Sample records for thermal decomposition kinetics
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Further insights into the kinetics of thermal decomposition during continuous cooling.
Liavitskaya, Tatsiana; Guigo, Nathanaël; Sbirrazzuoli, Nicolas; Vyazovkin, Sergey
2017-07-26
Following the previous work (Phys. Chem. Chem. Phys., 2016, 18, 32021), this study continues to investigate the intriguing phenomenon of thermal decomposition during continuous cooling. The phenomenon can be detected and its kinetics can be measured by means of thermogravimetric analysis (TGA). The kinetics of the thermal decomposition of ammonium nitrate (NH 4 NO 3 ), nickel oxalate (NiC 2 O 4 ), and lithium sulfate monohydrate (Li 2 SO 4 ·H 2 O) have been measured upon heating and cooling and analyzed by means of the isoconversional methodology. The results have confirmed the hypothesis that the respective kinetics should be similar for single-step processes (NH 4 NO 3 decomposition) but different for multi-step ones (NiC 2 O 4 decomposition and Li 2 SO 4 ·H 2 O dehydration). It has been discovered that the differences in the kinetics can be either quantitative or qualitative. Physical insights into the nature of the differences have been proposed.
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Thermal decomposition kinetics of ammonium uranyl carbonate
International Nuclear Information System (INIS)
Kim, E.H.; Park, J.J.; Park, J.H.; Chang, I.S.; Choi, C.S.; Kim, S.D.
1994-01-01
The thermal decomposition kinetics of AUC [ammonium uranyl carbonate; (NH 4 ) 4 UO 2 (CO 3 ) 3 [ in an isothermal thermogravimetric (TG) reactor under N 2 atmosphere has been determined. The kinetic data can be represented by the two-dimensional nucleation and growth model. The reaction rate increases and activation energy decreases with increasing particle size and precipitation time which appears in the particle size larger than 30 μm in the mechano-chemical phenomena. (orig.)
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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.
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International Nuclear Information System (INIS)
Karelin, A.I.; Lobas, O.P.; Zhiganov, A.N.; Vasil'ev, K.F.; Zhiganova, A.A.
1987-01-01
A study was made on ammonium nitrate effect on the mechanism and kinetics of dehydration and thermal decomposition of ammonium polyuranates. Sufficient effect of nitrate ion content in ammonium polyuranate samples on their thermal stability was noted. Kinetic parameters of thermal decomposition of ammonium polyuranates were evaluated. Mechanism of dehydration and thermal decomposition of ammonium polyuranates in the presence of ammonium nitrate was suggested. It was shown that increase of ammonium nitrate content in ammonium polyuranate precipitate resulted to reduction of the specific surface of prepared uranium mixed oxide
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International Nuclear Information System (INIS)
Karelin, A.I.; Lobas, O.P.; Zhiganov, A.N.; Vasil'ev, K.F.; Zhiganova, A.A.
1988-01-01
The influence of ammonium nitrate on the mechanism and kinetics of dehydration and thermal decomposition of ammonium polyuranates was studied. An appreciable influence of the nitrate ion content in the samples of ammonium polyuranates on the development of thermal stability has been noted. The kinetic parameters of the thermal decomposition of ammonium polyuranates have been evaluated. A mechanism of the dehydration and thermal decomposition of ammonium polyuranates in the presence of ammonium nitrate has been proposed. It was shown that increase in the content of ammonium nitrate in the precipitate of ammonium polyuranates leads to a decrease in the specific surface of uranoso-uranic oxide
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International Nuclear Information System (INIS)
Hassan, R.M.; Farid, T.; El-Bellihi, A.A.
1992-01-01
The thermal decomposition of γ-irradiated and unirradiated complexes of mandelhydroxamic acid (HMA), Co (HMA) 2 .1/2H 2 O, Mn (HMA) 2 .2H 2 O, Ba (HMA) 2 .2H 2 O and Cd (HMA) 2 .2H 2 O have been studied thermogravimetrically (under isothermal conditions). The thermal dehydration of each complex occured in one step, while the decomposition of dehydrated complexes occured in two steps. The kinetic parameters for dehydration were computed by different models. The thermal dehydration is regulated by random nucleation A 3 for Co-, Mn-, and Cd-complexes and by phase-boundary (R 3 ) for Ba-complex. The effect of γ-irradiation on the kinetic parameters of thermal decomposition is discussed. Radiation did not modify the mechanism of the reaction but accelarated the dehydration steps in the case of Mn- and Co-complexes. (author) 7 refs.; 1 fig.; 4 tabs
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A High Temperature Kinetic Study for the Thermal Unimolecular Decomposition of Diethyl Carbonate
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.
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A High Temperature Kinetic Study for the Thermal Unimolecular Decomposition of Diethyl Carbonate
Alabbad, Mohammed; Giri, Binod; Szőri, Milan; Viskolcz, Bé la; Farooq, Aamir
2017-01-01
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.
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International Nuclear Information System (INIS)
Ismail, I.M.K.; Hawkins, T.
2005-01-01
Recently, interest in aluminium hydride (alane) as a rocket propulsion ingredient has been renewed due to improvements in its manufacturing process and an increase in thermal stability. When alane is added to solid propellant formulations, rocket performance is enhanced and the specific impulse increases. Preliminary work was performed at AFRL on the characterization and evaluation of two alane samples. Decomposition kinetics were determined from gravimetric TGA data and volumetric vacuum thermal stability (VTS) results. Chemical analysis showed the samples had 88.30% (by weight) aluminium and 9.96% hydrogen. The average density, as measured by helium pycnometery, was 1.486 g/cc. Scanning electron microscopy showed that the particles were mostly composed of sharp edged crystallographic polyhedral such as simple cubes, cubic octahedrons and hexagonal prisms. Thermogravimetric analysis was utilized to investigate the decomposition kinetics of alane in argon atmosphere and to shed light on the mechanism of alane decomposition. Two kinetic models were successfully developed and used to propose a mechanism for the complete decomposition of alane and to predict its shelf-life during storage. Alane decomposes in two steps. The slowest (rate-determining) step is solely controlled by solid state nucleation of aluminium crystals; the fastest step is due to growth of the crystals. Thus, during decomposition, hydrogen gas is liberated and the initial polyhedral AlH 3 crystals yield a final mix of amorphous aluminium and aluminium crystals. After establishing the kinetic model, prediction calculations indicated that alane can be stored in inert atmosphere at temperatures below 10 deg. C for long periods of time (e.g., 15 years) without significant decomposition. After 15 years of storage, the kinetic model predicts ∼0.1% decomposition, but storage at higher temperatures (e.g. 30 deg. C) is not recommended
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Determination of Kinetic Parameters for the Thermal Decomposition of Parthenium hysterophorus
Directory of Open Access Journals (Sweden)
Dhaundiyal Alok
2018-02-01
Full Text Available A kinetic study of pyrolysis process of Parthenium hysterophorous is carried out by using thermogravimetric analysis (TGA equipment. The present study investigates the thermal degradation and determination of the kinetic parameters such as activation E and the frequency factor A using model-free methods given by Flynn Wall and Ozawa (FWO, Kissinger-Akahira-Sonuse (KAS and Kissinger, and model-fitting (Coats Redfern. The results derived from thermal decomposition process demarcate decomposition of Parthenium hysterophorous among the three main stages, such as dehydration, active and passive pyrolysis. It is shown through DTG thermograms that the increase in the heating rate caused temperature peaks at maximum weight loss rate to shift towards higher temperature regime. The results are compared with Coats Redfern (Integral method and experimental results have shown that values of kinetic parameters obtained from model-free methods are in good agreement. Whereas the results obtained through Coats Redfern model at different heating rates are not promising, however, the diffusion models provided the good fitting with the experimental data.
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Effect of pre-heating on the thermal decomposition kinetics of cotton
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-...
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Kinetic study and thermal decomposition behavior of viscoelastic memory foam
International Nuclear Information System (INIS)
Garrido, María A.; Font, Rafael; Conesa, Juan A.
2016-01-01
Highlights: • The thermal degradation has been studied under three different atmospheres. • Pyrolysis and combustion kinetic models have been proposed. • Evolved products under different atmospheres have been analyzed by TG-FTIR and TG-MS. - Abstract: A systematic investigation of the thermal decomposition of viscoelastic memory foam (VMF) was performed using thermogravimetric analysis (TGA) to obtain the kinetic parameters, and thermogravimetric analysis coupled to Fourier Transformed Infrared Spectrometry (TGA-FTIR) and thermogravimetric analysis coupled to Mass Spectrometry (TGA-MS) to obtain detailed information of evolved products on pyrolysis and oxidative degradations. Two consecutive nth-order reactions were employed to correlate the experimental data from dynamic and isothermal runs performed at three different heating rates (5, 10 and 20 K/min) under an inert atmosphere. On the other hand, for the kinetic study of the oxidative decomposition, the data from combustion (synthetic air) and poor oxygen combustion (N_2:O_2 = 9:1) runs, at three heating rates and under dynamic and isothermal conditions, were correlated simultaneously. A kinetic model consisting of three consecutive reactions presented a really good correlation in all runs. TGA-FTIR analysis showed that the main gases released during the pyrolysis of VMF were determined as ether and aliphatic hydrocarbons, whereas in combustion apart from the previous gases, aldehydes, amines and CO_2 have also been detected as the main gases. These results were confirmed by the TGA-MS.
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International Nuclear Information System (INIS)
Sakurai, K.R.; Schaeffer, D.A.; Herley, P.J.
1978-01-01
A thermogravimetric study of the kinetics of thermal nuclei formation and growth has been carried out for the dehydration and decomposition of single crystal strontium permanganate trihydrate, cadmium permanganate hexahydrate, and calcium permanganate pentahydrate. The isothermal dehydration of strontium parmanganate trihydrate occurs in two stages between 50 and 100 0 C. The dehydration kinetics suggest that the two dehydration stages are based on a single-step nucleation process followed by a growth process without nuclei overlap. The resulting activation energies are consistent with the proposed nucleation theory. For the dehydration kinetics of cadmium permanganate hexahydrate, an overlapping nucleation growth mechanism appears to be operating between 30 and 60 0 C. The results are irreproducible for the dehydration of calcium permanganate pentahydrate at 100 0 C. The thermal decomposition studies indicate that the data of the sigmoidal, isothermal fractional decomposition vs. time curves are reproducible for whole and ground crystals of each dehydrated permanganate. All of the data plots contain an induction or slow rate period, an acceleratory and a decay period. The induction period can be shortened by irradiation with 60 Co γ-rays prior to decomposition. Activation energies obtained for all three materials for the various thermal decomposition periods are found to be similar to those published previously on other alkali and alkaline-earth permanganates. (Auth.)
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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...
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Kinetics of the thermal decomposition of nickel iodide
International Nuclear Information System (INIS)
Nakajima, Hayato; Shimizu, Saburo; Onuki, Kaoru; Ikezoe, Yasumasa; Sato, Shoichi
1984-01-01
Thermal decomposition kinetics of NiI 2 under constant I 2 partial pressure was studied by thermogravimetry. The reaction is considered as a reaction step of the thermochemical hydrogen production process in the Ni-I-S system. At temperatures from 775K to 869K and under I 2 pressures from 0 to 960Pa, the decomposition started at the NiI 2 pellet surface and the reactant-product interface moved interior at a constant rate until the decomposed fraction, α, reached 0.6. The overall reaction rate at a constant temperature can be expressed as the difference of the constant decomposition (forward) rate, which is proportional to the equilibrium dissociation pressure of NiI 2 , and the iodide formation (backward) rate, which is proportional to the I 2 pressure. The apparent activation energy of the decomposition was 147 kJ.mol -1 , which is very close to the heat of reaction, 152 kJ.mol -1 calculated from the equilibrium dissociation pressure. The electron microscopic observations, revealed that the reaction product obtained by decomposing NiI 2 under pure He atomosphere was composed of relatively well grown cubic Ni crystals. Whereas, the decomposed product obtained under I 2 -He mixture was composed of larger but disordered crystals. (author)
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Erbium hydride decomposition kinetics.
Energy Technology Data Exchange (ETDEWEB)
Ferrizz, Robert Matthew
2006-11-01
Thermal desorption spectroscopy (TDS) is used to study the decomposition kinetics of erbium hydride thin films. The TDS results presented in this report are analyzed quantitatively using Redhead's method to yield kinetic parameters (E{sub A} {approx} 54.2 kcal/mol), which are then utilized to predict hydrogen outgassing in vacuum for a variety of thermal treatments. Interestingly, it was found that the activation energy for desorption can vary by more than 7 kcal/mol (0.30 eV) for seemingly similar samples. In addition, small amounts of less-stable hydrogen were observed for all erbium dihydride films. A detailed explanation of several approaches for analyzing thermal desorption spectra to obtain kinetic information is included as an appendix.
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Gai, Chao; Zhang, Yuanhui; Chen, Wan-Ting; Zhang, Peng; Dong, Yuping
2013-12-01
The thermal decomposition behavior of two microalgae, Chlorella pyrenoidosa (CP) and Spirulina platensis (SP), were investigated on a thermogravimetric analyzer under non-isothermal conditions. Iso-conversional Vyazovkin approach was used to calculate the kinetic parameters, and the universal integral method was applied to evaluate the most probable mechanisms for thermal degradation of the two feedstocks. The differential equations deduced from the models were compared with experimental data. For the range of conversion fraction investigated (20-80%), the thermal decomposition process of CP could be described by the reaction order model (F3), which can be calculated by the integral equation of G(α) = [(1 - α)(-2) - 1]/2. And the apparent activation energy was in the range of 58.85-114.5 kJ/mol. As for SP, it can be described by the reaction order model (F2), which can be calculated by the integral equation of G(α) = (1 - α)(-1) - 1, and the range of apparent activation energy was 74.35-140.1 kJ/mol. Copyright © 2013 Elsevier Ltd. All rights reserved.
