Lajimi, S. A. M.; Heppler, G. R.; Abdel-Rahman, E. M.

    2017-01-01

    The mechanical-thermal noise (MTN) equivalent rotation rate (Ωn) is computed by using the linear approximation of the system response and the nonlinear "slow" system. The slow system, which is obtained using the method of multiple scales, is used to identify the linear single-valued response of the system. The linear estimate of the noise equivalent rate fails as the drive direction stroke increases. It becomes imperative in these conditions to use a more complex nonlinear estimate of the noise equivalent rate developed here for the first time in literature. The proposed design achieves a high performance regarding noise equivalent rotation rate.

  17. Basic thermal-mechanical properties and thermal shock, fatigue resistance of swaged + rolled potassium doped tungsten

    Science.gov (United States)

    Zhang, Xiaoxin; Yan, Qingzhi; Lang, Shaoting; Xia, Min; Ge, Changchun

    2014-09-01

    The potassium doped tungsten (W-K) grade was achieved via swaging + rolling process. The swaged + rolled W-K alloy exhibited acceptable thermal conductivity of 159.1 W/m K and ductile-to-brittle transition temperature of about 873 K while inferior mechanical properties attributed to the coarse pores and small deformation degree. Then the thermal shock, fatigue resistance of the W-K grade were characterized by an electron beam facility. Thermal shock tests were conducted at absorbed power densities varied from 0.22 to 1.1 GW/m2 in a step of 0.22 GW/m2. The cracking threshold was in the range of 0.44-0.66 GW/m2. Furthermore, recrystallization occurred in the subsurface of the specimens tested at 0.66-1.1 GW/m2 basing on the analysis of microhardness and microstructure. Thermal fatigue tests were performed at 0.44 GW/m2 up to 1000 cycles and no cracks emerged throughout the tests. Moreover, recrystallization occurred after 1000 cycles.

  18. Using IR spectroscopy and multivariate curve resolution to elucidate mechanism of heat-induced decomposition of an organic complex

    DEFF Research Database (Denmark)

    Karpushkin, Evgeny; Gvozdik, Nataliya; Kucheryavskiy, Sergey V.

    the opportunity to carry out simultaneous thermogravimetry/differential scanning calorimetry analysis and IR/Raman/mass spectrometry investigation of the evolving gaseous products. However, elucidation of the mechanism of the reactions occurring upon heat- ing is not completely straightforward, due to a number...... and discuss the results of TGA-DSC-IR study of heat-induced decomposition of tris(acetylacetonato)manganese(III) complex. Using this process as an example, we have indicated the complications of the evolved gas analysis and demonstrated that they can be partially overcome taking advantage of multivariate...... the meaningful information from the set of the evolved gas spectra. The elaborated approach is fairly general and applicable for study of a variety of the processes accompanied by evolution of gaseous products....

  19. In situ polyphenyl derivatisation and the effect of thermal decomposition of adsorbed and chemisorbed polyphenyls on the structure of multi-wall carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Gergely, Andras, E-mail: doohan11@chemres.hu [Department of Surface Modification and Nanostructures, Institute of Nanochemistry and Catalysis, Chemical Research Center of the Hungarian Academy of Sciences, Pusztaszeri ut 59-67, Budapest 1025 (Hungary); Ujszaszy, Kalman [Mass Spectrometry Department, Institute of Structural Chemistry, Pusztaszeri ut 59-67, Chemical Research Center of the Hungarian Academy of Sciences, Budapest 1025 (Hungary); Peltz, Csaba [EGIS Pharmaceuticals PLC, Kereszturi ut 30-38, Budapest 1106 (Hungary); Kiraly, Peter; Tarkanyi, Gabor [NMR Spectroscopy Department, Institute of Structural Chemistry, Chemical Research Center of the Hungarian Academy of Sciences, Pusztaszeri ut 59-67, Budapest 1025 (Hungary); Mihaly, Judith [Department of Biological Nanochemistry, Institute of Nanochemistry and Catalysis, Chemical Research Center of the Hungarian Academy of Sciences, Pusztaszeri ut 59-67, Budapest 1025 (Hungary); Kalman, Erika [Department of Surface Modification and Nanostructures, Institute of Nanochemistry and Catalysis, Chemical Research Center of the Hungarian Academy of Sciences, Pusztaszeri ut 59-67, Budapest 1025 (Hungary)

    2011-05-01

    This study presents the exploitation of an alternative reaction route of deamination of arylamines to perform in situ derivatisation of multi-walled carbon nanotubes (MWCNTs) with polyphenyl (PPh) species of various masses. As a result of consecutive derivatisation, high conversion of PPh grafting of the MWCNTs was realised with the collateral outgrowth of physical modification with adsorbed additional PPhs. Applied derivatisation process exceeds the monolayer coverage related superficial saturation limitations in the overall grafting yield of the nanotubes. Thus, a linear relationship was recognized between the overall quantities of chemisorbed PPhs composed of D{sub 5}-phenylene oligomers and the applied excess of diazonium activated reagents, corresponding to {sup 2}H MAS NMR spectroscopy results. According to mass spectrometry (MS) investigations, uniform thermal decomposition of the chemisorbed PPhs modified MWCNTs was found besides the more intense and altered decomposition characteristic-featured adsorbate-chemisorbate PPhs contained MWCNTs during sequential pyrolysis under inert atmosphere. This is attributed to the pyrolysis provoked isomerisation, decomposition and the formation of adsorbed and chemisorbed PPh moieties. As a result, a mediated and an even more pronounced degradation in the order of graphitic lattice of the MWCNTs were evidenced in the adsorbate-chemisorbate and the chemisorbate PPhs contained samples by FT-Raman spectroscopy and transmission electron microscopy (TEM), respectively. {sup 2}H MAS NMR supplied results of relevant amount of deuterium in the chemisorbate PPh contained sample without traces of aromatic related MS detected volatile products, these allow us to conclude about a thermally stable derivatisation that is interpreted as an endohedral modification of the nanotubes.

  20. MOF-derived hollow NiO-ZnO composite micropolyhedra and their application in catalytic thermal decomposition of ammonium perchlorate

    Science.gov (United States)

    Yang, Ji-Min

    2017-07-01

    Ni(II)-doped Zn-based coordination polymer particles (Ni(II)-doped Zn-CPPs) with controllable shape and size were successfully synthesized by solvothermal method, which further transformed to porous ZnO-NiO composite micropolyhedra without significant alterations in shape by calcination in air. Those products were characterized by powder X-ray diffraction (XRD), field emission scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), infrared spectroscopy (IR) and gas adsorption measurements. The catalytic activity of ZnO-NiO composites for the thermal decomposition of ammonium perchlorate (AP) was investigated. The result shows that all ZnO-NiO composites efficiently catalyzed the thermal decomposition of AP, and NiO-ZnO composite hollow octahedrons have the highest catalytic efficiency compared with that of most materials reported to now, indicating that porous ZnO-NiO composite micropolyhedra could be a promising candidate material for application in AP-based propellant.

  1. Thermodynamic studies of studtite thermal decomposition pathways via amorphous intermediates UO{sub 3}, U{sub 2}O{sub 7}, and UO{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Xiaofeng [Earth and Environmental Sciences Division, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Wu, Di [Peter A. Rock Thermochemistry Laboratory and NEAT ORU, University of California, Davis, CA 95616 (United States); The Gene and Lina Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, WA 99163 (United States); Xu, Hongwu [Earth and Environmental Sciences Division, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Burns, Peter C. [Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, IN 46556 (United States); Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556 (United States); Navrotsky, Alexandra, E-mail: anavrotsky@ucdavis.edu [Peter A. Rock Thermochemistry Laboratory and NEAT ORU, University of California, Davis, CA 95616 (United States)

    2016-09-15

    The thermal decomposition of studtite (UO{sub 2})O{sub 2}(H{sub 2}O){sub 2}·2H{sub 2}O results in a series of intermediate X-ray amorphous materials with general composition UO{sub 3+x} (x = 0, 0.5, 1). As an extension of a structural study on U{sub 2}O{sub 7}, this work provides detailed calorimetric data on these amorphous oxygen-rich materials since their energetics and thermal stability are unknown. These were characterized in situ by thermogravimetry, and mass spectrometry. Ex situ X-ray diffraction and infrared spectroscopy characterized their chemical bonding and local structures. This detailed characterization formed the basis for obtaining formation enthalpies by high temperature oxide melt solution calorimetry. The thermodynamic data demonstrate the metastability of the amorphous UO{sub 3+x} materials, and explain their irreversible and spontaneous reactions to generate oxygen and form metaschoepite. Thus, formation of studtite in the nuclear fuel cycle, followed by heat treatment, can produce metastable amorphous UO{sub 3+x} materials that pose the risk of significant O{sub 2} gas. Quantitative knowledge of the energy landscape of amorphous UO{sub 3+x} was provided for stability analysis and assessment of conditions for decomposition.

  2. Estudo cinético da decomposição térmica do pentaeretritol-tetranitrado (PETN Kinetic study of the thermal decomposition of pentaerythritol-tetranitrate (PETN

    Directory of Open Access Journals (Sweden)

    Gilson da Silva

    2008-01-01

    Full Text Available The pentaerythritol-tetranitrate (PETN is a nitroether used in explosives and propellant formulations. Due to its suitable properties, PETN is used in booster manufacture. Knowing the thermal decomposition behavior of an energetic material is very important for storage and manipulation, and the purpose of this work is to study the kinetic parameters of the decomposition of PETN, compare the results with literature data and to study the decomposition activation energy differences between two crystalline forms of PETN (tetragonal and needle by means of differential scanning calorimetry (DSC. Fourier transform infrared spectroscopy (FT-IR is used to study the two crystalline forms.

  3. Mechanical Testing of Carbon Based Woven Thermal Protection Materials

    Science.gov (United States)

    Pham, John; Agrawal, Parul; Arnold, James O.; Peterson, Keith; Venkatapathy, Ethiraj

    2013-01-01

    Three Dimensional Woven thermal protection system (TPS) materials are one of the enabling technologies for mechanically deployable hypersonic decelerator systems. These materials have been shown capable of serving a dual purpose as TPS and as structural load bearing members during entry and descent operations. In order to ensure successful structural performance, it is important to characterize the mechanical properties of these materials prior to and post exposure to entry-like heating conditions. This research focuses on the changes in load bearing capacity of woven TPS materials after being subjected to arcjet simulations of entry heating. Preliminary testing of arcjet tested materials [1] has shown a mechanical degradation. However, their residual strength is significantly more than the requirements for a mission to Venus [2]. A systematic investigation at the macro and microstructural scales is reported here to explore the potential causes of this degradation. The effects of heating on the sizing (an epoxy resin coating used to reduce friction and wear during fiber handling) are discussed as one of the possible causes for the decrease in mechanical properties. This investigation also provides valuable guidelines for margin policies for future mechanically deployable entry systems.

  4. Thermal-mechanical behavior of fuel element in SCWR design

    Energy Technology Data Exchange (ETDEWEB)

    Xu, R.; Yetisir, M.; Hamilton, H. [Atomic Energy of Canada Limited, Chalk River, ON (Canada)

    2014-07-01

    This paper presents a study on thermal-mechanical behavior of a fuel element proposed for the Canadian Supercritical Water Cooled Reactor (SCWR). In the Canadian SCWR, the coolant pressure is 25 MPa, and the temperature is 350{sup o}C at the inlet and 625{sup o}C at the outlet of the reactor core. Critical design decisions for fuel design will be the selection of the fuel sheath material and details of the fuel element design options (sheath thickness, pellet-clad gap, internal pressure, etc.). The analysis presented in this paper predicted temperature, stress and strain in the fuel element of the Canadian SCWR with a collapsible sheath using ANSYS. Typical conditions for the evaluation of the fuel behavior, such as linear heat generation rate, coolant temperature and sheath surface heat transfer coefficient, were extracted from core and fuel channel designs. The temperature distribution in the fuel element is predicted by a thermal model and then the thermal model is coupled sequentially with a structural model to predict fuel sheath deformation under the predicted temperature distribution and external (coolant) pressure. Nonlinear thermo-mechanical simulations include nonlinear buckling with elastic-plastic deformation. Three sheath collapse phenomena are considered: (1) elastic collapse by buckling, (2) longitudinal ridging and (3) plastic collapse by yielding. The numerical models are validated against analytical and experimental data. The presented results show the temperature distribution, deformed shape, stress and strain of the fuel element, allowing the designers to select appropriate sheath material and element design options for the SCWR fuel element design. (author)

  5. Statistical mechanics of influence maximization with thermal noise

    Science.gov (United States)

    Lynn, Christopher W.; Lee, Daniel D.