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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.
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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
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Ahmed, M. F.; Hussain, A.; Malik, A. Q.
2016-08-01
Use of energetic materials has long been considered for only military purposes. However, it is very recent that their practical applications in wide range of commercial fields such as mining, road building, under water blasting and rocket propulsion system have been considered. About 5mg of 2,4,6-trinitrotoluene (TNT) in serviceable (Svc) as well as unserviceable (Unsvc) form were used for their thermal decomposition and kinetic parameters investigation. Thermogravimetric/ differential thermal analysis (TG/DTA), X-ray diffraction (XRD) and Scanning electron microscope (SEM) were used to characterize two types of TNT. Arrhenius kinetic parameters like activation energy (E) and enthalpy (AH) of both TNT samples were determined using TG curves with the help of Horowitz and Metzger method. Simultaneously, thermal decomposition range was evaluated from DTA curves. Distinct diffraction peaks showing crystalline nature were obtained from XRD analysis. SEM results indicated that Unsvc TNT contained a variety of defects like cracks and porosity. Similarly, it is observed that thermal as well as kinetic behavior of both TNT samples vary to a great extent. Likewise, a prominent change in the activation energies (E) of both samples is observed. This in-depth study provides a way forward in finding solutions for the safe reutilization of decanted TNT.
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Synthesis and thermal decomposition kinetics of Th(IV) complex with unsymmetrical Schiff base ligand
International Nuclear Information System (INIS)
Fan Yuhua; Bi Caifeng; Liu Siquan; Yang Lirong; Liu Feng; Ai Xiaokang
2006-01-01
A new unsymmetrical Schiff base ligand (H 2 LLi) was synthesized using L-lysine, o-vanillin and salicylaladyde. Thorium(IV) complex of this ligand [Th(H 2 L)(NO 3 )](NO 3 ) 2 x 3H 2 O have been prepared and characterized by elemental analyses, IR, UV and molar conductance. The thermal decomposition kinetics of the complex for the second stage was studied under non-isothermal condition by TG and DTG methods. The kinetic equation may be expressed as: dα/dt = A x e -E/RT x 1/2 (1-α) x [-ln(1-α)] -1 . The kinetic parameters (E, A), activation entropy ΔS ≠ and activation free-energy ΔG ≠ were also calculated. (author)
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Thermal decomposition kinetics of antimony oxychloride in air
Institute of Scientific and Technical Information of China (English)
阳卫军; 唐谟堂; 金胜明
2002-01-01
The DTA and XRD techniques were employed to study thermal decomposition mechanism of antimony oxychloride SbOCl in the air. The thermal decomposition reaction occurs in four steps, and the former three steps as: SbOCl(s)→Sb4O5Cl2(s)+SbCl3(g)→Sb8O11Cl2(s)+SbCl3(g)→Sb2O3(s)+SbCl3(g). The forth step is the oxidation of Sb2O3 by air, Sb2O3(s)+O2→Sb2O4(s). The activation energy and the order of the thermal decomposition reaction of antimony oxychloride in three steps presented in DTA curves were calculated according to Kinssinger methods from DTA curves. The values of activation energy and the order are respectively 91.97kJ/mol, 0.73 in the first step, 131.14kJ/mol, 0.63 in the second step and 146.94kJ/mol, 1.58 in the third step.
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Institute of Scientific and Technical Information of China (English)
ZHANG,Jian-Jun; REN,Ning; XU,Su
2007-01-01
The complex [Sm(p-MBA)3phen]2 (p-MBA, p-methylbenzoate; phen, 1,10-phenanthroline) was prepared and characterized by elemental analysis, IR and UV spectra. The thermal decomposition process of [Sm(p-MBA)3phen]2 was studied under a static air atmosphere by TG-DTG and IR techniques. Thermal decomposition kinetics was investigated employing a newly proposed method, together with the integral isoconversional non-linear method. Meanwhile, the thermodynamic parameters (△H≠, AG≠ and △S≠) were also calculated. The lifetime equation at mass-loss of 10% was deduced as lnτ= -24.7825+18070.43/T by isothermal thermogravimetric analysis.
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International Nuclear Information System (INIS)
Kroon, Maaike C.; Buijs, Wim; Peters, Cor J.; Witkamp, Geert-Jan
2007-01-01
The long-term thermal stability of ionic liquids is of utmost importance for their industrial application. Although the thermal decomposition temperatures of various ionic liquids have been measured previously, experimental data on the thermal decomposition mechanisms and kinetics are scarce. It is desirable to develop quantitative chemical tools that can predict thermal decomposition mechanisms and temperatures (kinetics) of ionic liquids. In this work ab initio quantum chemical calculations (DFT-B3LYP) have been used to predict thermal decomposition mechanisms, temperatures and the activation energies of the thermal breakdown reactions. These quantum chemical calculations proved to be an excellent method to predict the thermal stability of various ionic liquids
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Thermal decomposition of beryllium perchlorate tetrahydrate
International Nuclear Information System (INIS)
Berezkina, L.G.; Borisova, S.I.; Tamm, N.S.; Novoselova, A.V.
1975-01-01
Thermal decomposition of Be(ClO 4 ) 2 x4H 2 O was studied by the differential flow technique in the helium stream. The kinetics was followed by an exchange reaction of the perchloric acid appearing by the decomposition with potassium carbonate. The rate of CO 2 liberation in this process was recorded by a heat conductivity detector. The exchange reaction yielding CO 2 is quantitative, it is not the limiting one and it does not distort the kinetics of the process of perchlorate decomposition. The solid products of decomposition were studied by infrared and NMR spectroscopy, roentgenography, thermography and chemical analysis. A mechanism suggested for the decomposition involves intermediate formation of hydroxyperchlorate: Be(ClO 4 ) 2 x4H 2 O → Be(OH)ClO 4 +HClO 4 +3H 2 O; Be(OH)ClO 4 → BeO+HClO 4 . Decomposition is accompained by melting of the sample. The mechanism of decomposition is hydrolytic. At room temperature the hydroxyperchlorate is a thick syrup-like compound crystallizing after long storing
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An investigation on thermal decomposition of DNTF-CMDB propellants
Energy Technology Data Exchange (ETDEWEB)
Zheng, Wei; Wang, Jiangning; Ren, Xiaoning; Zhang, Laying; Zhou, Yanshui [Xi' an Modern Chemistry Research Institute, Xi' an 710065 (China)
2007-12-15
The thermal decomposition of DNTF-CMDB propellants was investigated by pressure differential scanning calorimetry (PDSC) and thermogravimetry (TG). The results show that there is only one decomposition peak on DSC curves, because the decomposition peak of DNTF cannot be separated from that of the NC/NG binder. The decomposition of DNTF can be obviously accelerated by the decomposition products of the NC/NG binder. The kinetic parameters of thermal decompositions for four DNTF-CMDB propellants at 6 MPa were obtained by the Kissinger method. It is found that the reaction rate decreases with increasing content of DNTF. (Abstract Copyright [2007], Wiley Periodicals, Inc.)
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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.
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Thermal stability and kinetics of decomposition of ammonium nitrate in the presence of pyrite
International Nuclear Information System (INIS)
Gunawan, Richard; Zhang Dongke
2009-01-01
The interaction between ammonium nitrate based industrial explosives and pyrite-rich minerals in mining operations can lead to the occurrence of spontaneous explosion of the explosives. In an effort to provide a scientific basis for safe applications of industrial explosives in reactive mining grounds containing pyrite, ammonium nitrate decomposition, with and without the presence of pyrite, was studied using a simultaneous Differential Scanning Calorimetry and Thermogravimetric Analyser (DSC-TGA) and a gas-sealed isothermal reactor, respectively. The activation energy and the pre-exponential factor of ammonium nitrate decomposition were determined to be 102.6 kJ mol -1 and 4.55 x 10 7 s -1 without the presence of pyrite and 101.8 kJ mol -1 and 2.57 x 10 9 s -1 with the presence of pyrite. The kinetics of ammonium nitrate decomposition was then used to calculate the critical temperatures for ammonium nitrate decomposition with and without the presence of pyrite, based on the Frank-Kamenetskii model of thermal explosion. It was shown that the presence of pyrite reduces the temperature for, and accelerates the rate of, decomposition of ammonium nitrate. It was further shown that pyrite can significantly reduce the critical temperature of ammonium nitrate decomposition, causing undesired premature detonation of the explosives. The critical temperature also decreases with increasing diameter of the blast holes charged with the explosive. The concept of using the critical temperature as indication of the thermal stability of the explosives to evaluate the risk of spontaneous explosion was verified in the gas-sealed isothermal reactor experiments.
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Thermal stability and kinetics of decomposition of ammonium nitrate in the presence of pyrite.
Gunawan, Richard; Zhang, Dongke
2009-06-15
The interaction between ammonium nitrate based industrial explosives and pyrite-rich minerals in mining operations can lead to the occurrence of spontaneous explosion of the explosives. In an effort to provide a scientific basis for safe applications of industrial explosives in reactive mining grounds containing pyrite, ammonium nitrate decomposition, with and without the presence of pyrite, was studied using a simultaneous Differential Scanning Calorimetry and Thermogravimetric Analyser (DSC-TGA) and a gas-sealed isothermal reactor, respectively. The activation energy and the pre-exponential factor of ammonium nitrate decomposition were determined to be 102.6 kJ mol(-1) and 4.55 x 10(7)s(-1) without the presence of pyrite and 101.8 kJ mol(-1) and 2.57 x 10(9)s(-1) with the presence of pyrite. The kinetics of ammonium nitrate decomposition was then used to calculate the critical temperatures for ammonium nitrate decomposition with and without the presence of pyrite, based on the Frank-Kamenetskii model of thermal explosion. It was shown that the presence of pyrite reduces the temperature for, and accelerates the rate of, decomposition of ammonium nitrate. It was further shown that pyrite can significantly reduce the critical temperature of ammonium nitrate decomposition, causing undesired premature detonation of the explosives. The critical temperature also decreases with increasing diameter of the blast holes charged with the explosive. The concept of using the critical temperature as indication of the thermal stability of the explosives to evaluate the risk of spontaneous explosion was verified in the gas-sealed isothermal reactor experiments.
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Czech Academy of Sciences Publication Activity Database
Asadi, M.; Asadi, Z.; Savaripoor, N.; Dušek, Michal; Eigner, Václav; Shorkaei, M.R.; Sedaghat, M.
2015-01-01
Roč. 136, Feb (2015), 625-634 ISSN 1386-1425 R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : Oxovanadium(IV) complexes * Schiff base * Kinetic s of thermal decomposition * Electrochemistry Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.653, year: 2015
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Energy Technology Data Exchange (ETDEWEB)
Yang, Hee-Chul, E-mail: nhcyang@kaeri.re.kr; Kim, Hyung-Ju; Lee, Si-Young; Yang, In-Hwan; Chung, Dong-Yong
2017-06-15
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(PO{sub 3}){sub 4}, into uranium pyrophosphate, UP{sub 2}O{sub 7}, have been studied from the view point of reaction kinetics and acting mechanisms. A mixture of U(PO{sub 3}){sub 4} and UP{sub 2}O{sub 7} was prepared from the pyrolysis residue of uranium-bearing spent TBP. A kinetic analysis of the reaction of U(PO{sub 3}){sub 4} into UP{sub 2}O{sub 7} 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(PO{sub 3}){sub 4} into UP{sub 2}O{sub 7} followed a single-step reaction with an activation energy of 175.29 ± 1.58 kJ mol{sup −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 UP{sub 2}O{sub 7} during the solid-state decomposition of U(PO{sub 3}){sub 4}. - Highlights: •Thermal decomposition kinetics of U(PO{sub 3}){sub 4} into UP{sub 2}O{sub 7} was investigated. •The thermal decomposition followed a single-step reaction with an activation energy of 175.3 ± 1.6 kJ mol{sup −1}. •The most probable kinetic model was determined as a type of nucleation and nuclei-growth models, the Avrami-Erofeev (A3).
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Kinetic study of lithium-cadmium ternary amalgam decomposition
International Nuclear Information System (INIS)
Cordova, M.H.; Andrade, C.E.
1992-01-01
The effect of metals, which form stable lithium phase in binary alloys, on the formation of intermetallic species in ternary amalgams and their effect on thermal decomposition in contact with water is analyzed. Cd is selected as ternary metal, based on general experimental selection criteria. Cd (Hg) binary amalgams are prepared by direct contact Cd-Hg, whereas Li is formed by electrolysis of Li OH aq using a liquid Cd (Hg) cathodic well. The decomposition kinetic of Li C(Hg) in contact with 0.6 M Li OH is studied in function of ageing and temperature, and these results are compared with the binary amalgam Li (Hg) decomposition. The decomposition rate is constant during one hour for binary and ternary systems. Ageing does not affect the binary systems but increases the decomposition activation energy of ternary systems. A reaction mechanism that considers an intermetallic specie participating in the activated complex is proposed and a kinetic law is suggested. (author)
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Simões, P. N.; Pedroso, L. M.; Portugal, A. A.; Campos, J. L.
1998-01-01
Ammonium nitrate (AN) has been extensively used both in explosive and propellant formulations. Unlike AN, there is a lack of information about the thermal decomposition and related kinetic analysis of phase stabilized ammonium nitrate (PSAN). Simultaneous thermal analysis (DSC-TG) has been used in the thermal characterisation of a specific type of PSAN containing 1.0% of NiO (stabilizing agent) and 0.5% of Petro (anti-caking agent) as additives. Repeated runs covering the nominal heating rate...
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International Nuclear Information System (INIS)
Zhang Haiyan; Zhang Jianjun; Ren Ning; Xu, Su-Ling; Zhang Yonghua; Tian Liang; Song Huihua
2008-01-01
The complex of [Sm(2,4-DClBA) 3 (bipy)] 2 (2,4-DClBA, 2,4-dichlorobenzoate; bipy, 2,2'-bipyridine) was synthesized and characterized by elemental analysis, molar conductivity, IR and UV spectra. The thermal decomposition process of the complex was studied by means of TG-DTG and IR techniques. And its thermal decomposition kinetics was investigated via the analysis of the TG-DTG curves by jointly using double equal-double steps method and nonlinear integral isoconversional method. The activation energy E, the pre-exponential factor A and the most probable mechanism functions of the first decomposition stage were obtained. Meanwhile, the thermodynamic parameters (ΔH ≠ , ΔG ≠ and ΔS ≠ ) were also calculated. The lifetime equation at weight-loss of 10% was deduced as ln τ = -35.53 + 20200/T by isothermal thermogravimetric analysis
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KINETIC STUDY FOR THE THERMAL DECOMPOSITION OF HEMICELLULOSE ISOLATED FROM CORN STALK
Directory of Open Access Journals (Sweden)
Gao-Jin Lv
2010-04-01
Full Text Available In order to study the thermal decomposition characteristics of hemicellulose, a highly efficient procedure was carried out to extract hemicellulose from corn stalk. Several different sugar units were observed by 13C NMR spectra to show the presence and species of hemicellulose. Following isolation of the hemicellulose, experimental research on its thermal behavior were carried out with a thermogravimetric analyzer under inert atmosphere at heating rates ranging from 10 to 50°C/min, and the kinetic parameters were calculated by the Kissinger and Ozawa methods, respectively. It was found that the thermal degradation of hemicellulose mainly occurred in the temperature range 180-340°C with a final residue yield of 24% at 700°C. An increase of the heating rate could slightly increase both the temperatures at which the peak weight loss rate was observed and the maximum value of weight loss rate. The activation energy (E and the pre-exponential factor (lnA obtained by the Kissinger and Ozawa methods were 213.3kJ mol-1, 211.6kJ mol-1 and 46.2min-1, 45.9min-1, respectively. Even though the data showed little difference, the fitting degree of the Ozawa method was better than that of the Kissinger method. The experimental results and kinetic parameters may provide useful data for effective design and improvement of thermochemical conversion units.
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Thermal decomposition studies of CuInS2
Institute of Scientific and Technical Information of China (English)
Sunil H. CHAKI
2008-01-01
Single crystals of copper indium disulphide (CuInS2) have been successfully grown by the chemical vapour transport (CVT) technique using iodine as the transporting agent. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were carried out for the CVT grown CuInS2 single crystals. It was revealed that the crystals are thermally stable between the ambient temperature (300 K) and 845 K and that the decomposi-tion occurs sequentially in three steps. The kinetic para-meters, e.g., activation energy, order of reaction, and frequency factor were evaluated using non-mechanistic equations for thermal decomposition.
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International Nuclear Information System (INIS)
Gvozdev, A.A.
1987-01-01
The effect of NO or O 2 admixtures on kinetics of the irreversible thermal decomposition of nitrogen dioxide at temperatures 460-520 deg C and pressures 4-7 MPa has been studied. It follows from experimental data that the rate of N 2 O 4 formation reduces with the increase of partial pressure of oxygen or decrease of partial pressure of nitrogen oxide. The same regularity is seen for the rate of nitrogen formation. The rate constants of N 2 O formation in dissociating nitrogen tetroxide with oxygen or nitrogen oxide additions agree satisfactorily with previously published results, obtained in stoichiometric mixtures. The appreciable discrepancy at 520 deg C is bind with considerable degree of nitrogen oxide transformation which constitutes approximately 14%. It is determined that the kinetics of formation of the products of irreversible N 2 O and N 2 decomposition in stoichiometric and non-stoichiometric 2NO 2 ↔ 2NO+O 2 mixtures is described by identical 3NO → N 2 O+NO 2 and N 2 O+NO → N 2 +NO 2 reactions
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Directory of Open Access Journals (Sweden)
Quancheng Zhou
Full Text Available The thermal decomposition of Perilla frutescens polysaccharide was examined by thermogravimetry, differential thermogravimetry, and differential thermal analysis. The results showed that the mass loss of the substance proceeded in three steps. The first stage can be attributed to the expulsion of the water from ambient temperature to 182°C. The second stage corresponded to devolatilization from 182°C to 439°C. The residue slowly degraded in the third stage. The weight loss in air is faster than that in nitrogen, because the oxygen in air accelerated the pyrolytic reaction speed reaction. The heating rate significantly affected the pyrolysis of the sample. Similar activation energies of the degradation process (210-211 kJ mol⁻¹ were obtained by the FWO, KAS, and Popescu techniques. According to Popescu mechanism functions, the possible kinetic model was estimated to be Avrami-Erofeev 20 g(α = [-ln(1-α]⁴.
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Thermal Decomposition of Aluminium Chloride Hexahydrate
Czech Academy of Sciences Publication Activity Database
Hartman, Miloslav; Trnka, Otakar; Šolcová, Olga
2005-01-01
Roč. 44, č. 17 (2005), s. 6591-6598 ISSN 0888-5885 R&D Projects: GA ČR(CZ) GA203/02/0002 Institutional research plan: CEZ:AV0Z40720504 Keywords : aluminum chloride hexahydrate * thermal decomposition * reaction kinetics Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.504, year: 2005
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Pollutant content in marine debris and characterization by thermal decomposition
International Nuclear Information System (INIS)
Iñiguez, M.E.; Conesa, J.A.; Fullana, A.
2017-01-01
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 400–500 K, the atmosphere does not affect the thermal degradation of the mentioned waste. However, at temperatures between 500 and 800 K 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). - Highlights: • The analysis and characterization of waste from marine environment were performed. • Its pollutant content has been determined, considering PAHs, PCDD/Fs and dl-PCBs. • Thermal decomposition of MDs was studied at different atmospheres and heating rates. • Kinetic models for the combustion of the five main plastics of MDs were proposed. • Composition of the waste is calculated using thermal behavior of different plastics.
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Park, J; Lin, M C
2009-12-03
The thermal decomposition of ammonium nitrate, NH(4)NO(3) (AN), in the gas phase has been studied at 423-56 K by pyrolysis/mass spectrometry under low-pressure conditions using a Saalfeld reactor coated with boric acid. The sublimation of NH(4)NO(3) at 423 K was proposed to produce equal amounts of NH(3) and HNO(3), followed by the decomposition reaction of HNO(3), HNO(3) + M --> OH + NO(2) + M (where M = third-body and reactor surface). The absolute yields of N(2), N(2)O, H(2)O, and NH(3), which can be unambiguously measured and quantitatively calibrated under a constant pressure at 5-6.2 torr He are kinetically modeled using the detailed [H,N,O]-mechanism established earlier for the simulation of NH(3)-NO(2) (Park, J.; Lin, M. C. Technologies and Combustion for a Clean Environment. Proc. 4th Int. Conf. 1997, 34-1, 1-5) and ADN decomposition reactions (Park, J.; Chakraborty, D.; Lin, M. C. Proc. Combust. Inst. 1998, 27, 2351-2357). Since the homogeneous decomposition reaction of HNO(3) itself was found to be too slow to account for the consumption of reactants and the formation of products, we also introduced the heterogeneous decomposition of HNO(3) in our kinetic modeling. The heterogeneous decomposition rate of HNO(3), HNO(3) + (B(2)O(3)/SiO(2)) --> OH + NO(2) + (B(2)O(3)/SiO(2)), was determined by varying its rate to match the modeled result to the measured concentrations of NH(3) and H(2)O; the rate could be represented by k(2b) = 7.91 x 10(7) exp(-12 600/T) s(-1), which appears to be consistent with those reported by Johnston and co-workers (Johnston, H. S.; Foering, L.; Tao, Y.-S.; Messerly, G. H. J. Am. Chem. Soc. 1951, 73, 2319-2321) for HNO(3) decomposition on glass reactors at higher temperatures. Notably, the concentration profiles of all species measured could be satisfactorily predicted by the existing [H,N,O]-mechanism with the heterogeneous initiation process.
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Park, J.; Lin, M. C.
2009-10-01
The thermal decomposition of ammonium nitrate, NH4NO3 (AN), in the gas phase has been studied at 423-56 K by pyrolysis/mass spectrometry under low-pressure conditions using a Saalfeld reactor coated with boric acid. The sublimation of NH4NO3 at 423 K was proposed to produce equal amounts of NH3 and HNO3, followed by the decomposition reaction of HNO3, HNO3 + M → OH + NO2 + M (where M = third-body and reactor surface). The absolute yields of N2, N2O, H2O, and NH3, which can be unambiguously measured and quantitatively calibrated under a constant pressure at 5-6.2 torr He are kinetically modeled using the detailed [H,N,O]-mechanism established earlier for the simulation of NH3-NO2 (Park, J.; Lin, M. C. Technologies and Combustion for a Clean Environment. Proc. 4th Int. Conf. 1997, 34-1, 1-5) and ADN decomposition reactions (Park, J.; Chakraborty, D.; Lin, M. C. Proc. Combust. Inst. 1998, 27, 2351-2357). Since the homogeneous decomposition reaction of HNO3 itself was found to be too slow to account for the consumption of reactants and the formation of products, we also introduced the heterogeneous decomposition of HNO3 in our kinetic modeling. The heterogeneous decomposition rate of HNO3, HNO3 + (B2O3/SiO2) → OH + NO2 + (B2O3/SiO2), was determined by varying its rate to match the modeled result to the measured concentrations of NH3 and H2O; the rate could be represented by k2b = 7.91 × 107 exp(-12 600/T) s-1, which appears to be consistent with those reported by Johnston and co-workers (Johnston, H. S.; Foering, L.; Tao, Y.-S.; Messerly, G. H. J. Am. Chem. Soc. 1951, 73, 2319-2321) for HNO3 decomposition on glass reactors at higher temperatures. Notably, the concentration profiles of all species measured could be satisfactorily predicted by the existing [H,N,O]-mechanism with the heterogeneous initiation process.
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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.
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Dhyani, Vaibhav; Kumar Awasthi, Mukesh; Wang, Quan; Kumar, Jitendra; Ren, Xiuna; Zhao, Junchao; Chen, Hongyu; Wang, Meijing; Bhaskar, Thallada; Zhang, Zengqiang
2018-03-01
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.
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Kinetics of the decomposition reaction of phosphorite concentrate
Directory of Open Access Journals (Sweden)
Huang Run
2014-01-01
Full Text Available Apatite is the raw material, which is mainly used in phosphate fertilizer, and part are used in yellow phosphorus, red phosphorus, and phosphoric acid in the industry. With the decrease of the high grade phosphorite lump, the agglomeration process is necessary for the phosphorite concentrate after beneficiation process. The decomposition behavior and the phase transformation are of vital importance for the agglomeration process of phosphorite. In this study, the thermal kinetic analysis method was used to study the kinetics of the decomposition of phosphorite concentrate. The phosphorite concentrate was heated under various heating rate, and the phases in the sample heated were examined by the X-ray diffraction method. It was found that the main phases in the phosphorite are fluorapatiteCa5(PO43F, quartz SiO2,and dolomite CaMg(CO32.The endothermic DSC peak corresponding to the mass loss caused by the decomposition of dolomite covers from 600°C to 850°C. The activation energy of the decomposition of dolomite, which increases with the increase in the extent of conversion, is about 71.6~123.6kJ/mol. The mechanism equation for the decomposition of dolomite agrees with the Valensi equation and G-B equation.
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Effect of particle size on thermal decomposition of alkali metal picrates
International Nuclear Information System (INIS)
Liu, Rui; Zhang, Tonglai; Yang, Li; Zhou, Zunning
2014-01-01
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
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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.
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Asadi, Mozaffar; Asadi, Zahra; Savaripoor, Nooshin; Dusek, Michal; Eigner, Vaclav; Shorkaei, Mohammad Ranjkesh; Sedaghat, Moslem
2015-02-05
A series of new VO(IV) complexes of tetradentate N2O2 Schiff base ligands (L(1)-L(4)), were synthesized and characterized by FT-IR, UV-vis and elemental analysis. The structure of the complex VOL(1)⋅DMF was also investigated by X-ray crystallography which revealed a vanadyl center with distorted octahedral coordination where the 2-aza and 2-oxo coordinating sites of the ligand were perpendicular to the "-yl" oxygen. The electrochemical properties of the vanadyl complexes were investigated by cyclic voltammetry. A good correlation was observed between the oxidation potentials and the electron withdrawing character of the substituents on the Schiff base ligands, showing the following trend: MeO5-H>5-Br>5-Cl. Furthermore, the kinetic parameters of thermal decomposition were calculated by using the Coats-Redfern equation. According to the Coats-Redfern plots the kinetics of thermal decomposition of studied complexes is of the first-order in all stages, the free energy of activation for each following stage is larger than the previous one and the complexes have good thermal stability. The preparation of VOL(1)⋅DMF yielded also another compound, one kind of vanadium oxide [VO]X, with different habitus of crystals, (platelet instead of prisma) and without L(1) ligand, consisting of a V10O28 cage, diaminium moiety and dimethylamonium as a counter ions. Because its crystal structure was also new, we reported it along with the targeted complex. Copyright © 2014 Elsevier B.V. All rights reserved.
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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.
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Thermal decomposition kinetics of sorghum straw via thermogravimetric analysis.