    2017-03-01

    The problem of optimally distributing a budget of influence among individuals in a social network, known as influence maximization, has typically been studied in the context of contagion models and deterministic processes, which fail to capture stochastic interactions inherent in real-world settings. Here, we show that by introducing thermal noise into influence models, the dynamics exactly resemble spins in a heterogeneous Ising system. In this way, influence maximization in the presence of thermal noise has a natural physical interpretation as maximizing the magnetization of an Ising system given a budget of external magnetic field. Using this statistical mechanical formulation, we demonstrate analytically that for small external-field budgets, the optimal influence solutions exhibit a highly non-trivial temperature dependence, focusing on high-degree hub nodes at high temperatures and on easily influenced peripheral nodes at low temperatures. For the general problem, we present a projected gradient ascent algorithm that uses the magnetic susceptibility to calculate locally optimal external-field distributions. We apply our algorithm to synthetic and real-world networks, demonstrating that our analytic results generalize qualitatively. Our work establishes a fruitful connection with statistical mechanics and demonstrates that influence maximization depends crucially on the temperature of the system, a fact that has not been appreciated by existing research.

  6. Flue Gas Desulfurization by Mechanically and Thermally Activated Sodium Bicarbonate

    Directory of Open Access Journals (Sweden)

    Walawska Barbara

    2014-09-01

    Full Text Available This paper presents the results of study on structural parameters (particle size, surface area, pore volume and the sorption ability of mechanically and thermally activated sodium bicarbonate. The sorption ability of the modified sorbent was evaluated by: partial and overall SO2 removal efficiency, conversion rate, normalized stoichiometric ratio (NSR. Sodium bicarbonate was mechanically activated by various grinding techniques, using three types of mills: fluid bed opposed jet mill, fine impact mill and electromagnetic mill, differing in grinding technology. Grounded sorbent was thermally activated, what caused a significant development of surface area. During the studies of SO2 sorption, a model gas with a temperature of 300°C, of composition: sulfur dioxide at a concentration of 6292 mg/mn3, oxygen, carbon dioxide and nitrogen as a carrier gas, was used. The best development of surface area and the highest SO2 removal efficiency was obtained for the sorbent treated by electromagnetic grinding, with simultaneous high conversion rate.

  7. Thermal stability of nafion membranes under mechanical stress

    Energy Technology Data Exchange (ETDEWEB)

    Quintilii, M.; Struis, R. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1997-06-01

    The feasibility of adequately modified fluoro-ionomer membranes (NAFION{sup R}) is demonstrated for the selective separation of methanol synthesis products from the raw reactor gas at temperatures around 200{sup o}C. For an economically relevant application of this concept on a technical scale the Nafion membranes should be thin ({approx_equal}10 {mu}m) and thermally stable over a long period of time (1-2 years). In cooperation with industry (Methanol Casale SA, Lugano (CH)), we test the thermal stability of Nafion hollow fibers and supported Nafion thin sheet membranes at temperatures between 160 and 200{sup o}C under mechanical stress by applying a gas pressure difference over the membrane surface ({Delta}P{<=} 40 bar). Tests with the hollow fibers revealed that Nafion has visco-elastic properties. Tests with 50 {mu}m thin Nafion sheets supported by a porous metal carrier at 200{sup o}C and {Delta}P=39 bar showed no mechanical defects over a period of 92 days. (author) 5 figs., 4 refs.

  8. Woven glass fabric reinforced laminates based on polyolefin wastes: Thermal, mechanical and dynamic-mechanical properties

    Science.gov (United States)

    Russo, Pietro; Acierno, Domenico; Simeoli, Giorgio; Lopresto, Valentina

    2014-05-01

    Potentialities of polyolefin wastes in place of virgin polypropylene to produce composite laminates have been investigated. Plaques reinforced with a woven glass fabric were prepared by film-stacking technique and systematically analyzed in terms of thermal, mechanical and dynamic-mechanical properties. In case of PP matrices, the use of a typical compatibilizer to improve the adhesion at the interface has been considered. Thermal properties emphasized the chemical nature of plastic wastes. About mechanical properties, static tests showed an increase of flexural parameters for compatibilized systems due to the coupling effect between grafted maleic anhydride and silane groups on the surface of the glass fabric. These effects, maximized for composites based on car bumper wastes, is perfectly reflected in terms of storage modulus and damping ability of products as determined by single-cantilever bending dynamic tests.

  9. Mechanisms of thermal interaction of corium with coolants (sodium, water)

    Energy Technology Data Exchange (ETDEWEB)

    Yuri I Zagorulko; Viktor G Zhmurin; Andrey N Volov; Michail V Kashcheev; Yuri P Kovalev [SSC RF-IPPE named after A.I. Leypunsky, Bondarenko sq. 1, Obninsk, 249033, Kaluga region (Russian Federation)

    2005-07-01

    Full text of publication follows: Experimental assessments of corium thermal-energy-to-mechanical-work conversion factors at thermal interaction (TI) with coolants (sodium, water) and the effects of material transport (coolant, its vapor, corium fragments) caused by this interaction provide a basis for testing the physical and computational TI models. It is evident that the physical TI model should provide an adequate description of all parameters to be measured experimentally (pressure history in the system, amplitude-frequency characteristics of vibrational spectra, rate and acceleration of material transport, final corium fragments size distribution and their morphology) in terms of initial conditions of interaction, inertia and geometrical constraints imposed on the system. The paper presents a generalized analysis of experimental results of TI study in systems 'coolant (sodium, water)/corium (melts of thermit mixtures U+MoO{sub 3}, Zr+Fe{sub 2}O{sub 3})' as to possible mechanisms of thermal interaction in these systems. The study was performed with free channels and those encumbered by rod bundles of hexagonal geometry. In all tests, the sodium temperature was {approx} 823 K, that of water {approx} 293 K, at mass ratios M{sub corium}/M{sub coolant} {approx_equal} 0.3-0.6. The corium outflow conditions were set with regard to modeling of fission gas presence (argon in sodium experiments, air in tests with water) at melt temperatures of {approx} 3000 K and gas pressures up to 0.6-1 MPa. The rate of melt outflow amounted to 20 m/s. The kinematic parameters of material transport and impact loads caused by this transport were determined by means of two independent techniques. The first technique was based on measuring residual deformations of bend of calibrated plate elements (copper, steel). The assemblies of these elements were located at a specified distance above the coolant level in the plane perpendicular to the axis of the channel (the interaction

  10. Thermal mechanical analysis of applications with internal heat generation

    Science.gov (United States)

    Govindarajan, Srisharan Garg

    control blade, spatial variations in temperature within the control blade occur from the non-uniform heat generation within the BORAL as a result of the non-uniform thermal neutron flux along the longitudinal direction when the control blade is partially withdrawn. There is also variation in the heating profile through the thickness and about the circumferential width of the control blade. Mathematical curve-fits are generated for the non-uniform volumetric heat generation profile caused by the thermal neutron absorption and the functions are applied as heating conditions within a finite element model of the control blade built using the commercial finite element code Abaqus FEA. The finite element model is solved as a fully coupled thermal mechanical problem as in the case of the annular target. The resulting deflection is compared with the channel gap to determine if there is a significant risk of the control blade binding during reactor operation. Hence, this dissertation will consist of two sections. The first section will seek to present the thermal and structural safety analyses of the annular targets for the production of molybdenum-99. Since there hasn't been any detailed, documented, study on these annular targets in the past, the work complied in this dissertation will help to understand the thermal-mechanical behavior and failure margins of the target during in-vessel irradiation. As the work presented in this dissertation provides a general performance analysis envelope for the annular target, the tools developed in the process can also be used as useful references for future analyses that are specific to any reactor. The numerical analysis approach adopted and the analytical models developed, can also be applied to other applications, outside the Mo-99 project domain, where internal heat generation exists such as in electronic components and nuclear reactor control blades. The second section will focus on estimating the thermally induced deflection and hence

  11. Potential macro-detritivore range expansion into the subarctic stimulates litter decomposition: a new positive feedback mechanism to climate change?

    OpenAIRE

    Geffen, van, LCMM; Berg, M.P.; Aerts, R.

    2011-01-01

    As a result of low decomposition rates, high-latitude ecosystems store large amounts of carbon. Litter decomposition in these ecosystems is constrained by harsh abiotic conditions, but also by the absence of macro-detritivores. We have studied the potential effects of their climate change-driven northward range expansion on the decomposition of two contrasting subarctic litter types. Litter of Alnus incana and Betula pubescens was incubated in microcosms together with monocultures and all pos...

  12. Computational thermal, chemical, fluid, and solid mechanics for geosystems management.

    Energy Technology Data Exchange (ETDEWEB)

    Davison, Scott; Alger, Nicholas; Turner, Daniel Zack; Subia, Samuel Ramirez; Carnes, Brian; Martinez, Mario J.; Notz, Patrick K.; Klise, Katherine A.; Stone, Charles Michael; Field, Richard V., Jr.; Newell, Pania; Jove-Colon, Carlos F.; Red-Horse, John Robert; Bishop, Joseph E.; Dewers, Thomas A.; Hopkins, Polly L.; Mesh, Mikhail; Bean, James E.; Moffat, Harry K.; Yoon, Hongkyu

    2011-09-01

    This document summarizes research performed under the SNL LDRD entitled - Computational Mechanics for Geosystems Management to Support the Energy and Natural Resources Mission. The main accomplishment was development of a foundational SNL capability for computational thermal, chemical, fluid, and solid mechanics analysis of geosystems. The code was developed within the SNL Sierra software system. This report summarizes the capabilities of the simulation code and the supporting research and development conducted under this LDRD. The main goal of this project was the development of a foundational capability for coupled thermal, hydrological, mechanical, chemical (THMC) simulation of heterogeneous geosystems utilizing massively parallel processing. To solve these complex issues, this project integrated research in numerical mathematics and algorithms for chemically reactive multiphase systems with computer science research in adaptive coupled solution control and framework architecture. This report summarizes and demonstrates the capabilities that were developed together with the supporting research underlying the models. Key accomplishments are: (1) General capability for modeling nonisothermal, multiphase, multicomponent flow in heterogeneous porous geologic materials; (2) General capability to model multiphase reactive transport of species in heterogeneous porous media; (3) Constitutive models for describing real, general geomaterials under multiphase conditions utilizing laboratory data; (4) General capability to couple nonisothermal reactive flow with geomechanics (THMC); (5) Phase behavior thermodynamics for the CO2-H2O-NaCl system. General implementation enables modeling of other fluid mixtures. Adaptive look-up tables enable thermodynamic capability to other simulators; (6) Capability for statistical modeling of heterogeneity in geologic materials; and (7) Simulator utilizes unstructured grids on parallel processing computers.

  13. Microcracking in composite laminates under thermal and mechanical loading. Thesis

    Science.gov (United States)

    Maddocks, Jason R.

    1995-01-01

    Composites used in space structures are exposed to both extremes in temperature and applied mechanical loads. Cracks in the matrix form, changing the laminate thermoelastic properties. The goal of the present investigation is to develop a predictive methodology to quantify microcracking in general composite laminates under both thermal and mechanical loading. This objective is successfully met through a combination of analytical modeling and experimental investigation. In the analysis, the stress and displacement distributions in the vicinity of a crack are determined using a shear lag model. These are incorporated into an energy based cracking criterion to determine the favorability of crack formation. A progressive damage algorithm allows the inclusion of material softening effects and temperature-dependent material properties. The analysis is implemented by a computer code which gives predicted crack density and degraded laminate properties as functions of any thermomechanical load history. Extensive experimentation provides verification of the analysis. AS4/3501-6 graphite/epoxy laminates are manufactured with three different layups to investigate ply thickness and orientation effects. Thermal specimens are cooled to progressively lower temperatures down to -184 C. After conditioning the specimens to each temperature, cracks are counted on their edges using optical microscopy and in their interiors by sanding to incremental depths. Tensile coupons are loaded monotonically to progressively higher loads until failure. Cracks are counted on the coupon edges after each loading. A data fit to all available results provides input parameters for the analysis and shows them to be material properties, independent of geometry and loading. Correlation between experiment and analysis is generally very good under both thermal and mechanical loading, showing the methodology to be a powerful, unified tool. Delayed crack initiation observed in a few cases is attributed to a

  14. Development of CdS Nanostructures by Thermal Decomposition of Aminocaproic Acid-Mixed Cd-Thiourea Complex Precursor: Structural, Optical and Photocatalytic Characterization.

    Science.gov (United States)

    Patel, Jayesh D; Mighri, Frej; Ajji, Abdellah; Chaudhuri, Tapas K

    2015-04-01

    The present work deals with two different CdS nanostructures produced via hydrothermal and solvothermal decompositions of aminocaproic acid (ACA)-mixed Cd-thiourea complex precursor at 175 °C. Both nanostructures were extensively characterized for their structural, morphological and optical properties. The powder X-ray diffraction characterization showed that the two CdS nanostructures present a wurtzite morphology. Scanning electron microscopy and energy-dispersive X-ray characterizations revealed that the hydrothermal decomposition produced well-shaped CdS flowers composed of six dendritic petals, and the solvothermal decomposition produced CdS microspheres with close stoichiometric chemical composition. The UV-vis absorption and photoluminescence spectra of CdS dendritic flowers and microsphere nanostructures showed that both nanostructures present a broad absorption between 200 and 700 nm and exhibit strong green emissions at 576 and 520 nm upon excitations at 290 nm and 260 nm, respectively. The transmission electron microscopy (TEM) and Brunauer-Emmett-Teller (BET) characterizations confirmed that CdS microspheres were mesoporous and were composed of small nanocrystals. A possible growth mechanism in the formation of the CdS nanostructures was proposed based on morphology evolution as a function of the reaction time. Furthermore, the as-synthesized CdS nanostructures were found to exhibit highly efficient photocatalytic activities for the degradation of methyl orange (MeO) and rhodamine B (RhB) dyes.