Dhyani, Vaibhav; Kumar, Jitendra; Bhaskar, Thallada
2017-12-01
The thermal decomposition of sorghum straw was investigated by non-isothermal thermogravimetric analysis, where the determination of kinetic triplet (activation energy, pre-exponential factor, and reaction model), was the key objective. The activation energy was determined using different isoconversional methods: Friedman, Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS), Starink, Iterative method of Chai & Chen, Vyazovkin AIC method, and Li & Tang equation. The pre-exponential factor was calculated using Kissinger's equation; while the reaction model was predicted by comparison of z-master plot obtained from experimental values with the theoretical plots. The values of activation energy obtained from isoconversional methods were further used for evaluation of thermodynamic parameters, enthalpy, entropy and Gibbs free energy. Results showed three zones of pyrolysis having average activation energy values of 151.21kJ/mol, 116.15kJ/mol, and 136.65kJ/mol respectively. The data was well fitting with two-dimension 'Valensi' model for conversion values from 0 to 0.4 with a coefficient of determination (R 2 ) value of 0.988, and with third order reaction model for values from 0.4 to 0.9 with an R 2 value of 0.843. Copyright © 2017 Elsevier Ltd. All rights reserved.
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Ren, Xiu'e; Chen, Jianbiao; Li, Gang; Wang, Yanhong; Lang, Xuemei; Fan, Shuanshi
2018-08-01
The study concerned the thermal oxidative degradation kinetics of agricultural residues, peanut shell (PS) and sunflower shell (SS). The thermal behaviors were evaluated via thermogravimetric analysis and the kinetic parameters were determined by using distributed activation energy model (DAEM) and global kinetic model (GKM). Results showed that thermal oxidative decomposition of two samples processed in three zones; the ignition, burnout, and comprehensive combustibility between two agricultural residues were of great difference; and the combustion performance could be improved by boosting heating rate. The activation energy ranges calculated by the DAEM for the thermal oxidative degradation of PS and SS were 88.94-145.30 kJ mol -1 and 94.86-169.18 kJ mol -1 , respectively. The activation energy obtained by the GKM for the oxidative decomposition of hemicellulose and cellulose was obviously lower than that for the lignin oxidation at identical heating rate. To some degree, the determined kinetic parameters could acceptably simulate experimental data. Copyright © 2018 Elsevier Ltd. All rights reserved.
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Energy Technology Data Exchange (ETDEWEB)
Singh, Gurdip; Kapoor, Inder Pal Singh; Dubey, Shalini [Department of Chemistry, D. D. U. Gorakhpur University, Gorakhpur (India); Siril, Prem Felix [Laboratoire de Chimie Physique (LCP), Universite de Paris Sud, Orsay (France)
2009-02-15
Binary transition metal ferrite (BTMF) nanocrystals of formula MFe{sub 2}O{sub 4}(M=Cu,Co,Ni) were prepared by the coprecipitation method and characterized by X-ray diffraction (XRD). XRD patterns gave average particle size by using Scherrer's equation for CuFe{sub 2}O{sub 4}(CuF), CoFe{sub 2}O{sub 4}(CoF), and NiFe{sub 2}O{sub 4} (NiF) as 39.9, 27.3, and 43.8 nm, respectively. The catalytic activity measurements on the thermal decomposition of ammonium perchlorate (AP) were carried out by using thermogravimetry (TG), differential thermal analysis (DTA), and ignition delay studies. Isothermal TG data up to a mass loss of 45% have been used to evaluate kinetic parameters by using model fitting as well as isoconversional method. The order of catalytic activity was found to be: CoFe{sub 2}O{sub 4}>NiFe{sub 2}O{sub 4}. (Abstract Copyright [2009], Wiley Periodicals, Inc.)
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Thermal decomposition of pyrite
International Nuclear Information System (INIS)
Music, S.; Ristic, M.; Popovic, S.
1992-01-01
Thermal decomposition of natural pyrite (cubic, FeS 2 ) has been investigated using X-ray diffraction and 57 Fe Moessbauer spectroscopy. X-ray diffraction analysis of pyrite ore from different sources showed the presence of associated minerals, such as quartz, szomolnokite, stilbite or stellerite, micas and hematite. Hematite, maghemite and pyrrhotite were detected as thermal decomposition products of natural pyrite. The phase composition of the thermal decomposition products depends on the terature, time of heating and starting size of pyrite chrystals. Hematite is the end product of the thermal decomposition of natural pyrite. (author) 24 refs.; 6 figs.; 2 tabs
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Decomposition kinetics of expanded austenite with high nitrogen contents
DEFF Research Database (Denmark)
Christiansen, Thomas; Somers, Marcel A. J.
2006-01-01
This paper addresses the decomposition kinetics of synthesized homogeneous expanded austenite formed by gaseous nitriding of stainless steel AISI 304L and AISI 316L with nitrogen contents up to 38 at.% nitrogen. Isochronal annealing experiments were carried out in both inert (N2) and reducing (H2......) atmospheres. Differential thermal analysis (DTA) and thermogravimetry were applied for identification of the decomposition reactions and X-ray diffraction analysis was applied for phase analysis. CrN precipitated upon annealing; the activation energies are 187 kJ/mol and 128 kJ/mol for AISI 316L and AISI 304L...
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Kinetics and mechanism of thermal processes of nonreversible decomposition of the system N2O4-NO
International Nuclear Information System (INIS)
Nesterenko, V.B.; Nichipor, G.V.
1989-01-01
Consideration is given to kinetics and mechanism of decomposition of nitrogen oxide in gaseous phase at devated pressures and temperature, decomposition of N 2 O 4 -NO system under flow conditions, as well as to kinetics and mechanism of formation of nitrons oxide. 37 refs.; 13 figs.; 13 tabs
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International Nuclear Information System (INIS)
Chandran, K.; Brahmananda, C.V.S.; Anthonysamy, S.; Srinivasan, T.G.; Ganesan, V.
2013-01-01
Tributyl phosphate (TBP) is used in the reprocessing industry for the separation of uranium and plutonium from the spent nuclear fuels by PUREX process. A variety of dialkylalky/phosphonates were synthesised and their extraction behaviour on actinides was studied in this laboratory. The superior extraction characteristics of phosphonates make them useful for several metal recovery applications in the nuclear fuel cycle. However, higher solubility of phosphonates in aqueous phase as compared to TBP, introduces higher chances of the formation of thermally active 'red oil' like substances during the evaporation of aqueous streams. Thermal stability of neat and nitric acid solvated homologues of four dibutylalkyl phosphonates namely, dibutylpropyl phosphonate (DBPrP), dibutylbutyl phosphonate (DBBP), dibutylpentyl phosphonate (DBPP), dibutylhexyl phosphonate (DBHeP), and two dipentylalkyl phosphonates viz. dipentylbutyl phosphonate (DPBP), dipentylhexyl phosphonate (DPHeP) were studied. Experiments were conducted using an adiabatic calorimeter in heat-wait-search mode. Various stoichiometry of nitric acid-solvated DBalP and DPalP were prepared by equilibrating the respective organic with 4-15.6 M nitric acid followed by separation. Neat DBalP and DPalP are stable up to the temperature of ∼ 555 K while their acid-solvates decomposed in the temperature range 380-403 K. The results also indicated that the presence of nitric acid accelerated the decomposition of phosphonates. Decomposition of these acid solvated phosphonates is found to be exothermic and follows first order kinetics. The onset temperature, adiabatic temperature rise, pressure rise, decomposition enthalpy and activation energy were found to strongly depend on the nitric acid content of the acid-solvates. The studies also indicate that dibutylalkyl and dipentylalkyl phosphonates are also prone to form 'red oil' like substances under extreme conditions and can lead to run-away reactions
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Mechanism and kinetics of thermal decomposition of ammoniacal complex of copper oxalate
International Nuclear Information System (INIS)
Prasad, R.
2003-01-01
A complex precursor has been synthesized by dissolving copper oxalate in liquor ammonia followed by drying. The thermal decomposition of the precursor has been studied in different atmospheres, air/nitrogen. The mechanism of decomposition of the precursor in air is not as simple one as in nitrogen. In nitrogen, it involves endothermic deammoniation followed by decomposition to finely divided elemental particles of copper. Whereas in air, decomposition and simultaneous oxidation of the residual products (oxidative decomposition), make the process complex and relatively bigger particle of cupric oxide are obtained as final product. The products of decomposition in different atmospheres have been characterized by X-ray diffraction and particle size analysis. The stoichiometric formula, Cu(NH 3 ) 2 C 2 O 4 of the precursor is established from elemental analysis and TG measurements, and it is designated as copper amino oxalate (CAO). In nitrogen atmosphere, the deammoniation and decomposition have been found to be zero and first order, respectively. The values of activation energy have been found to be 102.52 and 95.38 kJ/mol for deammoniation and decomposition, respectively
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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.
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Kinetic analysis of the thermal decomposition of Li4Ti5O12 pellets
Directory of Open Access Journals (Sweden)
Hugo A. Mosqueda
2011-12-01
Full Text Available A single dynamic kinetic analysis, describing the surface decomposition of Li4Ti5O12 pellets, has been performed. Samples were analyzed by X-ray diffraction and scanning electron microscopy. The analyses were performed between 1000 and 1100°C and different times, perceiving the Li4Ti5O12 decomposition to Li2Ti3O7, with a loss of lithium. As expected, more rapid decomposition behaviour was found at higher temperatures. Finally, the activation energy for this decomposition of Li4Ti5O12 to Li2Ti3O7 was estimated to be equal to 383 kJ/mol.
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Thermal decomposition of lutetium propionate
DEFF Research Database (Denmark)
Grivel, Jean-Claude
2010-01-01
The thermal decomposition of lutetium(III) propionate monohydrate (Lu(C2H5CO2)3·H2O) in argon was studied by means of thermogravimetry, differential thermal analysis, IR-spectroscopy and X-ray diffraction. Dehydration takes place around 90 °C. It is followed by the decomposition of the anhydrous...... °C. Full conversion to Lu2O3 is achieved at about 1000 °C. Whereas the temperatures and solid reaction products of the first two decomposition steps are similar to those previously reported for the thermal decomposition of lanthanum(III) propionate monohydrate, the final decomposition...... of the oxycarbonate to the rare-earth oxide proceeds in a different way, which is here reminiscent of the thermal decomposition path of Lu(C3H5O2)·2CO(NH2)2·2H2O...
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García-Garrido, C; Sánchez-Jiménez, P E; Pérez-Maqueda, L A; Perejón, A; Criado, José M
2016-10-26
The polymer-to-ceramic transformation kinetics of two widely employed ceramic precursors, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (TTCS) and polyureamethylvinylsilazane (CERASET), have been investigated using coupled thermogravimetry and mass spectrometry (TG-MS), Raman, XRD and FTIR. The thermally induced decomposition of the pre-ceramic polymer is the critical step in the synthesis of polymer derived ceramics (PDCs) and accurate kinetic modeling is key to attaining a complete understanding of the underlying process and to attempt any behavior predictions. However, obtaining a precise kinetic description of processes of such complexity, consisting of several largely overlapping physico-chemical processes comprising the cleavage of the starting polymeric network and the release of organic moieties, is extremely difficult. Here, by using the evolved gases detected by MS as a guide it has been possible to determine the number of steps that compose the overall process, which was subsequently resolved using a semiempirical deconvolution method based on the Frasier-Suzuki function. Such a function is more appropriate that the more usual Gaussian or Lorentzian functions since it takes into account the intrinsic asymmetry of kinetic curves. Then, the kinetic parameters of each constituent step were independently determined using both model-free and model-fitting procedures, and it was found that the processes obey mostly diffusion models which can be attributed to the diffusion of the released gases through the solid matrix. The validity of the obtained kinetic parameters was tested not only by the successful reconstruction of the original experimental curves, but also by predicting the kinetic curves of the overall processes yielded by different thermal schedules and by a mixed TTCS-CERASET precursor.
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Pollutant content in marine debris and characterization by thermal decomposition.
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.
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Pressure Dependent Decomposition Kinetics of the Energetic Material HMX up to 3.6 GPa
Energy Technology Data Exchange (ETDEWEB)
Glascoe, E A; Zaug, J M; Burnham, A K
2009-05-29
The effect of pressure on the thermal decomposition rate of the energetic material HMX was studied. HMX was precompressed in a diamond anvil cell (DAC) and heated at various rates. The parent species population was monitored as a function of time and temperature using Fourier transform infrared (FTIR) spectroscopy. Decomposition rates were determined by fitting the fraction reacted to the extended-Prout-Tompkins nucleation-growth model and the Friedman isoconversional method. The results of these experiments and analysis indicate that pressure accelerates the decomposition at low to moderate pressures (i.e. between ambient pressure and 1 GPa) and decelerates the decomposition at higher pressures. The decomposition acceleration is attributed to pressure enhanced autocatalysis whereas the deceleration at high pressures is attributed pressure inhibiting bond homolysis step(s), which would result in an increase in volume. These results indicate that both {beta} and {delta} phase HMX are sensitive to pressure in the thermally induced decomposition kinetics.
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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.
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International Nuclear Information System (INIS)
Lee, Jae Hun; Kim, Kwang Seok; Kim, Hyo
2013-01-01
An in-depth study to determine the thermal decomposition kinetics parameters such as the activation energy E_a, the reaction order n, and the pre-exponential factor A of epoxy/carbon fiber composite material has been conducted. We employ not only the modified peak property method that is proposed here, but also the conventional method in analyzing the experimental data, and compare the results to show the performance of the proposed model. The pyrolysis tests for the epoxy/carbon fiber composite materials are conducted by using thermogravimetric analyser at various heating rates. As a result, the best prediction to the experimental data can be obtained by the modified peak property method. Besides, among the methods applied here, the modified peak property method provides most convenient way to recover the parameters: it does not require a curve fitting of the data nor a long iterative computation
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Kinetic concepts of thermally stimulated reactions in solids
Vyazovkin, Sergey
Historical analysis suggests that the basic kinetic concepts of reactions in solids were inherited from homogeneous kinetics. These concepts rest upon the assumption of a single-step reaction that disagrees with the multiple-step nature of solid-state processes. The inadequate concepts inspire such unjustified anticipations of kinetic analysis as evaluating constant activation energy and/or deriving a single-step reaction mechanism for the overall process. A more adequate concept is that of the effective activation energy, which may vary with temperature and extent of conversion. The adequacy of this concept is illustrated by literature data as well as by experimental data on the thermal dehydration of calcium oxalate monohydrate and thermal decomposition of calcium carbonate, ammonium nitrate and 1,3,5,7- tetranitro-1,3,5,7-tetrazocine.