  15. Structural, thermal, optical and photoacoustic study of nanostructured FeSb{sub 2} prepared by mechanical alloying

    Energy Technology Data Exchange (ETDEWEB)

    Poffo, C.M. [Departamento de Engenharia Mecânica, Universidade Federal de Santa Catarina, Campus Universitário Trindade, S/N, C.P. 476, 88040-900 Florianópolis, Santa Catarina (Brazil); Lima, J.C. de, E-mail: fsc1jcd@fisica.ufsc.br [Departamento de Física, Universidade Federal de Santa Catarina, Campus Universitário Trindade, S/N, C.P. 476, 88040-900 Florianópolis, Santa Catarina (Brazil); Souza, S.M.; Trichês, D.M. [Departamento de Física, Universidade Federal do Amazonas, 3000 Japiim, 69077-000 Manaus, Amazonas (Brazil); Grandi, T.A. [Departamento de Física, Universidade Federal de Santa Catarina, Campus Universitário Trindade, S/N, C.P. 476, 88040-900 Florianópolis, Santa Catarina (Brazil); Biasi, R.S. de [Seção de Engenharia Mecânica e de Materiais, Instituto Militar de Engenharia, 22290-270 Rio de Janeiro, RJ (Brazil)

    2013-03-15

    Mechanical alloying of elemental Fe and Sb powders yielded nanostructured FeSb{sub 2}, an amorphous phase, along with unreacted Sb. The volume fractions of FeSb{sub 2}, Sb nanocrystals and interfacial/amorphous components were estimated from the X-ray diffraction pattern of the as-miller powder. The thermal stability of FeSb{sub 2} was investigated by heating the powder at 250 °C and 400 °C. The XRD pattern of the sample annealed at 250 °C showed nucleation of Fe{sub 3}O{sub 4} and decomposition of FeSb{sub 2}. For an annealing temperature of 400 °C, besides crystallization of the amorphous phase, the volume fractions of Sb and Fe{sub 3}O{sub 4} increased and the volume fraction of FeSb{sub 2} decreased. The optical band gap energy for samples as-milled and annealed at 400 °C was measured, and a slight decrease in the band gap was observed in the annealed sample. Thermal diffusivity parameter of the as-milled sample and of the annealed sample at 400 °C was also measured, as well as other transport properties. We also studied the contribution of the thermal diffusivity of the interfacial/amorphous component to the thermal diffusivity of the as-milled sample.

  16. High temperature shock tube studies on the thermal decomposition of O3 and the reaction of dimethyl carbonate with O-atoms.

    Science.gov (United States)

    Peukert, S L; Sivaramakrishnan, R; Michael, J V

    2013-05-09

    The shock tube technique was used to study the thermal decomposition of ozone, O3, with a view to using this as a thermal precursor of O-atoms at high temperatures. The formation of O-atoms was measured behind reflected shock waves by using atomic resonance absorption spectrometry (ARAS). The experiments span a T-range, 819 K ≤ T ≤ 1166 K, at pressures 0.13 bar ≤ P ≤ 0.6 bar. Unimolecular rate theory provides an excellent representation of the falloff characteristics from the present and literature data on ozone decomposition at high temperatures. The present decomposition study on ozone permits its usage as a thermal source for O-atoms allowing measurements for, O + CH3OC(O)OCH3 → OH + CH3OC(O)OCH2 [A]. Reflected shock tube experiments monitoring the formation and decay of O-atoms were performed on reaction A using mixtures of O3 and CH3OC(O)OCH3, (DMC), in Kr bath gas over the T-range, 862 K ≤ T ≤ 1167 K, and pressure range, 0.15 bar ≤ P ≤ 0.33 bar. A detailed model was used to fit the O-atom temporal profile to obtain experimental rate constants for reaction A. Rate constants from the present experiments for O + DMC can be represented by the Arrhenius expression: kA(T) = 2.70 × 10(-11) exp(-2725 K/T) cm(3) molecule(-1) s(-1) (862-1167 K). Transition state theory calculations employing CCSD(T)/cc-pv∞z//M06-2X/cc-pvtz energetics and molecular properties for reaction A are in good agreement with the experimental rate constants. The theoretical rate constants can be well represented (to within ±10%) over the 500-2000 K temperature range by: kA(T) = 1.87 × 10(-20)T(2.924) exp(-2338 K/T) cm(3) molecule(-1) s(-1). The present study represents the first experimental measurement and theoretical study on this bimolecular reaction which is of relevance to the high temperature oxidation of DMC.

  17. Mechanical, Thermal and Functional Properties of Green Lightweight Foamcrete

    Directory of Open Access Journals (Sweden)

    Md Azree Othuman Mydin

    2012-09-01

    Full Text Available In recent times, the construction industry has revealed noteworthy attention in the use of lightweight foamcrete as a building material due to its many favourable characteristics such as lighter weight, easy to fabricate, durable and cost effective. Foamcrete is a material consisting of Portland cement paste or cement filler matrix (mortar with a homogeneous pore structure created by introducing air in the form of small bubbles. With a proper control in dosage of foam and methods of production, a wide range of densities (400 – 1600 kg/m 3 of foamcrete can be produced thus providing flexibility for application such as structural elements, partition, insulating materials and filling grades. Foamcrete has so far been applied primarily as a filler material in civil engineering works. However, its good thermal and acoustic performance indicates its strong potential as a material in building construction. The focus of this paper is to classify literature on foamcrete in terms of its mechanical, thermal and functional properties.

  18. Optical, mechanical and thermal behaviors of Nitrilotriacetic acid single crystal

    Science.gov (United States)

    Deepa, B.; Philominathan, P.

    2017-11-01

    An organic nonlinear single crystal of Nitrilotriacetic acid (NTAA) was grown for the first time by employing a simple slow evaporation technique. Single crystal X-ray diffraction (XRD) analysis reveals that the grown crystal belongs to the monoclinic system with noncentrosymmetric space group CC. Fourier transform infrared (FTIR) spectral study ascertains the presence of functional groups in NTAA. The molecular structure of the grown crystal was confirmed by Nuclear Magnetic Resonance (NMR) spectral analysis. The optical parameters such as transmittance, absorption coefficient and band gap were calculated from UV-Visible and fluorescence studies. Dielectric measurements were carried out for different frequency and temperature. The mechanical strength of the grown crystal was measured using Vickers microhardness test. The high thermal stability and the melting point of the grown crystal were also estimated using thermogravimetric (TGA) and differential thermal analyses (DTA). The confirmation of the grown crystals belonging to nonlinear optical crystals was performed by Kurtz-Perry technique and found as suitable candidate for optoelectronics applications.

  19. Semi-empirical method for calculating the activation energies of the unimolecular thermal decomposition of vinyl ethers

    Science.gov (United States)

    Sargsyan, G. N.; Shakhrokh, B.; Harutyunyan, A. B.

    2015-02-01

    A semi-empirical method is proposed for calculating the activation energy of the unimolecular decomposition of complex compounds using the example of vinyl (ethyl, propyl, and butyl) ethers. The method is based on the concept of the formation of intramolecular hydrogen bonds and the possibility of calculating the energy of deformation of ether molecules upon activation, resulting in the potential surface of the transition state undergoing distortion and the transfer of a hydrogen atom from an alkyl group to a vinyl group. The energy of deformation is calculated using the Mathcad 2001i and MM2 computer programs.

  20. Studies on the thermal decomposition of lanthanum(III) valerate and lanthanum(III) caproate in argon

    DEFF Research Database (Denmark)

    Grivel, Jean-Claude; Yue, Zhao; Suarez Guevara, Maria Josefina

    2015-01-01

    The decomposition of La-valerate (La(C4H9CO2)3·xH2O (x ≈ 0.45)) and La-caproate (La(C5H11CO2)3·xH2O (x ≈ 0.30)) was studied upon heating at 5 C/min in a flow of argon. Using a variety of techniques including simultaneous TG-DTA, FTIR, X-ray diffraction with both laboratory Cu Kα and synchrotron...

  1. Thermal and Quantum Mechanical Noise of a Superfluid Gyroscope

    Science.gov (United States)

    Chui, Talso; Penanen, Konstantin

    2004-01-01

    A potential application of a superfluid gyroscope is for real-time measurements of the small variations in the rotational speed of the Earth, the Moon, and Mars. Such rotational jitter, if not measured and corrected for, will be a limiting factor on the resolution potential of a GPS system. This limitation will prevent many automation concepts in navigation, construction, and biomedical examination from being realized. We present the calculation of thermal and quantum-mechanical phase noise across the Josephson junction of a superfluid gyroscope. This allows us to derive the fundamental limits on the performance of a superfluid gyroscope. We show that the fundamental limit on real-time GPS due to rotational jitter can be reduced to well below 1 millimeter/day. Other limitations and their potential mitigation will also be discussed.

  2. Untangling the Reaction Mechanisms Involved in the Explosive Decomposition of Model Compounds of Energetic Materials

    Science.gov (United States)

    2014-06-11

    and Reports, 1215 Jefferson Davis Highway, Suite 1204, Arlington VA, 22202-4302. Respondents should be aware that notwithstanding any other...provision of law, no person shall be subject to any oenalty for failing to comply with a collection of information if it does not display a currently valid...mechanisms of complex molecules in extraterrestrial environments and in combustion systems”. (2013) Received Book Chapter TOTAL: PERCENT_SUPPORTEDNAME

  3. Application of Non-Isothermal Thermogravimetric Method to Interpret the Decomposition Kinetics of , and

    Science.gov (United States)

    Pouretedal, H. R.; Ebadpour, R.

    2014-05-01

    The non-isothermal thermogravimetric method was used to study the thermal decomposition of , and at heating rates of (5, 10, 15, and 20) . The activation energy of thermal decomposition reactions was computed by isoconversional methods of Ozawa-Flynn-Wall, Kissinger-Akahiro-Sunose, and Friedman equations. Also, the kinetic triplet of the thermal decomposition of salts was determined by the model-fitting method of the modified Coats-Redfern equation. The activation energies of , and of (293 to 307, 160 to 209, and 192 to 245) , respectively, are obtained by non-isothermal isoconversional methods. The modified Coats and Redfern method showed that the most probable mechanism functions of (model A3: Arami-Erofeev equation) and (model F2: second order) can be used to predict the decomposition mechanisms of , , and , respectively.

  4. Potential macro-detritivore range expansion into the subarctic stimulates litter decomposition: a new positive feedback mechanism to climate change?

    NARCIS (Netherlands)

    Geffen, van K.G.; Berg, M.P.; Aerts, R.

    2011-01-01

    As a result of low decomposition rates, high-latitude ecosystems store large amounts of carbon. Litter decomposition in these ecosystems is constrained by harsh abiotic conditions, but also by the absence of macro-detritivores. We have studied the potential effects of their climate change-driven

  5. Mechanisms of thermal balance in flying Centris pallida (Hymenoptera: Anthophoridae).

    Science.gov (United States)

    Roberts, S P; Harrison, J F; Hadley, N F

    1998-08-01

    Thermoregulation of the thorax is critical for bees and other endothermic insects to achieve high rates of flight muscle power production. However, the mechanisms allowing insects to regulate thorax temperatures during flight are not well understood. To test whether variations in metabolic heat production, evaporation or heat transfer from the thorax to the abdomen contribute to the maintenance of stable body temperatures during flight in the bee Centris pallida, we measured CO2 production, water vapor loss, wingbeat frequency and body segment temperatures during flight at varying air temperatures (Ta). While hovering in the field and while flying in the respirometer, C. pallida males maintain extremely stable, elevated thorax temperatures (45+/-2 degrees C; mean +/- S.E.M.). Measurements of head, thorax and abdomen temperatures as a function of Ta during hovering flight in the field indicated that C. pallida males were not actively increasing heat transfer from the thorax to the head or abdomen at high Ta values. As Ta increased from 26 to 35 degrees C, increases in evaporative water loss were relatively small compared with the decrease in carbon dioxide emission. As Ta values increased from 26 to 35 degrees C, the factorial decreases in metabolic heat production and the elevation of thorax temperature above Ta were closely matched (35 %), suggesting that variation in metabolic heat production is the major mechanism of thermoregulation in flying C. pallida. The thermal effects on rates of water loss and metabolic water production resulted in a strong positive water balance at cooler Ta values, but a strong negative water balance at Ta values above 31 degrees C. During the first minute of flight in the respirometry chamber, wingbeat frequency was independent of Ta. However, by the fourth minute, there was a significant negative relationship between Ta and wingbeat frequency, which was similar to the thermal relationship observed for wingbeat frequency in the field

  6. Mechanism of crack initiation and crack growth under thermal and mechanical fatigue loading

    Energy Technology Data Exchange (ETDEWEB)

    Utz, S.; Soppa, E.; Silcher, H.; Kohler, C. [Stuttgart Univ. (Germany). Materials Testing Inst.