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Energy Technology Data Exchange (ETDEWEB)
Kapoor, Inder Pal Singh; Srivastava, Pratibha; Singh, Gurdip [Department of Chemistry, DDU Gorakhpur University, Gorakhpur (India)
2009-08-15
Nanocrystalline transition metal oxides (NTMOs) have been successfully prepared by three different methods: novel quick precipitation method (Cr{sub 2}O{sub 3} and Fe{sub 2}O{sub 3}); surfactant mediated method (CuO), and reduction of metal complexes with hydrazine as reducing agent (Mn{sub 2}O{sub 3}). The nano particles have been characterized by X-ray diffraction (XRD) which shows an average particle diameter of 35-54 nm. Their catalytic activity was measured in the thermal decomposition of ammonium perchlorate (AP). AP decomposition undergoes a two step process where the addition of metal oxide nanocrystals led to a shifting of the high temperature decomposition peak toward lower temperature. The kinetics of the thermal decomposition of AP and catalyzed AP has also been evaluated using model fitting and isoconversional method. (Abstract Copyright [2009], Wiley Periodicals, Inc.)
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Thermal and kinetic behaviors of biomass and plastic wastes in co-pyrolysis
International Nuclear Information System (INIS)
Çepelioğullar, Özge; Pütün, Ayşe E.
2013-01-01
Graphical abstract: - Highlights: • Co-pyrolysis of biomass together with the plastic wastes in thermogravimetric analyzer. • Investigations into thermal and kinetic behaviors at high temperature regions. • Determination of the kinetic parameters. - Abstract: In this study, co-pyrolysis characteristics and kinetics of biomass-plastic blends were investigated. Cotton stalk, hazelnut shell, sunflower residue, and arid land plant Euphorbia rigida, were blended in definite ratio (1:1, w/w) with polyvinyl chloride (PVC) and polyethylene terephthalate (PET). Experiments were conducted with a heating rate of 10 °C min −1 from room temperature to 800 °C in the presence of N 2 atmosphere with a flow rate of 100 cm 3 min −1 . After thermal decomposition in TGA, a kinetic analysis was performed to fit thermogravimetric data and a detailed discussion of co-pyrolysis mechanism was achieved. Experimental results demonstrated that the structural differences between biomass and plastics directly affect their thermal decomposition behaviors. Biomass pyrolysis generally based on three main steps while plastic material’s pyrolysis mechanism resulted in two steps for PET and three steps for PVC. Also, the required activation energies needed to achieve the thermal degradation for plastic were found higher than the biomass materials. In addition, it can be concluded that the evaluation of plastic materials together with biomass created significant changes not only for the thermal behaviors but also for the kinetic behaviors
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Energy Technology Data Exchange (ETDEWEB)
Longuet, Baptiste [Laboratoire Energetique Explosions et Structures Universite d' Orleans (Germany); Gillard, Philippe [Laboratoire Energetic Explosions et Structures, Universite d' Orleans, Bourges (France)
2009-02-15
The thermal decomposition of ammonium perchlorate has been extensively studied in the past. Nevertheless, the various results published illustrate, on the one hand, significant differences regarding the influence of different parameters on the decomposition and on the other hand, a lack of useful quantitative laws to predict the thermal behaviour of this crystal under a range of conditions (temperature, duration of exposure, presence of confinement). (Abstract Copyright [2009], Wiley Periodicals, Inc.)
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Thermal decomposition of synthetic antlerite prepared by microwave-assisted hydrothermal method
Energy Technology Data Exchange (ETDEWEB)
Koga, Nobuyoshi [Chemistry Laboratory, Graduate School of Education, Hiroshima University, 1-1-1 Kagamiyama, Higashi-Hiroshima 739-8524 (Japan)], E-mail: nkoga@hiroshima-u.ac.jp; Mako, Akira; Kimizu, Takaaki; Tanaka, Yuu [Chemistry Laboratory, Graduate School of Education, Hiroshima University, 1-1-1 Kagamiyama, Higashi-Hiroshima 739-8524 (Japan)
2008-01-30
Copper(II) hydroxide sulfate was synthesized by a microwave-assisted hydrothermal method from a mixed solution of CuSO{sub 4} and urea. Needle-like crystals of ca. 20-30 {mu}m in length precipitated by irradiating microwave for 1 min were characterized as Cu{sub 3}(OH){sub 4}SO{sub 4} corresponding to mineral antlerite. The reaction pathway and kinetics of the thermal decomposition of the synthetic antlerite Cu{sub 3}(OH){sub 4}SO{sub 4} were investigated by means of thermoanalytical techniques complemented by powder X-ray diffractometry and microscopic observations. The thermal decomposition of Cu{sub 3}(OH){sub 4}SO{sub 4} proceeded via two separated reaction steps of dehydroxylation and desulfation to produce CuO, where crystalline phases of Cu{sub 2}OSO{sub 4} and CuO appeared as the intermediate products. The kinetic characteristics of the respective steps were discussed in comparison with those of the synthetic brochantite Cu{sub 4}(OH){sub 6}SO{sub 4} reported previously.
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Kinetic study of hydrogen peroxide decomposition by catalase in a flow-mix microcalorimetric system
International Nuclear Information System (INIS)
Fidaleo, Marcello; Lavecchia, Roberto
2003-01-01
The kinetics of hydrogen peroxide decomposition by the enzyme catalase was studied at pH 7.4 in the temperature range 10-30 deg. C. Experiments were performed by the LKB-2277 Thermal Activity Monitor equipped with a flow-mix cylinder. The calorimetric reaction unit was schematised as a tubular reactor operating under plug-flow conditions. A first-order kinetic expression, with respect to both the substrate and the enzyme, was used to describe the rate of hydrogen peroxide decomposition. Regression analysis of calorimetric data provided a molar reaction enthalpy of -87.55 kJ mol -1 and an activation energy of 11 kJ mol -1 . Analysis of model residuals and the normal probability plot indicated that the results obtained were statistically significant
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Thermal decomposition process of silver behenate
International Nuclear Information System (INIS)
Liu Xianhao; Lu Shuxia; Zhang Jingchang; Cao Weiliang
2006-01-01
The thermal decomposition processes of silver behenate have been studied by infrared spectroscopy (IR), X-ray diffraction (XRD), combined thermogravimetry-differential thermal analysis-mass spectrometry (TG-DTA-MS), transmission electron microscopy (TEM) and UV-vis spectroscopy. The TG-DTA and the higher temperature IR and XRD measurements indicated that complicated structural changes took place while heating silver behenate, but there were two distinct thermal transitions. During the first transition at 138 deg. C, the alkyl chains of silver behenate were transformed from an ordered into a disordered state. During the second transition at about 231 deg. C, a structural change took place for silver behenate, which was the decomposition of silver behenate. The major products of the thermal decomposition of silver behenate were metallic silver and behenic acid. Upon heating up to 500 deg. C, the final product of the thermal decomposition was metallic silver. The combined TG-MS analysis showed that the gas products of the thermal decomposition of silver behenate were carbon dioxide, water, hydrogen, acetylene and some small molecule alkenes. TEM and UV-vis spectroscopy were used to investigate the process of the formation and growth of metallic silver nanoparticles
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The processing of aluminum gasarites via thermal decomposition of interstitial hydrides
Licavoli, Joseph J.
Gasarite structures are a unique type of metallic foam containing tubular pores. The original methods for their production limited them to laboratory study despite appealing foam properties. Thermal decomposition processing of gasarites holds the potential to increase the application of gasarite foams in engineering design by removing several barriers to their industrial scale production. The following study characterized thermal decomposition gasarite processing both experimentally and theoretically. It was found that significant variation was inherent to this process therefore several modifications were necessary to produce gasarites using this method. Conventional means to increase porosity and enhance pore morphology were studied. Pore morphology was determined to be more easily replicated if pores were stabilized by alumina additions and powders were dispersed evenly. In order to better characterize processing, high temperature and high ramp rate thermal decomposition data were gathered. It was found that the high ramp rate thermal decomposition behavior of several hydrides was more rapid than hydride kinetics at low ramp rates. This data was then used to estimate the contribution of several pore formation mechanisms to the development of pore structure. It was found that gas-metal eutectic growth can only be a viable pore formation mode if non-equilibrium conditions persist. Bubble capture cannot be a dominant pore growth mode due to high bubble terminal velocities. Direct gas evolution appears to be the most likely pore formation mode due to high gas evolution rate from the decomposing particulate and microstructural pore growth trends. The overall process was evaluated for its economic viability. It was found that thermal decomposition has potential for industrialization, but further refinements are necessary in order for the process to be viable.
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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.
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Parandaman, A.; Sudhakar, G.; Rajakumar, B.
Thermal reactions of Tetramethylsilane (TMS) diluted in argon were studied behind the reflected shock waves in a single-pulse shock tube (SPST) over the temperature range of 1085-1221 K and pressures varied between 10.6 and 22.8 atm. The stable products resulting from the decomposition of TMS were identified and quantified using gas chromatography and also verified with Fourier Transform Infrared (FTIR) spectrometer. The major reaction products are methane (CH4) and ethylene (C2H4). The minor reaction products are ethane (C2H6) and propylene (C3H6). The initiation of mechanism in the decomposition of TMS takes plays via the Si-C bond scission by ejecting the methyl radicals (CH3) and trimethylsilyl radicals ((CH3)3Si). The measured temperature dependent rate coefficient for the total decomposition of TMS was to be ktotal = 1.66 ×1015 exp (-64.46/RT) s-1 and for the formation of CH4 reaction channel was to be k = 2.20 × 1014 exp (-60.15/RT) s-1, where the activation energies are given in kcal mol-1. A kinetic scheme containing 17 species and 28 elementary reactions was used for the simulation using chemical kinetic simulator over the temperature range of 1085-1221 K. The agreement between the experimental and simulated results was satisfactory.
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Energy Technology Data Exchange (ETDEWEB)
Morris, R.E.; Mera, A.E.; Brady, R.F. Jr. [Naval Research Laboratory, Washington, DC (USA)
2000-07-01
A high pressure reactor has been constructed and used for in situ spectroscopic measurements of reaction kinetics in supercritical fluids. The thermal decomposition of 2,2{prime}-azobis(isobutyronitrile) (AIBN) in supercritical carbon dioxide (SC-CO{sub 2}) was studied as part of an effort to characterize free-radical autoxidation of hydrocarbon fuels under supercritical conditions. The findings show that AIBN decomposes both thermally and photochemically in SC-CO{sub 2} to form the 2-cyano-2-propyl free radical which dimerizes to form tetramethylsuccinic dinitrile and dimethyl-N-(2-cyano-2-propyl) ketenimine. Examination of the decomposition kinetics of the ketenimine revealed that it was photochemically stable in the kinetic reactor, but decomposed thermally to form the dinitrile. 21 refs., 4 figs., 1 tab.
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Decomposition mechanisms and non-isothermal kinetics of LiHC_2O_4·H_2O
Institute of Scientific and Technical Information of China (English)
无
2012-01-01
The thermal decomposition process of LiHC2O4·H2O from 30 to 600 ℃ was investigated by the thermogravimetric and differential scanning calorimetry (TG-DSC). The phases decomposited at different temperature were characterized by X-ray diffraction (XRD), which indicated the decompositions at 150, 170, and 420℃, relating to LiHC2O4, Li2C2O4, Li2C2O4, and Li2CO3, respectively. Reaction mechanisms in the whole sintering process were determined, and the model fitting kinetic approaches were applied to data for non...
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Thermal Plasma decomposition of fluoriated greenhouse gases
Energy Technology Data Exchange (ETDEWEB)
Choi, Soo Seok; Watanabe, Takayuki [Tokyo Institute of Technology, Yokohama (Japan); Park, Dong Wha [Inha University, Incheon (Korea, Republic of)
2012-02-15
Fluorinated compounds mainly used in the semiconductor industry are potent greenhouse gases. Recently, thermal plasma gas scrubbers have been gradually replacing conventional burn-wet type gas scrubbers which are based on the combustion of fossil fuels because high conversion efficiency and control of byproduct generation are achievable in chemically reactive high temperature thermal plasma. Chemical equilibrium composition at high temperature and numerical analysis on a complex thermal flow in the thermal plasma decomposition system are used to predict the process of thermal decomposition of fluorinated gas. In order to increase economic feasibility of the thermal plasma decomposition process, increase of thermal efficiency of the plasma torch and enhancement of gas mixing between the thermal plasma jet and waste gas are discussed. In addition, noble thermal plasma systems to be applied in the thermal plasma gas treatment are introduced in the present paper.
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Kinetics study of thermal decomposition of calcium carboxylate salts
International Nuclear Information System (INIS)
Landoll, Michael P.; Holtzapple, Mark T.