    2013-07-01

    The present contribution is focused on the experimental investigations and numerical simulations of the deformation behaviour and crack development in the austenitic stainless steel X6CrNiNb18-10 under thermal and mechanical cyclic loading in HCF and LCF regimes. The main objective of this research is the understanding of the basic mechanisms of fatigue damage and the development of simulation methods, which can be applied further in safety evaluations of nuclear power plant components. In this context the modelling of crack initiation and crack growth inside the material structure induced by varying thermal or mechanical loads are of particular interest. The mechanisms of crack initiation depend among other things on the type of loading, microstructure, material properties and temperature. The Nb-stabilized austenitic stainless steel in the solution-annealed condition was chosen for the investigations. Experiments with two kinds of cyclic loading - pure thermal and pure mechanical - were carried out and simulated. The fatigue behaviour of the steel X6CrNiNb18-10 under thermal loading was studied within the framework of the joint research project [4]. Interrupted thermal cyclic tests in the temperature range of 150 C to 300 C combined with non-destructive residual stress measurements (XRD) and various microscopic investigations, e.g. in SEM (Scanning Electron Microscope), were used to study the effects of thermal cyclic loading on the material. This thermal cyclic loading leads to thermal induced stresses and strains. As a result intrusions and extrusions appear inside the grains (at the surface), at which microcracks arise and evolve to a dominant crack. Finally, these microcracks cause a continuous and significant decrease of residual stresses. The fatigue behaviour of the steel X6CrNiNb18-10 under mechanical loading at room temperature was studied within the framework of the research project [5], [8]. With a combination of interrupted LCF tests and EBSD

  7. Monodisperse and size-tunable CoO nanocrystals synthesized by thermal decomposition and as an active precursor for Fischer-Tropsch synthesis

    Science.gov (United States)

    Lv, Shuai; Zhao, Xin; Xia, Guofu; Jin, Chao; Wang, Li; Yang, Weimin; Zhang, Yuhua; Li, Jinlin

    2017-01-01

    CoO nanocrystals with tunable particle sizes were prepared by thermal decomposition of cobalt(II) acetate in different long-chain alkyl amines. These alkyl amines strongly affect the coordination of the amine group to the metal atoms and the metal-amine interaction, thereby mediating the eventual particle sizes in the condensation process. Moreover, CoO nanocrystals were applied for synthesis of supported catalyst, and exhibited higher catalytic activity in Fischer-Tropsch reaction, demonstrating that nanocrystals are active precursor. The TOF of CO on CoAl-n catalyst obtained from CoO nanocrystals is ∼1.5 times higher than that on conventional catalyst with the same particle size.

  8. Synthesis of nanostructured NiO/Co3O4 through thermal decomposition of a bimetallic (Ni/Co) metal-organic framework as catalyst for cyclooctene epoxidation

    Science.gov (United States)

    Abbasi, Alireza; Soleimani, Mohammad; Najafi, Mahnaz; Geranmayeh, Shokoofeh

    2017-04-01

    Hydrothermal approach has led to the formation of a three-dimensional metal-organic framework (MOF), [NiCo(μ2-tp)(μ4-tp)(4,4‧-bpy)2]n (1) (tp = terephthalic acid and 4,4‧-bpy = 4,4‧-bipyridine) which was characterized by means of single-crystal X-ray diffraction analysis, powder X-ray diffraction (PXRD), FT-IR spectroscopy, scanning electron microscopy (SEM) and inductive coupled plasma optical emission spectroscopy (ICP-OES). Thermal decomposition of the MOF afforded nanostructured mixed metal oxide, namely NiO/Co3O4. The XRD and SEM analysis confirm the formation of the mixed metal oxide. The nanostructured NiO/Co3O4 demonstrated good catalytic activity and selectivity in the epoxidation of cyclooctene in the presence of tert-butyl hydroperoxide (TBHP) as oxidant.

  9. Ion chromatography electrospray ionization mass spectrometry method development and investigation of lithium hexafluorophosphate-based organic electrolytes and their thermal decomposition products.

    Science.gov (United States)

    Kraft, Vadim; Grützke, Martin; Weber, Waldemar; Winter, Martin; Nowak, Sascha

    2014-08-08

    A method based on the coupling of ion chromatography (IC) and electrospray ionization mass spectrometry (ESI-MS) for the separation and determination of thermal decomposition products of LiPF6-based organic electrolytes is presented. The utilized electrolytes, LP30 and LP50, are commercially available and consist of 1mol/l LiPF6 dissolved in ethylene carbonate/dimethyl carbonate and ethylene carbonate/ethyl methyl carbonate, respectively. For the separation method development three ion chromatographic columns with different capacity and stationary phase were used and compared. Besides the known hydrolysis products of lithium hexafluorophosphate, several new organophosphates were separated and identified with the developed IC-ESI-MS method during aging investigations of the electrolytes. The chemical structures were elucidated with IC-ESI-MS/MS. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. Effect of high-temperature treatment in air on the surface area and porous texture of zirconium dioxide prepared by thermal decomposition of the nitrate

    Energy Technology Data Exchange (ETDEWEB)

    Arean, C.O.; Colinas, J.M.F.; Garcia, M.A.V. (Oviedo Univ. (Spain). Dept. of Inorganic Chemistry); Arjona, A.M. (Granada Univ. (Spain). Dept. of Inorganic Chemistry)

    1982-09-01

    Zirconium dioxide, prepared by thermal decomposition of zirconium nitrate, was heated in air at temperatures ranging from 573 to 1023 K. An analysis of nitrogen adsorption-desorption isotherms on the resulting materials allowed determination of the corresponding specific surface area and porous texture. All oxides calcined within the temperature range 573 to 873 K were found to be basically mesoporous; the most frequent pore radius increasing from 3 to 10.5 nm as the temperature was raised. BET surface areas decreased across the same temperature range, from 94 down to 20 m/sup 2/ g/sup -1/. The sample fired at 1023 K showed a BET surface area smaller than 5 m/sup 2/ g/sup -1/.

  11. Photodegradation at day, microbial decomposition at night - decomposition in arid lands

    Science.gov (United States)

    Gliksman, Daniel; Gruenzweig, Jose

    2014-05-01

    Our current knowledge of decomposition in dry seasons and its role in carbon turnover is fragmentary. So far, decomposition during dry seasons was mostly attributed to abiotic mechanisms, mainly photochemical and thermal degradation, while the contribution of microorganisms to the decay process was excluded. We asked whether microbial decomposition occurs during the dry season and explored its interaction with photochemical degradation under Mediterranean climate. We conducted a litter bag experiment with local plant litter and manipulated litter exposure to radiation using radiation filters. We found notable rates of CO2 fluxes from litter which were related to microbial activity mainly during night-time throughout the dry season. This activity was correlated with litter moisture content and high levels of air humidity and dew. Day-time CO2 fluxes were related to solar radiation, and radiation manipulation suggested photodegradation as the underlying mechanism. In addition, a decline in microbial activity was followed by a reduction in photodegradation-related CO2 fluxes. The levels of microbial decomposition and photodegradation in the dry season were likely the factors influencing carbon mineralization during the subsequent wet season. This study showed that microbial decomposition can be a dominant contributor to CO2 emissions and mass loss in the dry season and it suggests a regulating effect of microbial activity on photodegradation. Microbial decomposition is an important contributor to the dry season decomposition and impacts the annual litter turn-over rates in dry regions. Global warming may lead to reduced moisture availability and dew deposition, which may greatly influence not only microbial decomposition of plant litter, but also photodegradation.

  12. Mechanical Fault Diagnosis of High Voltage Circuit Breakers Based on Variational Mode Decomposition and Multi-Layer Classifier.

    Science.gov (United States)

    Huang, Nantian; Chen, Huaijin; Cai, Guowei; Fang, Lihua; Wang, Yuqiang

    2016-11-10

    Mechanical fault diagnosis of high-voltage circuit breakers (HVCBs) based on vibration signal analysis is one of the most significant issues in improving the reliability and reducing the outage cost for power systems. The limitation of training samples and types of machine faults in HVCBs causes the existing mechanical fault diagnostic methods to recognize new types of machine faults easily without training samples as either a normal condition or a wrong fault type. A new mechanical fault diagnosis method for HVCBs based on variational mode decomposition (VMD) and multi-layer classifier (MLC) is proposed to improve the accuracy of fault diagnosis. First, HVCB vibration signals during operation are measured using an acceleration sensor. Second, a VMD algorithm is used to decompose the vibration signals into several intrinsic mode functions (IMFs). The IMF matrix is divided into submatrices to compute the local singular values (LSV). The maximum singular values of each submatrix are selected as the feature vectors for fault diagnosis. Finally, a MLC composed of two one-class support vector machines (OCSVMs) and a support vector machine (SVM) is constructed to identify the fault type. Two layers of independent OCSVM are adopted to distinguish normal or fault conditions with known or unknown fault types, respectively. On this basis, SVM recognizes the specific fault type. Real diagnostic experiments are conducted with a real SF₆ HVCB with normal and fault states. Three different faults (i.e., jam fault of the iron core, looseness of the base screw, and poor lubrication of the connecting lever) are simulated in a field experiment on a real HVCB to test the feasibility of the proposed method. Results show that the classification accuracy of the new method is superior to other traditional methods.

  13. Mechanical Fault Diagnosis of High Voltage Circuit Breakers Based on Variational Mode Decomposition and Multi-Layer Classifier

    Directory of Open Access Journals (Sweden)

    Nantian Huang

    2016-11-01

    Full Text Available Mechanical fault diagnosis of high-voltage circuit breakers (HVCBs based on vibration signal analysis is one of the most significant issues in improving the reliability and reducing the outage cost for power systems. The limitation of training samples and types of machine faults in HVCBs causes the existing mechanical fault diagnostic methods to recognize new types of machine faults easily without training samples as either a normal condition or a wrong fault type. A new mechanical fault diagnosis method for HVCBs based on variational mode decomposition (VMD and multi-layer classifier (MLC is proposed to improve the accuracy of fault diagnosis. First, HVCB vibration signals during operation are measured using an acceleration sensor. Second, a VMD algorithm is used to decompose the vibration signals into several intrinsic mode functions (IMFs. The IMF matrix is divided into submatrices to compute the local singular values (LSV. The maximum singular values of each submatrix are selected as the feature vectors for fault diagnosis. Finally, a MLC composed of two one-class support vector machines (OCSVMs and a support vector machine (SVM is constructed to identify the fault type. Two layers of independent OCSVM are adopted to distinguish normal or fault conditions with known or unknown fault types, respectively. On this basis, SVM recognizes the specific fault type. Real diagnostic experiments are conducted with a real SF6 HVCB with normal and fault states. Three different faults (i.e., jam fault of the iron core, looseness of the base screw, and poor lubrication of the connecting lever are simulated in a field experiment on a real HVCB to test the feasibility of the proposed method. Results show that the classification accuracy of the new method is superior to other traditional methods.

  14. Potential macro-detritivore range expansion into the subarctic stimulates litter decomposition: a new positive feedback mechanism to climate change?

    Science.gov (United States)

    van Geffen, Koert G; Berg, Matty P; Aerts, Rien

    2011-12-01

    As a result of low decomposition rates, high-latitude ecosystems store large amounts of carbon. Litter decomposition in these ecosystems is constrained by harsh abiotic conditions, but also by the absence of macro-detritivores. We have studied the potential effects of their climate change-driven northward range expansion on the decomposition of two contrasting subarctic litter types. Litter of Alnus incana and Betula pubescens was incubated in microcosms together with monocultures and all possible combinations of three functionally different macro-detritivores (the earthworm Lumbricus rubellus, isopod Oniscus asellus, and millipede Julus scandinavius). Our results show that these macro-detritivores stimulated decomposition, especially of the high-quality A. incana litter and that the macro-detritivores tested differed in their decomposition-stimulating effects, with earthworms having the largest influence. Decomposition processes increased with increasing number of macro-detritivore species, and positive net diveristy effects occurred in several macro-detritivore treatments. However, after correction for macro-detritivore biomass, all interspecific differences in macro-detritivore effects, as well as the positive effects of species number on subarctic litter decomposition disappeared. The net diversity effects also appeared to be driven by variation in biomass, with a possible exception of net diversity effects in mass loss. Based on these results, we conclude that the expected climate change-induced range expansion of macro-detritivores into subarctic regions is likely to result in accelerated decomposition rates. Our results also indicate that the magnitude of macro-detritivore effects on subarctic decomposition will mainly depend on macro-detritivore biomass, rather than on macro-detritivore species number or identity.

  15. ATS-6 engineering performance report. Volume:Program and systems summaries: Mechanical and thermal details

    Science.gov (United States)

    Wales, R. O. (Editor)

    1981-01-01

    The overall mission and spacecraft systems, testing, and operations are summarized. The mechanical subsystems are reviewed, encompassing mechanical design requirements; separation and deployment mechanisms; design and performance evaluation; and the television camera reflector monitor. Thermal control and contamination are discussed in terms of thermal control subsystems, design validation, subsystems performance, the advanced flight experiment, and the quartz-crystal microbalance contamination monitor.

  16. Thermal and mechanical stability of retained austenite surrounded by martensite with different degrees of tempering

    NARCIS (Netherlands)

    Hidalgo Garcia, J.; Findley, K.O.; Santofimia Navarro, M.J.

    2017-01-01

    The mechanical and thermal stability of austenite in multiphase advanced high strength steels are influenced by the surrounding microstructure. The mechanisms underlying and the relations between thermal and mechanical stability are still dubious due to the difficulty of isolating other factors

  17. Evaluation of thermal protection structure mechanism of LMR reactor vessels and design improvement for thermal stress reduction

    Energy Technology Data Exchange (ETDEWEB)

    Joo, Young Sang; Koo, Gyeong Hoi; Kim, Jong Bum; Kim, Seok Hun; Lee, Jae Han

    2003-03-01

    LMR reactor vessels operated in high temperature have a severe thermal damage due to the significant temperature gradient in the hot pool free surface regions of reactor vessel. The thermal protection mechanism of LMR reactor vessel should be designed for the structural integrity in high temperature condition. In this study, the thermal protection mechanism of foreign LMR reactor vessels is investigated for the power upgrade of KALIMER and the modified reactor baffle design with a Y-piece type structure is proposed for the reduction of thermal damage for KALIMER reactor vessel. The modified reactor baffle design leads to reduce the thermal damage such as creep-fatigue and ratcheting in the transient operation condition.

  18. Effect of thermal-treatment sequence on sound absorbing and mechanical properties of porous sound-absorbing/thermal-insulating composites

    Directory of Open Access Journals (Sweden)

    Huang Chen-Hung

    2016-01-01

    Full Text Available Due to recent rapid commercial and industrial development, mechanical equipment is supplemented massively in the factory and thus mechanical operation causes noise which distresses living at home. In livelihood, neighborhood, transportation equipment, jobsite construction noises impact on quality of life not only factory noise. This study aims to preparation technique and property evaluation of porous sound-absorbing/thermal-insulating composites. Hollow three-dimensional crimp PET fibers blended with low-melting PET fibers were fabricated into hollow PET/low-melting PET nonwoven after opening, blending, carding, lapping and needle-bonding process. Then, hollow PET/low-melting PET nonwovens were laminated into sound-absorbing/thermal-insulating composites by changing sequence of needle-bonding and thermal-treatment. The optimal thermal-treated sequence was found by tensile strength, tearing strength, sound-absorbing coefficient and thermal conductivity coefficient tests of porous composites.

  19. New numerical model for thermal quenching mechanism in quartz based on two-stage thermal stimulation of thermoluminescence model

    Directory of Open Access Journals (Sweden)

    Ahmed Kadari

    2015-11-01

    Full Text Available The effect of thermal quenching plays an important role in the thermoluminescence (TL of quartz on which many applications of TL are based. The studies of the stability and kinetics of the 325 °C thermoluminescence peak in quartz are described by Wintle (1975, which show the occurrence of thermal quenching, the decrease in luminescence efficiency with rise in temperature. The thermal quenching of thermoluminescence in quartz was studied experimentally by several authors. The simulations work presented in the literature is based on the single-stage thermal stimulation model of thermoluminescence, in spite of that the mechanisms of this effect remain incomplete. This paper presents a new numerical model for thermal quenching in quartz, using the previously published two-stage thermal stimulation of thermoluminescence model.

  20. Application of new thermoanalytical methods for the investigation of thermal and thermo-oxidative degradation mechanisms and network formation polymers

    OpenAIRE

    Dümichen, Erik

    2016-01-01

    Due to the macromolecular structure of polymers, the application of thermoanalytical meth-ods is advantageous. Thus two new thermoanalytical techniques were developed. The use of these methods was demonstrated on the basis of real examples and the results were com-pared to established thermoanalytical methods. For the thermal and thermo-oxidative analysis of gaseous thermal decomposition products the thermogravimetry (TGA) was coupled with thermal desorption gas chromatography-mass spectro...

  1. Mechanism of Metal-Independent Decomposition of Organic Hydroperoxides and Formation of Alkoxyl Radicals by Halogenated Quinones

    National Research Council Canada - National Science Library

    Ben-Zhan Zhu; Hong-Tao Zhao; Balaraman Kalyanaraman; Jun Liu; Guo-Qiang Shan; Yu-Guo Du; Balz Frei

    2007-01-01

    The metal-independent decomposition of organic hydroperoxides and the formation of organic alkoxyl radicals in the absence or presence of halogenated quinones were studied with electron spin resonance (ESR...

  2. Mechanical-Electrochemical-Thermal Simulation of Lithium-Ion Cells

    Energy Technology Data Exchange (ETDEWEB)

    Santhanagopalan, Shriram; Zhang, Chao; Sprague, Michael A.; Pesaran, Ahmad

    2016-06-01

    Models capture the force response for single-cell and cell-string levels to within 15%-20% accuracy and predict the location for the origin of failure based on the deformation data from the experiments. At the module level, there is some discrepancy due to poor mechanical characterization of the packaging material between the cells. The thermal response (location and value of maximum temperature) agrees qualitatively with experimental data. In general, the X-plane results agree with model predictions to within 20% (pending faulty thermocouples, etc.); the Z-plane results show a bigger variability both between the models and test-results, as well as among multiple repeats of the tests. The models are able to capture the timing and sequence in voltage drop observed in the multi-cell experiments; the shapes of the current and temperature profiles need more work to better characterize propagation. The cells within packaging experience about 60% less force under identical impact test conditions, so the packaging on the test articles is robust. However, under slow-crush simulations, the maximum deformation of the cell strings with packaging is about twice that of cell strings without packaging.

  3. Structural insights into the thermal decomposition sequence of barium tetrahydrogenorthotellurate(VI), Ba[H{sub 4}TeO{sub 6}

    Energy Technology Data Exchange (ETDEWEB)

    Weil, Matthias, E-mail: Matthias.Weil@tuwien.ac.at [Institute for Chemical Technologies and Analytics, Division of Structural Chemistry, TU Wien, Getreidemarkt 9/164-SC, A-1060 Vienna (Austria); Stöger, Berthold [Institute for Chemical Technologies and Analytics, Division of Structural Chemistry, TU Wien, Getreidemarkt 9/164-SC, A-1060 Vienna (Austria); Gierl-Mayer, Christian [Institute for Chemical Technologies and Analytics, TU Wien, Getreidemarkt 9/164-SC, A-1060 Vienna (Austria); Libowitzky, Eugen [Institut für Mineralogie und Kristallographie, Fakultät für Geowissenschaften, Geographie und Astronomie, Universität Wien, Althanstr. 14 (UZA 2), A-1090 Vienna (Austria)

    2016-09-15

    The compounds Ba[H{sub 4}TeO{sub 6}] (I), Ba[H{sub 2}TeO{sub 5}] (II), Ba[Te{sub 2}O{sub 6}(OH){sub 2}] (III) and Ba[TeO{sub 4}] (IV) were prepared by application of a diffusion method (I), under hydrothermal conditions (II and III) and from solid state reactions (IV), respectively. Structure analysis on the basis of single crystal X-ray diffraction data revealed novel structure types for (I), (II) and (III) and isotypism of (IV) with PrSbO{sub 4} and LaSbO{sub 4}. Common feature of the four oxotellurate(VI) structures are [TeO{sub 6}] octahedra. Whereas in the crystal structure of (I) the octahedral units are isolated, they are condensed into chains via corner-sharing in (II) and via edge-sharing in (III) and (IV). The coordination numbers of the barium cations in the four structures range from seven to ten. Although hydrogen atom positions could not be located for the structures of (I) and (II), short interpolyhedral O···O contacts are evident for strong hydrogen bonding. The temperature behaviour of (I), (II) and (IV) was monitored by simultaneous thermal analysis (STA) measurements and in situ powder X-ray diffraction, revealing the decomposition sequence Ba[H{sub 4}TeO{sub 6}] → Ba[H{sub 2}TeO{sub 5}] → Ba[TeO{sub 4}]→ Ba[TeO{sub 3}] upon heating to temperatures up to 900 °C. - Graphical abstract: The crystal structures of the four oxotellurates(VI) were determined from single crystal data. The thermal decomposition of Ba[H{sub 4}TeO{sub 6}], monitored by temperature-dependent X-ray powder diffraction and simultaneous thermal analysis measurements, involves two condensation reactions according to Ba[H{sub 4}TeO{sub 6}]→Ba[H{sub 2}TeO{sub 5}]+H{sub 2}O(↑)→Ba[TeO{sub 4}]+ H{sub 2}O(↑). Display Omitted.

  4. Mechanical performance experiments on rock and cement, casing residual stress evaluation in the thermal recovery well based on thermal-structure coupling

    National Research Council Canada - National Science Library

    Chen, Yong; Peng, Xu; Yu, Hao

    2017-01-01

    .... In this paper, mechanical performance experiments on rock and cement are carried out first, and then a finite element mechanical model of thermal recovery wellbore based on thermal-structure coupling is established...

  5. Ozone Decomposition on the Surface of Metal Oxide Catalyst

    Directory of Open Access Journals (Sweden)

    Batakliev Todor Todorov

    2014-12-01

    Full Text Available The catalytic decomposition of ozone to molecular oxygen over catalytic mixture containing manganese, copper and nickel oxides was investigated in the present work. The catalytic activity was evaluated on the basis of the decomposition coefficient which is proportional to ozone decomposition rate, and it has been already used in other studies for catalytic activity estimation. The reaction was studied in the presence of thermally modified catalytic samples operating at different temperatures and ozone flow rates. The catalyst changes were followed by kinetic methods, surface measurements, temperature programmed reduction and IR-spectroscopy. The phase composition of the metal oxide catalyst was determined by X-ray diffraction. The catalyst mixture has shown high activity in ozone decomposition at wet and dry O3/O2 gas mixtures. The mechanism of catalytic ozone degradation was suggested.

  6. Descomposicion termica del diperoxido de pinacolona (3,6-diterbutil-3,6-dimetil-1,2,4,5-tetraoxaciclohexano en solución de 2-metoxietanol Thermal decomposition of pinacolone diperoxide (3,6-ditertbutyl-3,6-dimethyl-1,2,4,5-tetraoxacyclohexane in 2-methoxyethanol solution

    Directory of Open Access Journals (Sweden)

    Gladys N. Eyler

    2002-05-01

    Full Text Available The thermal decomposition reaction of pinacolone diperoxide (DPP; 0.02 mol kg-1 in 2-methoxyethanol solution studied in the temperature range of 110.0-150.0 °C, follows a first-order kinetic law up to at least 50% DPP conversion. The organic products observed were pinacolone, methane and tert-butane. A stepwise mechanism of decomposition was proposed where the first step is the homolytic unimolecular rupture of the O-O bond. The activation enthalpy and activation entropy for DPP in 2-methoxyethanol were calculated (deltaH# = 43.8 ± 1.0 kcal mol-1 and deltaS# = 31.9 ± 2.6 cal mol-1K-1 and compared with those obtained in other solvents to evaluate the solvent effect.

  7. Mechanically Stretchable and Electrically Insulating Thermal Elastomer Composite by Liquid Alloy Droplet Embedment

    Science.gov (United States)

    Jeong, Seung Hee; Chen, Si; Huo, Jinxing; Gamstedt, Erik Kristofer; Liu, Johan; Zhang, Shi-Li; Zhang, Zhi-Bin; Hjort, Klas; Wu, Zhigang

    2015-01-01

    Stretchable electronics and soft robotics have shown unsurpassed features, inheriting remarkable functions from stretchable and soft materials. Electrically conductive and mechanically stretchable materials based on composites have been widely studied for stretchable electronics as electrical conductors using various combinations of materials. However, thermally tunable and stretchable materials, which have high potential in soft and stretchable thermal devices as interface or packaging materials, have not been sufficiently studied. Here, a mechanically stretchable and electrically insulating thermal elastomer composite is demonstrated, which can be easily processed for device fabrication. A liquid alloy is embedded as liquid droplet fillers in an elastomer matrix to achieve softness and stretchability. This new elastomer composite is expected useful to enhance thermal response or efficiency of soft and stretchable thermal devices or systems. The thermal elastomer composites demonstrate advantages such as thermal interface and packaging layers with thermal shrink films in transient and steady-state cases and a stretchable temperature sensor. PMID:26671673

  8. Rate constants for the thermal decomposition of ethanol and its bimolecular reactions with OH and D : reflected shock tube and theoretical studies.