2013-01-01
The MixAlco™ process ferments lignocellulosic biomass to carboxylate salts that are thermally decomposed into ketones, which are then chemically converted to a wide variety of chemicals and fuels. To perform these decompositions, suitable reaction models are necessary to properly design, scale, and optimize commercial reactors. For three salt types (calcium acetate, and two types of mixed calcium carboxylate salts), activation energy was determined using three isoconversional methods that employed TGA curves at different heating rates. For all three salt types, activation energy varied significantly with conversion. The average activation energy for calcium acetate was 556.75 kJ mol −1 , and the activation energies for the two mixed calcium carboxylate salts were 232.87, and 176.55 kJ mol −1 . In addition, three functions of conversion were employed to see which one best modeled the experimental data. The Sestak–Berggren model provides the best universal fit for all three salt types. -- Highlights: •Calcium carboxylate salts from fermentation broth thermally decompose to ketones. •Activation energy varies with conversion for all three salt types. •Sestak–Berggren model provides best fit overall for all three salt types
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Kinetics study of thermal decomposition of sodium carboxylate salts
International Nuclear Information System (INIS)
Landoll, Michael P.; Holtzapple, Mark T.
2012-01-01
The MixAlco™ process ferments lignocellulosic biomass to carboxylate salts that are thermally decomposed into ketones, which are then chemically converted to a wide variety of chemicals and fuels. To perform these decompositions, suitable reaction models are necessary to properly design, scale, and optimize commercial reactors. For three salt types (sodium acetate, and two types of mixed sodium carboxylate salts), activation energy was determined using three isoconversional methods that employed TGA curves at different heating rates. For all three salt types, activation energy varied significantly with conversion. The average activation energy for sodium acetate was 226.65 kJ/mol, and the activation energies for the two mixed sodium carboxylate salts were 195.61, and 218.18 kJ/mol. In addition, three functions of conversion were employed to see which one best modeled the experimental data. The Sestak-Berggren model fits all three salt types best. -- Highlights: ► Sodium carboxylate salts from fermentation broth thermally decompose to ketones. ► Activation energy varies with conversion for all three salt types. ► Sestak-Berggren model provides best fit for all three salt types.
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International Nuclear Information System (INIS)
Behrens, R. Jr.
1987-01-01
A new type of instrument has been designed and constructed to measure quantitatively the gas phase species evolving during thermal decompositions. These measurements can be used for understanding the kinetics of thermal decomposition, determining the heats of formation and vaporization of high-temperature materials, and analyzing sample contaminants. The new design allows measurements to be made on the same time scale as the rates of the reactions being studied, provides a universal detection technique to study a wide range of compounds, gives quantitative measurements of decomposition products, and minimizes interference from the instrument on the measurements. The instrument design is based on a unique combination of thermogravimetric analysis (TGA), differential thermal analysis (DTA), and modulated beam mass spectroscopy (MBMS) which are brought together into a symbiotic relationship through the use of differentially pumped vacuum systems, modulated molecular beam techniques, and computer control and data-acquisition systems. A data analysis technique that calculates partial pressures in the reaction cell from the simultaneous microbalance force measurements and the modulated mass spectrometry measurements has been developed. This eliminates the need to know the ionization cross section, the ion dissociation channels, the quadrupole transmission, and the ion detector sensitivity for each thermal decomposition product prior to quantifying the mass spectral data. The operation of the instrument and the data analysis technique are illustrated with the thermal decomposition of contaminants from a precipitated palladium powder
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Detailed Chemical Kinetic Modeling of Hydrazine Decomposition
Meagher, Nancy E.; Bates, Kami R.
2000-01-01
The purpose of this research project is to develop and validate a detailed chemical kinetic mechanism for gas-phase hydrazine decomposition. Hydrazine is used extensively in aerospace propulsion, and although liquid hydrazine is not considered detonable, many fuel handling systems create multiphase mixtures of fuels and fuel vapors during their operation. Therefore, a thorough knowledge of the decomposition chemistry of hydrazine under a variety of conditions can be of value in assessing potential operational hazards in hydrazine fuel systems. To gain such knowledge, a reasonable starting point is the development and validation of a detailed chemical kinetic mechanism for gas-phase hydrazine decomposition. A reasonably complete mechanism was published in 1996, however, many of the elementary steps included had outdated rate expressions and a thorough investigation of the behavior of the mechanism under a variety of conditions was not presented. The current work has included substantial revision of the previously published mechanism, along with a more extensive examination of the decomposition behavior of hydrazine. An attempt to validate the mechanism against the limited experimental data available has been made and was moderately successful. Further computational and experimental research into the chemistry of this fuel needs to be completed.
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Pyrolysis and thermal oxidation kinetics of sugar mill press mud
International Nuclear Information System (INIS)
Gangavati, P.B.; Safi, M.J.; Singh, A.; Prasad, B.; Mishra, I.M.
2005-01-01
Press mud, a solid waste obtained from the sugar mills, has the potential of energy generation through pyrolysis and gasification. The paper reports its proximate and ultimate analyses, deformation and fusion ash temperatures, lower and higher heating values, physico-chemical and thermal degradation in nitrogen and air atmospheres. The thermal degradation was conducted in a thermogravimetric analyzer from room temperature to 900 deg C at heating rates of 20 and 40 K min -1 . The thermogravimetric, derivative thermogravimetric and differential thermal analyses were carried out to determine the rate of volatiles evolution, the effect of heating rates on the thermal degradation characteristics and to determine the global mass loss kinetics of thermal degradation. The thermal degradation was found to occur in several distinct phases: each phase giving volatile evolution in an independent parallel lump. Each decomposition phase was modeled by a single irreversible reaction with respect to the solid mass. Global mass loss kinetics was also determined for the entire decomposition process, as if occurring in one single step. The integral and differential techniques were used for the determination of kinetic parameters. Using the method of Agrawal and Sivasubramanian [R.K. Agrawal, M.S. Sivasubramanian, AIChE J. 33 (1987) 7] for the total degradation zone, the orders of reaction were found in the range of 1.00-2.50 in both the atmospheres (i.e. nitrogen and air) and the activation energy in the range of 27.84-33.44 and 57.41-88.92 kJ mol -1 in nitrogen and air, respectively. The pre-exponential factor was found in the range of 32.1-95.1 and 5.10 x 10 4 to 5.46 x 10 9 min -1 in nitrogen and air atmospheres, respectively
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MISCIBILITY AND THERMAL DEGRADATION KINETICS OF POLY-β-ALANINE/POLY(3-HYDROXYPROPIONATE BLENDS
Directory of Open Access Journals (Sweden)
Efkan CATIKER
2016-11-01
Full Text Available Poly-β-alanine (PBA and poly(3-hidroxypropionate (PHP were synthesized via base-catalyzed hydrogen transfer polymerization (HTP of acrylamide and acrylic acid, respectively. Blends of PBA/PHP with different composition (PHP content, 5% to 75% were studied using FTIR, DSC, TGA, XRD and polarized optical microscope to reveal both miscibility and thermal degradation kinetics of PBA/PHP blends. Optical images of blends were transparent and entirely uniform. Characteristic IR bands of both components shifted in higher frequencies with increasing fraction of other component. Melting temperature (Tm, thermal decomposition temperatures (Td and enthalpy of fusion (ΔHf of PHP decreased with increasing PBA fraction in blends. Thermal degradation kinetics of both components were studied by Freeman-Carroll method. Activation energies of thermal degradations of blend components were determined with a good regression coefficients (at least 0.994. Activation energies of decomposition decreased from 224.14 to 86.125 kJmol-1 with increasing PHP content. XRD spectra of blends exhibited lower peak intensities than those of neat polymers. The spectroscopic, thermal and optic methods revealed that PBA and PHP were miscible with a good compatibility in amorphous phase.
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Kinetic parameters for the thermal decomposition reactions of mixed oxides of selenium and tellurium
International Nuclear Information System (INIS)
Jerez, A.; Castro, A.; Pico, C.; Veiga, M.L.
1982-01-01
A comparative study of the thermal decomposition processes of Te 3 SeO 8 and TeSeO 4 has been carried out based on the results obtained directly by a Mettler TA 3000 apparatus and from calculations using other differential and integral methods. (orig.)
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International Nuclear Information System (INIS)
D’Cruz, Bessy; Samuel, Jadu; George, Leena
2014-01-01
Highlights: • CPM nanorods were synthesized by applying the principles of green chemistry. • The isoconversional method was used to analyze the effective activation energy. • The appropriate reaction models of the two decomposition stages were determined. • Photocatalytic water splitting was investigated in the presence of platinum co-catalyst. - Abstract: In here, the green synthesis and thermal characterization of a novel polyoxoanions of molybdenum containing phosphorus as hetero atom are reported. The composition and morphology of the nanorods were established by fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and inductively coupled plasma atomic emission spectroscopic (ICP-AES) techniques. Thermal properties of the nanoparticles were investigated by non-isothermal analysis under nitrogen atmosphere. The values activation energy of each stage of thermal decomposition for all heating rates was calculated by Flynn–Wall–Ozawa (FWO) and Kissinger–Akahira–Sunnose (KAS) methods. Invariant kinetic parameter (IKP) method and master plot method were also used to evaluate the kinetic parameters and mechanism for the thermal decomposition of cetylpyridinium phosphomolybdate (CPM). Photocatalytic water oxidation mechanism using CPM catalyst in the presence of platinum (Pt) co-catalyst enhances the H 2 evolution and was found to be 1.514 mmol/g/h
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Energy Technology Data Exchange (ETDEWEB)
D’Cruz, Bessy [Department of Chemistry, Mar Ivanios College, Thiruvananthapuram 695015 (India); Samuel, Jadu, E-mail: jadu_samuel@yahoo.co.in [Department of Chemistry, Mar Ivanios College, Thiruvananthapuram 695015 (India); George, Leena [Catalysis and Inorganic Chemistry Division, National Chemical Laboratory, Pune 411008 (India)
2014-11-20
Highlights: • CPM nanorods were synthesized by applying the principles of green chemistry. • The isoconversional method was used to analyze the effective activation energy. • The appropriate reaction models of the two decomposition stages were determined. • Photocatalytic water splitting was investigated in the presence of platinum co-catalyst. - Abstract: In here, the green synthesis and thermal characterization of a novel polyoxoanions of molybdenum containing phosphorus as hetero atom are reported. The composition and morphology of the nanorods were established by fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and inductively coupled plasma atomic emission spectroscopic (ICP-AES) techniques. Thermal properties of the nanoparticles were investigated by non-isothermal analysis under nitrogen atmosphere. The values activation energy of each stage of thermal decomposition for all heating rates was calculated by Flynn–Wall–Ozawa (FWO) and Kissinger–Akahira–Sunnose (KAS) methods. Invariant kinetic parameter (IKP) method and master plot method were also used to evaluate the kinetic parameters and mechanism for the thermal decomposition of cetylpyridinium phosphomolybdate (CPM). Photocatalytic water oxidation mechanism using CPM catalyst in the presence of platinum (Pt) co-catalyst enhances the H{sub 2} evolution and was found to be 1.514 mmol/g/h.
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Thermal decomposition of ammonium perchlorate—A TGA–FTIR–MS study: Part I
International Nuclear Information System (INIS)
Mallick, Lovely; Kumar, Sudarshan; Chowdhury, Arindrajit
2015-01-01
Highlights: • TGA–FTIR–MS study of ammonium perchlorate. • Decomposition was divided into low, intermediate, and high temperature regimes. • N 2 O and NO 2 were the major species at low and high temperature regimes, respectively. • N 2 O, NO 2 , HNO 3 , and HCl were quantified to aid kinetic evaluation. • NO was not detected as a major product at any stage. - Abstract: The thermal decomposition of ammonium perchlorate has been studied using thermogravimetric analysis (TGA), coupled with Fourier transform infrared (FTIR) spectroscopy and electron ionization (EI) mass spectrometry (MS) of the evolved gases. The thermal decomposition could be demarcated into three distinct regimes, the low temperature decomposition (LTD) regime and the high temperature decomposition (HTD) regime, with an intermediate regime between the two, named as the intermediate temperature decomposition (ITD) regime. Using FTIR spectroscopy, N 2 O was detected as the primary species during the LTD regime, followed by HCl, NO 2 , and HNO 3 , in lesser quantities. On the contrary, NO 2 was found to be the principal species, followed by almost equal concentrations of HCl, N 2 O, and HNO 3 in the HTD regime. Other important species, such as H 2 O, Cl 2 , O 2 , etc., although observed by MS, were not quantified. NO could not be identified in appreciable quantities in any of the regimes. Based on the species detected during the present work, and previous research, a reaction scheme has been proposed for AP decomposition in the LTD and the HTD regimes
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Basic dye decomposition kinetics in a photocatalytic slurry reactor
International Nuclear Information System (INIS)
Wu, C.-H.; Chang, H.-W.; Chern, J.-M.
2006-01-01
Wastewater effluent from textile plants using various dyes is one of the major water pollutants to the environment. Traditional chemical, physical and biological processes for treating textile dye wastewaters have disadvantages such as high cost, energy waste and generating secondary pollution during the treatment process. The photocatalytic process using TiO 2 semiconductor particles under UV light illumination has been shown to be potentially advantageous and applicable in the treatment of wastewater pollutants. In this study, the dye decomposition kinetics by nano-size TiO 2 suspension at natural solution pH was experimentally studied by varying the agitation speed (50-200 rpm), TiO 2 suspension concentration (0.25-1.71 g/L), initial dye concentration (10-50 ppm), temperature (10-50 deg. C), and UV power intensity (0-96 W). The experimental results show the agitation speed, varying from 50 to 200 rpm, has a slight influence on the dye decomposition rate and the pH history; the dye decomposition rate increases with the TiO 2 suspension concentration up to 0.98 g/L, then decrease with increasing TiO 2 suspension concentration; the initial dye decomposition rate increases with the initial dye concentration up to a certain value depending upon the temperature, then decreases with increasing initial dye concentration; the dye decomposition rate increases with the UV power intensity up to 64 W to reach a plateau. Kinetic models have been developed to fit the experimental kinetic data well
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Thermal decomposition of lanthanide and actinide tetrafluorides
International Nuclear Information System (INIS)
Gibson, J.K.; Haire, R.G.