    Energy Technology Data Exchange (ETDEWEB)

    Sivaramakrishnan, R.; Su, M.-C.; Michael, J. V.; Klippenstein, S. J.; Harding, L. B.; Ruscic, B. (Chemical Sciences and Engineering Division)

    2010-09-09

    The thermal decomposition of ethanol and its reactions with OH and D have been studied with both shock tube experiments and ab initio transition state theory-based master equation calculations. Dissociation rate constants for ethanol have been measured at high T in reflected shock waves using OH optical absorption and high-sensitivity H-atom ARAS detection. The three dissociation processes that are dominant at high T are: C{sub 2}H{sub 5}OH {yields} C{sub 2}H{sub 4} + H{sub 2}O; C{sub 2}H{sub 5}OH {yields} CH{sub 3} + CH{sub 2}OH; C{sub 2}H{sub 5}OH {yields} C{sub 2}H{sub 5} + OH. The rate coefficient for reaction C was measured directly with high sensitivity at 308 nm using a multipass optical White cell. Meanwhile, H-atom ARAS measurements yield the overall rate coefficient and that for the sum of reactions B and C, since H-atoms are instantaneously formed from the decompositions of CH{sub 2}OH and C{sub 2}H{sub 5} into CH{sub 2}O + H and C{sub 2}H{sub 4} + H, respectively. By difference, rate constants for reaction 1 could be obtained. One potential complication is the scavenging of OH by unreacted ethanol in the OH experiments, and therefore, rate constants for OH + C{sub 2}H{sub 5}OH {yields} products were measured using tert-butyl hydroperoxide (tBH) as the thermal source for OH. The present experiments can be represented by the Arrhenius expression k = (2.5 {+-} 0.43) x 10{sup -11} exp(- 911 {+-} 191 K/T) cm{sup 3} molecule{sup -1} s{sup -1} over the T range 857-1297 K. For completeness, we have also measured the rate coefficient for the reaction of D atoms with ethanol D + C{sub 2}H{sub 5}OH {yields} products whose H analogue is another key reaction in the combustion of ethanol. Over the T range 1054-1359 K, the rate constants from the present experiments can be represented by the Arrhenius expression, k = (3.98 {+-} 0.76) x 10{sup -10} exp(- 4494 {+-} 235 K/T) cm{sup 3} molecule{sup -1} s{sup -1}. The high-pressure rate coefficients for reactions B and C

  9. Fundamental understanding of the thermal degradation mechanisms of waste tires and their air pollutant generation in a N2 atmosphere.

    Science.gov (United States)

    Kwon, Eilhann; Castaldi, Marco J

    2009-08-01

    The thermal decomposition of waste tires has been characterized via thermo-gravimetric analysis (TGA) tests, and significant mass loss has been observed between 300 and 500 degrees C. A series of gas chromatography-mass spectrometer (GC-MS) measurements, in which the instrument was coupled to a TGA unit, have been carried out to investigate the thermal degradation mechanisms as well as the air pollutant generation including volatile organic carbons (VOCs) and polycyclic aromatic hydrocarbons (PAHs) in a nitrogen atmosphere. In order to understand fundamental information on the thermal degradation mechanisms of waste tires, the main constituents of tires, poly-isoprene rubber (IR) and styrene butadiene rubber (SBR), have been studied under the same conditions. All of the experimental work indicated that the bond scission on each monomer of the main constituents of tires was followed by hydrogenation and gas phase reactions. This helped to clarify the independent pathways and species attributable to IR and SBR during the pyrolysis process. To extend that understanding to a more practical level, a flow-through reactor was used to test waste tire, SBR and IR samples in the temperature range of 500-800 degrees C at a heating rate of approximately 200 degrees C. Lastly, the formation of VOCs (approximately 1-50 PPMV/10 mg of sample) and PAHs (approximately 0.2-7 PPMV/10 mg of sample) was observed at relatively low temperatures compared to conventional fuels, and its quantified concentration was significantly high due to the chemical structure of SBR and IR. The measurement of chemicals released during pyrolysis suggests not only a methodology for reducing the air pollutants but also the feasibility of petrochemical recovery during thermal treatment.

  10. Effect of EVA on thermal stability, flammability, mechanical properties of HDPE/EVA/Mg(OH)2 composites

    Science.gov (United States)

    Cao, R.; Deng, Z. L.; Ma, Y. H.; Chen, X. L.

    2017-06-01

    In this work, ethylene vinyl acetate (EVA) is introduced to improve the properties of high-density polyethylene (HDPE)/magnesium hydroxide (MH) composites. The thermal stability, flame retardancy and mechanical properties of HDPE/EVA/MH composites are investigated and discussed. With increasing content of EVA, the limiting oxygen index (LOI) of the composites increases. The thermal stability analysis shows that the initial decomposition temperature begins at a low temperature; however, the residues of the composites at 600°C increase when HDPE is replaced by small amounts of EVA. The early degradation absorbs heat, dilute oxygen and residue. During this process, it protects the matrix inside. Compared with the HDPE/MH and EVA/MH composites, the ternary HDPE/EVA/MH composites exhibit better flame retardancy by increasing the LOI values, and reducing the heat release rate (HRR) and total heat release (THR). With increasing content of EVA, the mechanical properties can also be improved, which is attributed to the good affinity between EVA and MH particles.

  11. Polystyrene/nano-SiO2 composite microspheres fabricated by Pickering emulsion polymerization: Preparation, mechanisms and thermal properties

    Directory of Open Access Journals (Sweden)

    W. H. Zhang

    2012-07-01

    Full Text Available We report the preparation, mechanisms and thermal properties of core-shell structured polymer/inorganic nanoparticle composite microspheres prepared by Pickering emulsion polymerization. Stable Pickering emulsion was firstly fabricated by using surface-modified nano-SiO2 particles as stabilizer. And then, two kinds of polystyrene/nano-SiO2 (PS/SiO2 composite microspheres with different sizes and morphologies were synthesized using hydrophobic azobisisobutyronitrile (AIBN and hydrophilic ammonium persulfate (APS as initiator, respectively. The possible mechanisms of Pickering emulsion polymerization initiated by different initiators were proposed according to the results of transmission electron microscope (TEM and scanning electron microscope (SEM. The chemical structure and molecular weight of the composite microspheres were characterized by Fourier transform infrared spectroscopy (FTIR, X-ray diffractometer (XRD and gel permeation chromatography coupled with a multi-angle laser light scattering photometer (GPC-MALLS. Thermogravimetric analysis (TGA and differential scanning calorimeter (DSC were used to comparatively analyze the thermal properties of nanocomposites and corresponding pure polymer. The results indicated that the decomposition temperature and glass transition temperature (Tg of nanocomposites were elevated to a certain degree due to the existence of nano-SiO2.

  12. Thermal decomposition of a hydrotalcite-containing Cu–Zn–Al precursor : thermal methods combined with an in situ DRIFT study

    NARCIS (Netherlands)

    López Granados, M.; Melián-Cabrera, I.; Fierro, J.L.G.

    2002-01-01

    A Cu–Zn–Al precursor (CZA) was synthesized efficiently by coprecipitation of the corresponding cations with sodium carbonate at constant pH and temperature. The starting precursor contained a mixture of two hydroxycarbonate phases: rosasite and a Cu–Zn hydrotalcite-like phase. The thermal

  13. Thermal fluctuations affect the transcriptome through mechanisms independent of average temperature

    OpenAIRE

    Jesper Givskov Sørensen; Mads Fristrup Schou; Torsten Nygaard Kristensen; Volker Loeschcke

    2016-01-01

    Terrestrial ectotherms are challenged by variation in both mean and variance of temperature. Phenotypic plasticity (thermal acclimation) might mitigate adverse effects, however, we lack a fundamental understanding of the molecular mechanisms of thermal acclimation and how they are affected by fluctuating temperature. Here we investigated the effect of thermal acclimation in Drosophila melanogaster on critical thermal maxima (CTmax) and associated global gene expression profiles as induced by ...

  14. Graph Decompositions

    DEFF Research Database (Denmark)

    Merker, Martin

    The topic of this PhD thesis is graph decompositions. While there exist various kinds of decompositions, this thesis focuses on three problems concerning edgedecompositions. Given a family of graphs H we ask the following question: When can the edge-set of a graph be partitioned so that each part...... induces a subgraph isomorphic to a member of H? Such a decomposition is called an H-decomposition. Apart from the existence of an H-decomposition, we are also interested in the number of parts needed in an H-decomposition. Firstly, we show that for every tree T there exists a constant k(T) such that every...... k(T)-edge-connected graph whose size is divisible by the size of T admits a T-decomposition. This proves a conjecture by Barát and Thomassen from 2006. Moreover, we introduce a new arboricity notion where we restrict the diameter of the trees in a decomposition into forests. We conjecture...

  15. Geologic, stratigraphic, thermal, and mechanical factors which influence repository design in the bedded salt environment

    Energy Technology Data Exchange (ETDEWEB)

    Ashby, J.P.; Nair, O.; Ortman, D.; Rowe, J.

    1979-12-01

    This report describes the geologic, stratigraphic, thermal, and mechanical considerations applicable to repository design. The topics discussed in the report include: tectonic activity; geologic structure; stratigraphy; rock mechanical properties; and hydrologic properties.

  16. Coupled Mechanical-Electrochemical-Thermal Analysis of Failure Propagation in Lithium-ion Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Chao; Santhanagopalan, Shriram; Pesaran, Ahmad

    2016-07-28

    This is a presentation given at the 12th World Congress for Computational Mechanics on coupled mechanical-electrochemical-thermal analysis of failure propagation in lithium-ion batteries for electric vehicles.

  17. Improving mechanical robustness of ultralow-k SiOCH plasma enhanced chemical vapor deposition glasses by controlled porogen decomposition prior to UV-hardening

    OpenAIRE

    Urbanowicz, Adam; Vanstreels, Kris; Verdonck,Patrick; Shamiryan, Denis; De Gendt, Stefan; Baklanov, Mikhail

    2010-01-01

    We report a new curing procedure of a plasma enhanced chemical vapor deposited SiCOH glasses for interlayer dielectric applications in microelectronic. It is demonstrated that SiOCH glasses with improved mechanical properties and ultralow dielectric constant can be obtained by controlled decomposition of the porogen molecules used to create nanoscale pores, prior to the UV-hardening step. The Young’s modulus (YM) of conventional SiOCH-based glasses with 32% open porosity hardened with porogen...

  18. Microwave-induced combustion: Thermal and morphological aspects for understanding the mechanism of ignition process for analytical applications.

    Science.gov (United States)

    Pedrotti, Matheus F; Pereira, Leticia S F; Bizzi, Cezar A; Paniz, Jose N G; Barin, Juliano S; Flores, Erico M M

    2017-11-01

    In the present work, for the first time a systematic study was performed using an infrared camera and scanning electron microscopy (SEM) coupled to energy dispersive X-ray spectrometry (EDS) to evaluate the mechanisms involved in microwave-induced combustion method, which has been extensively used for sample preparation. Cellulose and glass fiber discs, wetted with the igniter solution (6molL(-1) NH4NO3), were evaluated under microwave field in a monomode system. The temperature of the discs surface was recorded during microwave irradiation and the effect of NH4NO3 concentration and irradiation time on cellulose oxidation was evaluated. The morphology of the discs surface was characterized by SEM before and after irradiation in an inert atmosphere. According to the results, the surface temperature of the discs increased near to 100°C and remained in this temperature for few seconds while water evaporate. After that, temperature increased over 200°C due to the thermal decomposition of NH4NO3 salt, releasing a large amount of energy that accelerates cellulose oxidation. The higher the igniter concentration, the shorter was the microwave irradiation time for cellulose oxidation. The SEM images revealed that cellulose disc was more porous after microwave irradiation, enhancing oxygen diffusion within the paper and making easier its ignition. The EDS spectrum of cellulose and glass fiber discs showed that signal intensity for nitrogen decreased after microwave irradiation, showing that NH4NO3 was consumed during this process. Therefore, it was demonstrated that the ignition process is the result of synergic interaction of NH4NO3 thermal decomposition and organic matter oxidation (cellulose) releasing heat and feeding the chain reaction. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Thermal Explosion in a Mechanically Activated Ti-Ni System: Mathematical Model

    Science.gov (United States)

    Lapshin, O. V.; Shkoda, O. A.

    2017-01-01

    A mathematical model of a thermal explosion in a mechanically pre-activated Ti-Ni system is constructed in a macroscopic approximation. It is found out that preliminary mechanical activation considerably accelerates the reaction product synthesis. Using the experimental data obtained earlier, the thermal and kinetic constants of the synthesis are determined.

  20. A Rat Model of Full Thickness Thermal Injury Characterized by Thermal Hyperalgesia, Mechanical Allodynia, Pronociceptive Peptide Release and Tramadol Analgesia

    Science.gov (United States)

    2014-01-01

    4 weeks (n 2 per time point) post injury to visualize burn pathology . A board certified veterinary pathol ogist characterized the degree of burn...an animal model of thermal hyperalgesia and mechanical allodynia evoked by full thickness thermal injury that shares pathological characteristics with...sections were rinsed in potassium phosphate buffered saline (KPBS) and incubated in primary antibody solution rabbit anti CGRP (1:10,000; Immunostar; Hudson

  1. Synthesis, characterization and thermal decomposition of [Pd2 (C2-dmba (µ-SO4 (SO22

    Directory of Open Access Journals (Sweden)

    Caires Antonio Carlos Fávero

    1998-01-01

    Full Text Available The bridged sulphate complex [Pd2 (C²,dmba (µ-SO4 (SO22] has been obtained by reacting a saturated solution of SO2 in methanol and the cyclometallated compound [Pd(C²,N-dmba(µ-N3] 2; (dmba = N,N-dimethylbenzylamine, at room temperature for 24 h. Reaction product was characterized by elemental analysis, NMR comprising 13C{¹H} and ¹H nuclei and I.R. spectrum's measurements. Thermal behavior has been investigated and residual products identified by X-ray powder diffraction.

  2. Density functional theory calculations of the hydrazine decomposition mechanism on the planar and stepped Cu(111) surfaces.

    Science.gov (United States)

    Tafreshi, Saeedeh S; Roldan, Alberto; de Leeuw, Nora H

    2015-09-07

    We have investigated the adsorption of hydrazine (N2H4) and its reactivity on terraces and steps of Cu(111) surfaces by first-principles calculations in order to gain insight into the hydrazine decomposition mechanism. We have investigated different possibilities for the N-N and N-H bond cleavage for any intermediate states by analysing the reaction and barrier energies of each elementary step. We have found that hydrazine dehydrogenation via N-H bond scission is neither energetically nor kinetically favourable on the flat and stepped surfaces, but hydrazine prefers to form NH2via N-N bond decoupling on the Cu(111) with an activation energy below 1 eV. The NH2 molecule reacts fairly easily with co-adsorbed NH2 to form NH3 as well as with N2Hx (x = 1-4) by abstracting hydrogen to produce NH3 and N2 molecules on both the flat and stepped surfaces. We also found that all intermediates except NNH prefer N-N bond breaking as the most likely dissociation pathway, where the amide and imide intermediates produced can be hydrogenated to form NH3 in the presence of hydrogen. NNH is the only intermediate, which prefers to dissociate via a highly exothermic N-H bond breaking process to produce an N2 molecule after overcoming a small barrier energy. We also studied the production of H2 by recombination of hydrogen ad-atoms which, considering the activation energies, is particularly favoured under conditions of moderate temperatures. Our results agree well with experiments suggesting that N2H4 adsorbs dissociatively on copper above ∼300 K leading to N2, NH3 and H2. In general, the lower coordination of the steps is found to lead to higher reactivity than on the flat Cu(111) surface. Furthermore, the calculations show that the influence of step edge atoms is very different for the intra- and intermolecular dehydrogenation mechanisms. They also increase the barrier of N-N decoupling of all the existing species in the reaction.

  3. The effect of deformation treatment on the decomposition of supersaturated Ni(Nb,B) and Ni(Mo,B) solid solutions synthesized by mechanical alloying

    Energy Technology Data Exchange (ETDEWEB)

    Kubalova, L.M., E-mail: kubal@yandex.ru [K.L. Khetagurov North-Ossetian State University, Vatutina Str. 44-46, Vladikavkaz 362025 (Russian Federation); Fadeeva, V.I., E-mail: fadeeva@general.chem.msu.ru [Department of Chemistry, M.V. Lomonosov Moscow State University, Moscow 119991 (Russian Federation)

    2014-02-15

    Highlights: • Influence of deformation on decomposition of Ni-based solid solutions was studied. • X-ray diffraction analysis and scanning electron microscopy were used. • Decomposition of Ni(Nb,B), Ni(Mo,B) solid solutions takes place under deformation. • Formation of Ni{sub 21}(Nb,Mo){sub 2}B{sub 6}τ-phases after deformation treatment is observed. • Identity of MA and deformation on the decomposition of solid solutions is shown. -- Abstract: The effect of rotary-shear deformation during powders compacting on the decomposition of supersaturated Ni(Nb,B) and Ni(Mo,B) solid solutions is studied. The metastable fcc solid solutions were synthesized by mechanical alloying (MA) of the mixtures of components of Ni{sub 75}Nb{sub 12}B{sub 13} and Ni{sub 73}Mo{sub 14}B{sub 13} compositions. The powders were compacted on a Bridgman anvil. Col plastic deformation action is realized by using this technique. As a result the initial structure of nonequilibrium supersaturated solid solutions changed. The data of X-ray diffraction analysis and scanning electron microscopy showed a partial decomposition of Ni(Nb,B) and Ni(Mo,B) solid solutions, which leads to the formation of cubic boride τ phases – Ni{sub 21}Nb{sub 2}B{sub 6} with a lattice parameter of a = 1.0572 nm and, correspondingly, Ni{sub 21}Mo{sub 2}B{sub 6} phase with a lattice parameter of a = 1.0498 nm. The τ phase probably forms coherently to the fcc crystal lattice of solid solution because of its lattice parameter is equal to three lattice parameter of nickel. According to the data of local X-ray spectral analysis, the compacted alloys are heterogeneous and are contained boron-reach and also niobium- and molybdenum-rich regions.

  4. Mechanisms Underpinning Degradation of Protective Oxides and Thermal Barrier Coatings in High Hydrogen Content (HHC) - Fueled Turbines

    Energy Technology Data Exchange (ETDEWEB)

    Mumm, Daniel

    2013-08-31

    The overarching goal of this research program has been to evaluate the potential impacts of coal-derived syngas and high-hydrogen content fuels on the degradation of turbine hot-section components through attack of protective oxides and thermal barrier coatings. The primary focus of this research program has been to explore mechanisms underpinning the observed degradation processes, and connections to the combustion environments and characteristic non-combustible constituents. Based on the mechanistic understanding of how these emerging fuel streams affect materials degradation, the ultimate goal of the program is to advance the goals of the Advanced Turbine Program by developing materials design protocols leading to turbine hot-section components with improved resistance to service lifetime degradation under advanced fuels exposures. This research program has been focused on studying how: (1) differing combustion environments – relative to traditional natural gas fired systems – affect both the growth rate of thermally grown oxide (TGO) layers and the stability of these oxides and of protective thermal barrier coatings (TBCs); and (2) how low levels of fuel impurities and characteristic non-combustibles interact with surface oxides, for instance through the development of molten deposits that lead to hot corrosion of protective TBC coatings. The overall program has been comprised of six inter-related themes, each comprising a research thrust over the program period, including: (i) evaluating the role of syngas and high hydrogen content (HHC) combustion environments in modifying component surface temperatures, heat transfer to the TBC coatings, and thermal gradients within these coatings; (ii) understanding the instability of TBC coatings in the syngas and high hydrogen environment with regards to decomposition, phase changes and sintering; (iii) characterizing ash deposition, molten phase development and infiltration, and associated corrosive

  5. Thermal mechanical stress modeling of GCtM seals

    Energy Technology Data Exchange (ETDEWEB)

    Dai, Steve Xunhu [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States); Chambers, Robert [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

    2015-09-01

    Finite-element thermal stress modeling at the glass-ceramic to metal (GCtM) interface was conducted assuming heterogeneous glass-ceramic microstructure. The glass-ceramics were treated as composites consisting of high expansion silica crystalline phases dispersed in a uniform residual glass. Interfacial stresses were examined for two types of glass-ceramics. One was designated as SL16 glass -ceramic, owing to its step-like thermal strain curve with an overall coefficient of thermal expansion (CTE) at 16 ppm/ºC. Clustered Cristobalite is the dominant silica phase in SL16 glass-ceramic. The other, designated as NL16 glass-ceramic, exhibited clusters of mixed Cristobalite and Quartz and showed a near-linear thermal strain curve with a same CTE value.

  6. Improved Standard Electronic Modules, Thermal and Mechanical Analyses and Design

    Science.gov (United States)

    1978-09-01

    center frame. For greater detail on the computer solution to the Comuter -Aided Thermal Modeling, refer to Standard Electronic Modules Exploratory... solutions were obtained for all frame designs and component layout configurations using three metal alloys having different thermal conductivities...as a heat conducting element, was neglected. Concerning this, a separate computer solution was made considering the ISEM fin top as being .270 inch

  7. Enhanced mechanical and thermal properties of regenerated cellulose/graphene composite fibers.

    Science.gov (United States)

    Tian, Mingwei; Qu, Lijun; Zhang, Xiansheng; Zhang, Kun; Zhu, Shifeng; Guo, Xiaoqing; Han, Guangting; Tang, Xiaoning; Sun, Yaning

    2014-10-13

    In this study, a wet spinning method was applied to fabricate regenerated cellulose fibers filled with low graphene loading which was systematically characterized by SEM, TEM, FTIR and XRD techniques. Subsequently, the mechanical and thermal properties of the resulting fibers were investigated. With only 0.2 wt% loading of graphene, a ∼ 50% improvement of tensile strength and 25% enhancement of Young's modulus were obtained and the modified Halpin-Tsai model was built to predict the mechanical properties of composite fibers. Thermal analysis of the composite fibers showed remarkably enhanced thermal stability and dynamic heat transfer performance of graphene-filled cellulose composite fiber, also, the presence of graphene oxide can significantly enhance the thermal conductivity of the composite fiber. This work provided a facile way to improve mechanical and thermal properties of regenerated cellulose fibers. The resultant composite fibers have potential application in thermal insulation and reinforced fibrous materials. Copyright © 2014 Elsevier Ltd. All rights reserved.

  8. A Monte Carlo simulation of a simplified reactor by decomposition of the neutron spectrum into fission, intermediate and thermal distributions

    Energy Technology Data Exchange (ETDEWEB)

    Barcellos, Luiz Felipe F.C.; Bodmann, Bardo E.J.; Vilhena, Marco T. de, E-mail: luizfelipe.fcb@gmail.com, E-mail: bardo.bodmann@ufrgs.br, E-mail: vilhena@mat.ufrgs.br [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre (Brazil). Grupo de Estudos Nucleares. Escola de Engenharia; Leite, Sergio Q. Bogado, E-mail: sbogado@eletronuclear.gov.br [Eletrobras Termonuclear S.A. (ELETRONUCLEAR), Rio de Janeiro, RJ (Brazil)

    2015-07-01

    In this paper the neutron spectrum of a simulated hypothetical nuclear reactor is decomposed as a sum of three probability distributions. Two of the distributions preserve shape with time but not necessarily the integral. One of the two distributions is due to fission, i.e. high neutron energies and the second a Maxwell-Boltzmann distribution for low (thermal) neutron energies. The third distribution has an a priori unknown and possibly variable shape with time and is determined from parametrizations of Monte Carlo simulation. This procedure is effective in attaining two objectives, the first is to include effects due to up-scattering of neutrons, and the second is to optimize computational time of the stochastic method (tracking and interaction). The simulation of the reactor is done with a Monte Carlo computer code with tracking and using continuous energy dependence. This code so far computes down-scattering, but the computation of up-scattering was ignored, since it increases significantly computational processing time. In order to circumvent this problem, one may recognize that up-scattering is dominant towards the lower energy end of the spectrum, where we assume that thermal equilibrium conditions for neutrons immersed in their environment holds. The optimization may thus be achieved by calculating only the interaction rate for neutron energy gain as well as loss and ignoring tracking, i.e. up-scattering is 'simulated' by a statistical treatment of the neutron population. For the fission and the intermediate part of the neutron spectrum tracking is taken into account explicitly, where according to the criticality condition the integral of the fission spectrum may depend on time. This simulation is performed using continuous energy dependence, and as a rst case to be studied we assume a recurrent regime. The three calculated distributions are then used in the Monte Carlo code to compute the subsequent Monte Carlo steps with subsequent updates

  9. Agave nonwovens in polypropylene composites: mechanical and thermal studies

    CSIR Research Space (South Africa)

    John, MJ

    2015-03-01

    Full Text Available nonwovens on the mechanical and dynamic mechanical properties of composites were investigated. Composites containing agave-polypropylene (A-PP) nonwovens exhibited superior mechanical properties compared to the other two. Storage modulus of the composites...

  10. Thermal-Mechanical and Thermal Behavior of High-Temperature Structural Materials.

    Science.gov (United States)

    1979-12-31

    Physical Constants of Porcelain ," Nagoya Kogyo Gijutsu Shikensko Hokoku, 8 [5] 37-43 (1959); Ceram. Abstracts, 1959, Nov. p. 287a. 6. F. P. Knudsen...engineering materials appropriate for conditions which require high thermal shock resistance in combination with good thermal insulating ability"C. Finally

  11. Multiple mechanisms for trait effects on litter decomposition: moving beyond hone-field advantage with a new hypothesis.

    NARCIS (Netherlands)

    Freschet, G.T.; Aerts, R.; Cornelissen, J.H.C.