1988-01-01
The thermal stabilities of several lanthanide/actinide tetrafluorides have been studied using mass spectrometry to monitor the gaseous decomposition products, and powder X-ray diffraction (XRD) to identify solid products. The tetrafluorides, TbF 4 , CmF 4 , and AmF 4 , have been found to thermally decompose to their respective solid trifluorides with accompanying release of fluorine, while cerium tetrafluoride has been found to be significantly more thermally stable and to congruently sublime as CeF 4 prior to appreciable decomposition. The results of these studies are discussed in relation to other relevant experimental studies and the thermodynamics of the decomposition processes. 9 refs., 3 figs
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Czech Academy of Sciences Publication Activity Database
Asadi, Z.; Golzard, F.; Eigner, Václav; Dušek, Michal
2013-01-01
Roč. 66, č. 20 (2013), s. 3629-3646 ISSN 0095-8972 R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : X-ray crystallography * uranyl Schiff base complex * kinetics of thermal decomposition * cyclic voltammetry * kinetics and mechanism Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.224, year: 2013
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Thermal decomposition of ammonium perchlorate—A TGA–FTIR–MS study: Part I
Energy Technology Data Exchange (ETDEWEB)
Mallick, Lovely; Kumar, Sudarshan [Department of Aerospace Engineering, Indian Institute of Technology, Bombay, Mumbai 400076 (India); Chowdhury, Arindrajit, E-mail: arindra@iitb.ac.in [Department of Mechanical Engineering Indian Institute of Technology, Bombay, Mumbai 400076 (India)
2015-06-20
Highlights: • TGA–FTIR–MS study of ammonium perchlorate. • Decomposition was divided into low, intermediate, and high temperature regimes. • N{sub 2}O and NO{sub 2} were the major species at low and high temperature regimes, respectively. • N{sub 2}O, NO{sub 2}, HNO{sub 3}, and HCl were quantified to aid kinetic evaluation. • NO was not detected as a major product at any stage. - Abstract: The thermal decomposition of ammonium perchlorate has been studied using thermogravimetric analysis (TGA), coupled with Fourier transform infrared (FTIR) spectroscopy and electron ionization (EI) mass spectrometry (MS) of the evolved gases. The thermal decomposition could be demarcated into three distinct regimes, the low temperature decomposition (LTD) regime and the high temperature decomposition (HTD) regime, with an intermediate regime between the two, named as the intermediate temperature decomposition (ITD) regime. Using FTIR spectroscopy, N{sub 2}O was detected as the primary species during the LTD regime, followed by HCl, NO{sub 2}, and HNO{sub 3}, in lesser quantities. On the contrary, NO{sub 2} was found to be the principal species, followed by almost equal concentrations of HCl, N{sub 2}O, and HNO{sub 3} in the HTD regime. Other important species, such as H{sub 2}O, Cl{sub 2}, O{sub 2}, etc., although observed by MS, were not quantified. NO could not be identified in appreciable quantities in any of the regimes. Based on the species detected during the present work, and previous research, a reaction scheme has been proposed for AP decomposition in the LTD and the HTD regimes.
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Kinetics of hydrogen peroxide decomposition by catalase: hydroxylic solvent effects.
Raducan, Adina; Cantemir, Anca Ruxandra; Puiu, Mihaela; Oancea, Dumitru
2012-11-01
The effect of water-alcohol (methanol, ethanol, propan-1-ol, propan-2-ol, ethane-1,2-diol and propane-1,2,3-triol) binary mixtures on the kinetics of hydrogen peroxide decomposition in the presence of bovine liver catalase is investigated. In all solvents, the activity of catalase is smaller than in water. The results are discussed on the basis of a simple kinetic model. The kinetic constants for product formation through enzyme-substrate complex decomposition and for inactivation of catalase are estimated. The organic solvents are characterized by several physical properties: dielectric constant (D), hydrophobicity (log P), concentration of hydroxyl groups ([OH]), polarizability (α), Kamlet-Taft parameter (β) and Kosower parameter (Z). The relationships between the initial rate, kinetic constants and medium properties are analyzed by linear and multiple linear regression.
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Thermal Analysis and Degradation Kinetics of Dextran and Highly Substituted Dextran Acetates
International Nuclear Information System (INIS)
Amin, M.; Hussain, M. A.; Shahwar, D.; Hussain, M.
2015-01-01
Dextran acetates were synthesized to study their thermal behavior in comparison with pure dextran. The results have indicated that dextran is significantly stabilized after acetylation. Dextran acetates are thermally 65-74 degree C more stable as compared to pure dextran in terms of maximum decomposition temperature (Td/sub m/). Likewise, degradation of dextran acetates also starts and ends later than dextran as shown by relatively higher initial (Td/sub i/) 3-33 degree C and final decomposition temperature (Td/sub f/) 55-69 degree C. The dextran acetates can be arranged in increasing order of thermal stability: dextran acetate DS 2.91 < dextran DS 2.98 < dextran acetate DS 3. The activation energy (Ea) of dextran and dextran acetates was calculated with the help of Friedman, Broido and Chang kinetic models while order of reaction (n) was calculated from thermal data using Chang and Kissinger models. Several other important parameters were also calculated including frequency factor (Z), enthalpy (delta H), Gibbs free energy (delta G) and entropy (delta S). The integral procedural decomposition temperature (IPDT) and comprehensive index of intrinsic thermal stability (ITS) was also drawn from TG curves using Doyle's method. The dependence of IPDT, ITS and Ea on DS of the acetylation of dextran is also discussed. (author)
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Thermal decomposition and kinetics of coal and fermented cornstalk using thermogravimetric analysis.
He, Yuyuan; Chang, Chun; Li, Pan; Han, Xiuli; Li, Hongliang; Fang, Shuqi; Chen, Junying; Ma, Xiaojian
2018-07-01
The thermal behavior and kinetics of Yiluo coal (YC) and the residues of fermented cornstalk (FC) were investigated in this study. The Kissinger-Akahira-Sunose (KAS) and Flynn-Wall-Ozawa (FWO) methods were used for the kinetic analysis of the pyrolysis process. The results showed that the activation energy (E α ) was increased with the increase of the thermal conversion rate (α), and the average values of E α of YC, FC and the blend (m YC /m FC = 6/4) were 304.26, 224.94 and 233.46 kJ/mol, respectively. The order reaction model function for the blend was also developed by the master-plots method. By comparing the E a and the enthalpy, it was found that the blend was favored to format activated complex due to the lower potential energy barrier. Meanwhile, the average value of Gibbs free energy of the blend was 169.83 kJ/mol, and the changes of entropies indicated that the pyrolysis process was evolved from ordered-state to disordered-state. Copyright © 2018 Elsevier Ltd. All rights reserved.
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International Nuclear Information System (INIS)
Gualtieri, Alessandro F.; Gualtieri, Magdalena Lassinantti; Tonelli, Massimo
2008-01-01
The thermal transformation of asbestos into non-hazardous crystalline phases and their recycling is a promising solution for the 'asbestos problem'. The most common asbestos-containing industrial material produced worldwide is cement-asbestos. Knowledge of the kinetics of thermal transformation of asbestos fibers in cement-asbestos is of paramount importance for the optimization of the firing process at industrial scale. Here, environmental scanning electron microscopy (ESEM) was used for the first time to follow in situ the thermal transformation of chrysotile fibers present in cement-asbestos. It was found that the reaction kinetics of thermal transformation of chrysotile was highly slowed down in the presence of water vapor in the experimental chamber with respect to He. This was explained by chemisorbed water on the surface of the fibers which affected the dehydroxylation reaction and consequently the recrystallization into Mg-silicates. In the attempt to investigate alternative and faster firing routes for the decomposition of asbestos, a low melting glass was mixed with cement-asbestos and studied in situ to assess to which extent the decomposition of asbestos is favored. It was found that the addition of a low melting glass to cement-asbestos greatly improved the decomposition reaction and decreased the transformation temperatures
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Energy Technology Data Exchange (ETDEWEB)
Das, Mitali; Shu, Chi-Min, E-mail: shucm@yuntech.edu.tw
2016-01-15
Highlights: • Thermally degraded DBPH products are identified. • An appropriate mathematical model was selected for decomposition study. • Differential isoconversional analysis was performed to obtain kinetic parameters. • Simulation on thermal analysis model was conducted for the best storage conditions. - Abstract: This study investigated the thermal degradation products of 2,5-dimethyl-2,5-di-(tert-butylperoxy) hexane (DBPH), by TG/GC/MS to identify runaway reaction and thermal safety parameters. It also included the determination of time to maximum rate under adiabatic conditions (TMR{sub ad}) and self-accelerating decomposition temperature obtained through Advanced Kinetics and Technology Solutions. The apparent activation energy (E{sub a}) was calculated from differential isoconversional kinetic analysis method using differential scanning calorimetry experiments. The E{sub a} value obtained by Friedman analysis is in the range of 118.0–149.0 kJ mol{sup −1}. The TMR{sub ad} was 24.0 h with an apparent onset temperature of 82.4 °C. This study has also established an efficient benchmark for a thermal hazard assessment of DBPH that can be applied to assure safer storage conditions.
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Thermal decomposition of γ-irradiated lead nitrate
International Nuclear Information System (INIS)
Nair, S.M.K.; Kumar, T.S.S.
1990-01-01
The thermal decomposition of unirradiated and γ-irradiated lead nitrate was studied by the gas evolution method. The decomposition proceeds through initial gas evolution, a short induction period, an acceleratory stage and a decay stage. The acceleratory and decay stages follow the Avrami-Erofeev equation. Irradiation enhances the decomposition but does not affect the shape of the decomposition curve. (author) 10 refs.; 7 figs.; 2 tabs
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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.
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Energy Technology Data Exchange (ETDEWEB)
Dandl, H.; Emig, G. [Lehrstuhl fuer Technische Chemie I, Erlangen (Germany)
1998-03-27
A highly active catalyst for the decomposition of N{sub 2}O was prepared by the thermal treatment of CoLaAl-hydrotalcite. For this catalyst the reaction rate was determined at various partial pressures of N{sub 2}O, O{sub 2} and H{sub 2}O in a temperature range from 573K to 823K. The kinetic simulation resulted in a mechanistic model. The energies of activation and rate coefficients are estimated for the main steps of the reaction
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Energy Technology Data Exchange (ETDEWEB)
Pareige, C., E-mail: cristelle.pareige@univ-rouen.fr [Groupe de Physique des Matériaux, UMR 6634 CNRS, Université et INSA de Rouen, Avenue de l' Université, BP 12, 76801 Saint Etienne du Rouvray (France); Emo, J. [Groupe de Physique des Matériaux, UMR 6634 CNRS, Université et INSA de Rouen, Avenue de l' Université, BP 12, 76801 Saint Etienne du Rouvray (France); Saillet, S.; Domain, C. [EDF R& D Département Matériaux et Mécanique des Composants, Avenue des Renardières – Ecuelles, F-77250 Moret sur Loing (France); Pareige, P. [Groupe de Physique des Matériaux, UMR 6634 CNRS, Université et INSA de Rouen, Avenue de l' Université, BP 12, 76801 Saint Etienne du Rouvray (France)
2015-10-15
Evolution of spinodal decomposition and G-phase precipitation in ferrite of a thermally aged Mo-free duplex stainless steel was studied by Atom Probe Tomography (APT). Kinetics was compared to kinetics observed in ferrite of some Mo-bearing steels aged in similar conditions. This paper shows that formation of the G-phase particles proceeds via at least a two-step mechanism: enrichment of α/α′ inter-domains by G-former elements followed by formation of G-phase particles. As expected, G-phase precipitation is much less intense in the Mo-free steel than in Mo-bearing steels. The kinetic synergy observed in Mo-bearing steels between spinodal decomposition and G-phase precipitation is shown to also exist in Mo-free steel. Spinodal decomposition is less developed in the ferrite of the Mo-free steel investigated than in Mo-bearing steels: both the amplitude of the decomposition and the effective time exponent of the wavelength (0.06 versus 0.16) are much lower for the Mo-free steel. Neither the temperature of homogenisation nor quench effects or Ni and Mo contents could successfully explain the low time exponent of the spinodal decomposition observed in the Mo-free steel. The diffusion mechanisms could be at the origin of the different time exponents (diffusion along α/α′ interfaces or diffusion of small clusters).
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Review on Thermal Decomposition of Ammonium Nitrate
Chaturvedi, Shalini; Dave, Pragnesh N.
2013-01-01
In this review data from the literature on thermal decomposition of ammonium nitrate (AN) and the effect of additives to their thermal decomposition are summarized. The effect of additives like oxides, cations, inorganic acids, organic compounds, phase-stablized CuO, etc., is discussed. The effect of an additive mainly occurs at the exothermic peak of pure AN in a temperature range of 200°C to 140°C.
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Effect of Nano-Magnesium Hydride on the Thermal Decomposition Behaviors of RDX
International Nuclear Information System (INIS)
Yao, M.; Chen, L.; Rao, G.; Peng, J.; Zou, J.; Zeng, X.
2013-01-01
In order to improve the detonation performance of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) explosive, addictive with high heat values were used, and magnesium hydride (MgH 2 ) is one of the candidates. However, it is important to see whether MgH 2 is a safe addictive. In this paper, the thermal and kinetic properties of RDX and mixture of RDX/MgH 2 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 MgH 2 decreases both E and A of RDX, which means that the mixture of RDX/MgH 2 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/MgH 2 were given in this paper which confirmed the change of the decomposition mechanism.