    2012-01-01

    Evidence is growing that leaf litter generally decomposes faster than expected in its environment of origin, owing to specialization of litter and topsoil decomposer communities to break down litter encountered most often. Nevertheless, this home-field advantage (HFA) in decomposition is

  12. Analysis Methods of HTLS Conductors in Terms of Mechanical and Thermal Criteria

    Directory of Open Access Journals (Sweden)

    Paweł Kubek

    2013-03-01

    Full Text Available A thermal modernization allows increasing the thermal rating of the existing lines. This especially concerns the older overhead lines designed for the +40°C temperature conductor limit. This paper presents reconductoring as the attractive method of existing line thermal modernization. The article provides an overview of issues related to the selection of the HTLS conductor for thermal uprating of existing overhead transmission lines. Some aspects related to the extension of the thermal, electrical and mechanical models used so far for analysis of HTLS conductors are presented in the paper.

  13. Mechanical spectroscopy of thermal stress relaxation in aluminium alloys reinforced with short alumina fibres

    Energy Technology Data Exchange (ETDEWEB)

    Carreno-Morelli, E.; Schaller, R. [Ecole Polytechnique Federale, Lausanne (Switzerland). Inst. de Genie Atomique; Urreta, S.E.

    1998-05-01

    The mechanical behaviour under low temperature thermal cycling of aluminium-based composites reinforced with short Al{sub 2}O{sub 3} SAFFIL fibres has been investigated by mechanical spectroscopy (mechanical loss and elastic shear modulus measurements). A mechanical loss maximum has been observed during cooling which originates in the relaxation of thermal stresses at the interfaces due to the differential thermal expansion between matrix and reinforcement. The maximum height increases with the volumetric fibre content. In addition, if the matrix strength is increased by the appropriated choice of alloy and thermal treatment, the maximum diminishes and shifts to lower temperatures. No damage accumulation at the interfaces has been detected during long period thermal cycling in the range 100 to 500 K. A description of the damping behaviour is made in terms of the development of microplastic zones which surround the fibres. (orig.) 9 refs.

  14. Mechanical and Thermal Properties of Polymethyl Methacrylate-BN Nanotube Composites

    Directory of Open Access Journals (Sweden)

    C. Y. Zhi

    2008-01-01

    Full Text Available Polymethyl methacrylate (PMMA-BN nanotube (BNNT composites were fabricated and their mechanical and thermal properties were analyzed. Using a 1 wt.% BNNTs fraction in a polymer, the elastic modulus of PMMA was increased up to 19%. In addition, thermal stability and glass transition temperature of PMMA were also positively affected. The thermal conductivity of PMMA with BNNT additions increased three times. The resultant BNNT-PMMA composites possess the high electrical breakover voltages. Thus our studies clearly indicate that BNNTs are promising nanofillers for improvement of mechanical and thermal conductivity of dielectric polymers under preservation of their electrical insulation.

  15. Synthesis of MnxGa1-xFe2O4 magnetic nanoparticles by thermal decomposition method for medical diagnosis applications

    Science.gov (United States)

    Sánchez, Javier; Cortés-Hernández, Dora Alicia; Escobedo-Bocardo, José Concepción; Almanza-Robles, José Manuel; Reyes-Rodríguez, Pamela Yajaira; Jasso-Terán, Rosario Argentina; Bartolo-Pérez, Pascual; De-León-Prado, Laura Elena

    2017-04-01

    In this work, the synthesis of MnxGa1-xFe2O4 (x=0-1) nanosized particles by thermal decomposition method, using tetraethylene glycol (TEG) as a reaction medium, has been performed. The crystalline structure of the inverse spinel obtained in all the cases was identified by X-ray diffraction (XRD). Vibration sample magnetometry (VSM) was used to evaluate the magnetic properties of ferrites and to demonstrate their superparamagnetic behavior and the increase of magnetization values due to the Mn2+ ions incorporation into the FeGa2O4 structure. Transmission electron microscopy, energy dispersive spectroscopy (TEM-EDS) and X-ray photoelectron spectroscopy (XPS) were used to characterize the obtained magnetic nanoparticles (MNPs). These MNPs showed a near spherical morphology, an average particle size of 5.6±1.5 nm and a TEG coating layer on their surface. In all the cases MNPs showed no response when submitted to an alternating magnetic field (AMF, 10.2 kA/m, 354 kHz) using magnetic induction tests. These results suggest that the synthesized nanoparticles can be potential candidates for their use in biomedical areas.

  16. Thermal Decomposition Based Synthesis of Ag-In-S/ZnS Quantum Dots and Their Chlorotoxin-Modified Micelles for Brain Tumor Cell Targeting.

    Science.gov (United States)

    Chen, Siqi; Ahmadiantehrani, Mojtaba; Publicover, Nelson G; Hunter, Kenneth W; Zhu, Xiaoshan

    Cadmium-free silver-indium-sulfide (Ag-In-S or AIS) chalcopyrite quantum dots (QDs) as well as their core-shell structures (AIS/ZnS QDs) are being paid significant attention in biomedical applications because of their low toxicity and excellent optical properties. Here we report a simple and safe synthetic system to prepare high quality AIS and AIS/ZnS QDs using thermal decomposition. The synthetic system simply involves heating a mixture of silver acetate, indium acetate, and oleic acid in dodecanethiol at 170 °C to produce AIS QDs with a 13% quantum yield (QY). After ZnS shell growth, the produced AIS/ZnS QDs achieve a 41% QY. To facilitate phase transfer and bioconjugation of AIS/ZnS QDs for cellular imaging, these QDs were loaded into the core of PLGA-PEG (5k:5k) based micelles to form AIS/ZnS QD-micelles. Cellular imaging studies showed that chlorotoxin-conjugated QD-micelles can be specifically internalized into U-87 brain tumor cells. This work discloses that the scalable synthesis of AIS/ZnS QDs and the facile surface/interface chemistry for phase transfer and bioconjugation of these QDs may open an avenue for the produced QD-micelles to be applied to the detection of endogenous targets expressed on brain tumor cells, or more broadly to cell- or tissue-based diagnosis and therapy.

  17. Facile synthesis of ultrafine SnO{sub 2} nanoparticles on graphene nanosheets via thermal decomposition of tin-octoate as anode for lithium ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jinkai; Xie, Sanmu; Cao, Daxian; Lu, Xuan [Xi’an Jiaotong University, State Key Lab of Electrical Insulation and Power Equipment, Center of Nanomaterials for Renewable Energy (CNRE), School of Electrical Engineering (China); Meng, Lingjie, E-mail: menglingjie@mail.xjtu.edu.cn [Xi’an Jiaotong University, Department of Chemistry, School of Science (China); Yang, Guidong [Xi’an Jiaotong University, Department of Chemical Engineering, School of Chemical Engineering and Technology (China); Wang, Hongkang, E-mail: hongkang.wang@mail.xjtu.edu.cn [Xi’an Jiaotong University, State Key Lab of Electrical Insulation and Power Equipment, Center of Nanomaterials for Renewable Energy (CNRE), School of Electrical Engineering (China)

    2016-09-15

    We demonstrate a facile synthesis of ultrafine SnO{sub 2} nanoparticles within graphene nanosheets (GNSs) via thermal decomposition of tin-octoate, in which tin-octoate is firstly blended with GNSs followed by annealing in air at a low temperature (350 °C) and a short time (1 h). As anode for lithium ion batteries, the SnO{sub 2}/GNSs displays superior cycle and rate performance, delivering reversible capacities of 803 and 682 mA h/g at current densities of 200 and 500 mA/g after 120 cycles, respectively, much higher than that of pure SnO{sub 2} and GNSs counterparts (143 and 310 mA h/g at 500 mA/g after 120 cycles, respectively). The enhanced electrochemical performance is attributed to the ultrafine SnO{sub 2} nanoparticle size and introduction of GNSs. GNSs prevent the aggregation of the ultrafine SnO{sub 2} nanoparticles, which alleviate the stress and also provide more electrochemically active sites for lithium insertion and extraction. Moreover, GNSs with large specific surface area (~363 m{sup 2}/g) act as a good electrical conductor which greatly improves the electrode conductivity and also an excellent buffer matrix to tolerate the severe volume changes originated from the Li-Sn alloying-dealloying. This work provides a straight-forward synthetic approach for the design of novel composite anode materials with superior electrochemical performance.

  18. Facile synthesis of ultrafine SnO2 nanoparticles on graphene nanosheets via thermal decomposition of tin-octoate as anode for lithium ion batteries

    Science.gov (United States)

    Wang, Jinkai; Xie, Sanmu; Cao, Daxian; Lu, Xuan; Meng, Lingjie; Yang, Guidong; Wang, Hongkang

    2016-09-01

    We demonstrate a facile synthesis of ultrafine SnO2 nanoparticles within graphene nanosheets (GNSs) via thermal decomposition of tin-octoate, in which tin-octoate is firstly blended with GNSs followed by annealing in air at a low temperature (350 °C) and a short time (1 h). As anode for lithium ion batteries, the SnO2/GNSs displays superior cycle and rate performance, delivering reversible capacities of 803 and 682 mA h/g at current densities of 200 and 500 mA/g after 120 cycles, respectively, much higher than that of pure SnO2 and GNSs counterparts (143 and 310 mA h/g at 500 mA/g after 120 cycles, respectively). The enhanced electrochemical performance is attributed to the ultrafine SnO2 nanoparticle size and introduction of GNSs. GNSs prevent the aggregation of the ultrafine SnO2 nanoparticles, which alleviate the stress and also provide more electrochemically active sites for lithium insertion and extraction. Moreover, GNSs with large specific surface area ( 363 m2/g) act as a good electrical conductor which greatly improves the electrode conductivity and also an excellent buffer matrix to tolerate the severe volume changes originated from the Li-Sn alloying-dealloying. This work provides a straight-forward synthetic approach for the design of novel composite anode materials with superior electrochemical performance.

  19. A comparative study of magnetic properties of MnFe2O4 nanoparticles prepared by thermal decomposition and solvothermal methods

    Directory of Open Access Journals (Sweden)

    B Aslibeiki

    2017-09-01

    Full Text Available A comparative study of magnetic properties of MnFe2O4 ferrite nanoparticles prepared by two different methods has been reported. The first sample (S1 was synthesized by thermal decomposition of metal nitrates. And the second sample (S2 was prepared by solvothermal method using Tri-ethylene glycol (TEG. Magnetic hysteresis loops at 300 and 5 K; magnetization and AC susceptibility measurements versus temperature confirmed the effective role of TEG on the magnetic properties of nanoparticles. The results showed that, at 300 K the saturation magnetization (MS of S2 sample is 46% greater than that of S1 sample. At 5 K, the difference in MS of the samples raised to 60%. AC susceptibility measurements at different frequencies and also magnetization versus temperature under field cooling and zero field cooling processes revealed that, the TEG molecules influence the surface spins order of S2 sample. The sample S1 showed strongly interacting superspin glass state, while the sample S2 consists of weakly interacting superparamagnetic nanoparticles.

  20. Rapid synthesis and optical properties of hematite ({alpha}-Fe{sub 2}O{sub 3}) nanostructures using a simple thermal decomposition method

    Energy Technology Data Exchange (ETDEWEB)

    Al-Gaashani, R., E-mail: Rashad_jashani@yahoo.com [School of Applied Physics, Faculty Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor (Malaysia); Department of Physics, Thamar University, Dhamar, Republic of Yemen (Yemen); Radiman, S. [School of Applied Physics, Faculty Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor (Malaysia); Tabet, N. [Department of Physics and Center of Research Excellence in Renewable Energy, King Fahd University of Petroleum and Minerals, Dhahran (Saudi Arabia); Daud, A.R. [School of Applied Physics, Faculty Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor (Malaysia)

    2013-02-15

    Highlights: Black-Right-Pointing-Pointer A novel method for the synthesis of hematite nanopowder is reported. Black-Right-Pointing-Pointer The morphology of {alpha}-Fe{sub 2}O{sub 3} changed with altering the preparation temperature. Black-Right-Pointing-Pointer The coral like nano {alpha}-Fe{sub 2}O{sub 3} prepared at 500 and 600 Degree-Sign C showed novel optical behavior. Black-Right-Pointing-Pointer The coral like nano {alpha}-Fe{sub 2}O{sub 3} could be used to enhance efficiency of the solar cells. - Abstract: Hematite nanostructures were prepared by a simple technique using the thermal decomposition of iron (III) nitrate 9-hydrate at different temperatures under air atmosphere. Observations using field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) showed that the morphology of the nanostructures changed as the temperature was varied while their size increased with increasing preparation time. Samples prepared at 300, 400, and 500 Degree-Sign C were made of particles with a quantum dots (QDs) size. X-ray photoelectron spectroscopy (XPS), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) confirmed that the as-synthesized powders are pure {alpha}-Fe{sub 2}O{sub 3}. The optical energy gap of the samples varied from 3.2 eV to 2.7 eV as the preparation temperature increased from 300 Degree-Sign C to 600 Degree-Sign C.