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Directory of Open Access Journals (Sweden)
Zhao Fa-Jun
2018-02-01
Full Text Available Foaming agents, despite holding potential in steam injection technology for heavy oil recovery, are still poorly investigated. In this work, we analyzed the performance of the foaming agent NPL-10 in terms of foam height and half-life under various conditions of temperature, pH, salinity, and oil content by orthogonal experiments. The best conditions of use for NPL-10 among those tested are T=220°C, pH 7, salinity 10000 mg·L–1 and oil content 10 g·L–1. Thermal decomposition of NPL-10 was also studied by thermogravimetric and differential thermal analyses. NPL-10 decomposes above 220°C, and decomposition is a two-step process. The kinetic triplet (activation energy, kinetic function and pre-exponential factor and the corresponding rate law were calculated for each step. Steps 1 and 2 follow kinetics of different order (n = 2 and ½, respectively. These findings provide some criteria for the selection of foaming agents for oil recovery by steam injection.
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Hydrogen peroxide decomposition kinetics in aquaculture water
DEFF Research Database (Denmark)
Arvin, Erik; Pedersen, Lars-Flemming
2015-01-01
during the HP decomposition. The model assumes that the enzyme decay is controlled by an inactivation stoichiometry related to the HP decomposition. In order to make the model easily applicable, it is furthermore assumed that the COD is a proxy of the active biomass concentration of the water and thereby......Hydrogen peroxide (HP) is used in aquaculture systems where preventive or curative water treatments occasionally are required. Use of chemical agents can be challenging in recirculating aquaculture systems (RAS) due to extended water retention time and because the agents must not damage the fish...... reared or the nitrifying bacteria in the biofilters at concentrations required to eliminating pathogens. This calls for quantitative insight into the fate of the disinfectant residuals during water treatment. This paper presents a kinetic model that describes the HP decomposition in aquaculture water...
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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.
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Investigation into kinetics of decomposition of nitrates
International Nuclear Information System (INIS)
Belov, B.A.; Gorozhankin, Eh.V.; Efremov, V.N.; Sal'nikova, N.S.; Suris, A.L.
1985-01-01
Using the method of thermogravimetry, the decomposition of nitrates, Cd(NO 3 ) 2 x4H 2 O, La(NO 3 ) 2 x6H 2 O, Sr(NO 3 ) 2 , ZrO(NO 3 ) 2 x2H 2 O, Y(NO 3 ) 3 x6H 2 O, in particular, is studied in the 20-1000 deg C range. It is shown, that gaseous pyrolysis, products, remaining in the material, hamper greatly the heat transfer required for the decomposition which reduces the reaction order. An effective activation energy of the process is in a satisfactory agreement with the characteristic temperature of the last endotherm. Kinetic parameters are calculated by the minimization method using a computer
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Directory of Open Access Journals (Sweden)
Hongbo Y.
2015-06-01
Full Text Available The thermal decomposition of magnesium-aluminum layered double hydroxides (LDHs was investigated by thermogravimetry analysis and differential scanning calorimetry (DSC methods in argon environment. The influence of heating rates (including 2.5, 5, 10, 15 and 20K/min on the thermal behavior of LDHs was revealed. By the methods of Kissinger and Flynn-Wall-Ozawa, the thermal kinetic parameters of activation energy and pre-exponential factor for the exothermic processes under non-isothermal conditions were calculated using the analysis of corresponding DSC curves.
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International Nuclear Information System (INIS)
Zhang, Jiao-Qiang; Gao, Hong-Xu; Ji, Tie-Zheng; Xu, Kang-Zhen; Hu, Rong-Zu
2011-01-01
Highlights: → Non-isothermal decomposition kinetics, heat capacity and thermal safety on 37.2/44/16/2.2/0.2/0.4-GAP/CL-20/Al/N-100/PCA/auxiliaries mixture. → Apparent activation energy and pre-exponential constant obtained. → Thermal explosion temperature, adiabatic time-to-explosion, 50% drop height of impact sensitivity, and critical temperature of hot-spot initiation calculated. - Abstract: The specific heat capacity (C p ) of 37.2/44/16/2.2/0.2/0.4-GAP/CL-20/Al/N-100/PCA/auxiliaries mixture was determined with the continuous C p mode of microcalorimeter. The equation of C p with temperature was obtained. The standard molar heat capacity of GAP/CL-20/Al/N-100/PCA/auxiliaries mixture was 1.225 J mol -1 K -1 at 298.15 K. With the help of the peak temperature (T p ) from the non-isothermal DTG curves of the mixture at different heating rates (β), the apparent activation energy (E k and E o ) and pre-exponential constant (A K ) of thermal decomposition reaction obtained by Kissinger's method and Ozawa's method. Using density (ρ) and thermal conductivity (λ), the decomposition heat (Q d , taking half-explosion heat), Zhang-Hu-Xie-Li's formula, the values (T e0 and T p0 ) of T e and T p corresponding to β → 0, thermal explosion temperature (T be and T bp ), adiabatic time-to-explosion (t TIad ), 50% drop height (H 50 ) of impact sensitivity, and critical temperature of hot-spot initiation (T cr,hotspot ) of thermal explosion of the mixture were calculated. The following results of evaluating the thermal safety of the mixture were obtained: T be = 441.64 K, T bp = 461.66 K, t Tlad = 78.0 s (n = 2), t Tlad = 74.87s (n = 1), t Tlad = 71.85 s (n = 0), H 50 = 21.33 cm.
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Directory of Open Access Journals (Sweden)
Ying Deng
2016-01-01
Full Text Available Cubic phase cobalt (Co, which can be used as a key component for composite materials given its excellent ductility and internal structure, is not easy to obtain at room temperature. In this study, oxalic acid and cobalt nitrate are used as raw materials to synthesize the cobalt oxalate precursor, which has a stable structure with a five-membered chelate ring. Cobalt oxalate microspheres, having a high internal energy content, were prepared by using mechanical solid-state reaction in the presence of a surfactant, which can produce spherical micelles. The thermal decomposition of the precursor was carried out by maintaining it in a nitrogen atmosphere at 450°C for 3 h. At the end of the procedure, 100 nm cubic phase-Co microspheres, stable at room temperature, were obtained. Isothermal and nonisothermal kinetic mechanisms of cobalt grain growth were investigated. The cubic-Co grain growth activation energy, Q, was calculated in this study to be 71.47 kJ/mol. The required reaction temperature was low, making the production process simple and suitable for industrial applications.
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International Nuclear Information System (INIS)
Sawicka, Marlena; Storoniak, Piotr; Skurski, Piotr; Blazejowski, Jerzy; Rak, Janusz
2006-01-01
The thermal decomposition of quaternary methylammonium halides was studied using thermogravimetry coupled to FTIR (TG-FTIR) and differential scanning calorimetry (DSC) as well as the DFT, MP2 and G2 quantum chemical methods. There is almost perfect agreement between the experimental IR spectra and those predicted at the B3LYP/6-311G(d,p) level: this has demonstrated for the first time that an equimolar mixture of trimethylamine and a methyl halide is produced as a result of decomposition. The experimental enthalpies of dissociation are 153.4, 171.2, and 186.7 kJ/mol for chloride, bromide and iodide, respectively, values that correlate well with the calculated enthalpies of dissociation based on crystal lattice energies and quantum chemical thermodynamic barriers. The experimental activation barriers estimated from the least-squares fit of the F1 kinetic model (first-order process) to thermogravimetric traces - 283, 244 and 204 kJ/mol for chloride, bromide and iodide, respectively - agree very well with theoretically calculated values. The theoretical approach assumed in this work has been shown capable of predicting the relevant characteristics of the thermal decomposition of solids with experimental accuracy
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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.)
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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.
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The influence of VO2(B nanobelts on thermal decomposition of ammonium perchlorate
Directory of Open Access Journals (Sweden)
Zhang Yifu
2015-09-01
Full Text Available The influence of vanadium dioxide VO2(B on thermal decomposition of ammonium perchlorate (AP has not been reported before. In this contribution, the effect of VO2(B nanobelts on the thermal decomposition of AP was investigated by the Thermo- Gravimetric Analysis and Differential Thermal Analysis (TG/DTA. VO2(B nanobelts were hydrothermally prepared using peroxovanadium (V complexes, ethanol and water as starting materials. The thermal decomposition temperatures of AP in the presence of I wt.%, 3 wt.% and 6 wt.% of as-obtained VO2thermal decomposition temperature of AP Furthermore, the influence of the corresponding V2Os, which was obtained by thermal treatment of VO2(B nanobelts, on the thermal decomposition of AP was also investigated. The resufs showed that VO2(B nanobelts had a greater influence on the thermal decomposition temperature of AP than that of V2Os.
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International Nuclear Information System (INIS)
3, CEP 12.516-410 Guaratinguetá, SP (Brazil); U.T.P. – Universidad Tecnológica de Pereira, Faculty of Mechanical Engineering, Pereira, Risaralda (Colombia))" data-affiliation=" (UNESP – Univ Estadual Paulista, Campus of Guaratinguetá, Department of Energy, Laboratory of Combustion and Carbon Capture LC3, CEP 12.516-410 Guaratinguetá, SP (Brazil); U.T.P. – Universidad Tecnológica de Pereira, Faculty of Mechanical Engineering, Pereira, Risaralda (Colombia))" >Rios Quiroga, Luis Carlos; 3, CEP 12.516-410 Guaratinguetá, SP (Brazil))" data-affiliation=" (UNESP – Univ Estadual Paulista, Campus of Guaratinguetá, Department of Energy, Laboratory of Combustion and Carbon Capture LC3, CEP 12.516-410 Guaratinguetá, SP (Brazil))" >Balestieri, José 3, CEP 12.516-410 Guaratinguetá, SP (Brazil))" data-affiliation=" (UNESP – Univ Estadual Paulista, Campus of Guaratinguetá, Department of Energy, Laboratory of Combustion and Carbon Capture LC3, CEP 12.516-410 Guaratinguetá, SP (Brazil))" >Antonio Perrella; 3, CEP 12.516-410 Guaratinguetá, SP (Brazil))" data-affiliation=" (UNESP – Univ Estadual Paulista, Campus of Guaratinguetá, Department of Energy, Laboratory of Combustion and Carbon Capture LC3, CEP 12.516-410 Guaratinguetá, SP (Brazil))" >Ávila, Ivonete
2017-01-01
Highlights: • Kinetic parameters of thermal decomposition events were obtained. • Thermal analysis was used as a tool for understanding combustion processes. • Blends would be classified using thermogravimetric analysis technics. • Synergistic effect of ethanol mixed with gasoline was studied and defined. • Relative error and activation energy values were used to analyze the synergy. - Abstract: The use of ethanol as a fuel or as an additive blended with gasoline is very important for most countries, which aim to reduce the heavy dependence on fossil fuels and mitigate greenhouse gases emission. An increased use of ethanol-gasoline blends has placed great relevance on acquiring knowledge about their physical and chemical properties. Thus, knowledge of such properties favors a better understanding of the effect of the percentage of ethanol/gasoline blends on engine performance. Thence, the present study has established a correlation between activation energy and synergetic effects, obtained by a thermal analysis, and ethanol content in gasoline for different blends in order to use this technique as a tool to classify these blends in the process in order to obtain useful energy in spark ignition engines. For such a purpose, a kinetic study has been conducted through a simultaneous thermal analysis system – TGA (thermogravimetry analysis) and DTA (differential thermal analysis) by following the methodology of non-isothermal tests. Thermogravimetric tests were performed and fuel activation energies for gasoline, ethanol, and percentages of 5, 10, 15, 20, 25, 30, 50, and 75% (%v) ethanol mixed with gasoline, which was achieved by the model free kinetics. The analysis results suggest that the theoretical curves characteristics of the thermal decomposition of ethanol-gasoline blends are rather different due to their ethanol content. Furthermore, it was observed significant interactions and synergistic effects, especially regarding those with low ethanol
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Thermal decomposition of zirconium compounds with some aromatic hydroxycarboxylic acids
Energy Technology Data Exchange (ETDEWEB)
Koshel, A V; Malinko, L A; Karlysheva, K F; Sheka, I A; Shchepak, N I [AN Ukrainskoj SSR, Kiev. Inst. Obshchej i Neorganicheskoj Khimii
1980-02-01
By the thermogravimetry method investigated are processes of thermal decomposition of different zirconium compounds with mandelic, parabromomandelic, salicylic and sulphosalicylic acids. For identification of decomposition products the specimens have been kept at the temperature of effects up to the constant weight. Taken are IR-spectra, rentgenoarams, carried out is elementary analysis of decomposition products. It is stated that thermal decomposition of the investigated compounds passes in stages; the final product of thermolysis is ZrO/sub 2/. Nonhydrolized compounds are stable at heating in the air up to 200-265 deg. Hydroxy compounds begin to decompose at lower temperature (80-100 deg).
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3.6. The kinetics of sulfuric acid decomposition of calcined concentrate of borosilicate ore
International Nuclear Information System (INIS)
Mirsaidov, U.M.; Kurbonov, A.S.; Mamatov, E.D.
2015-01-01
Present article is devoted to kinetics of sulfuric acid decomposition of calcined concentrate of borosilicate ore. The experimental data of kinetics of extraction of boron oxide from danburite at sulfuric acid decomposition were obtained at 20-90 deg C temperature range and process duration 15-90 minutes. The flowsheet of obtaining of boric acid from borosilicate ores of Ak-Arkhar Deposit by sulfuric acid method was proposed.
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Silica from triethylammonium tris (oxalato) silicate (IV) thermal decomposition
International Nuclear Information System (INIS)
Ferracin, L.C.; Ionashiro, M.; Davolos, M.R.
1990-01-01
Silica can be obtained from differents precursors by differents methods. In this paper it has been investigated the thermal decomposition of triethylammonium tris (oxalato) silicate (IV) to render silica. Among the trisoxalato-complexes of silicon preparation methods reviewed it has been used the Bessler's one with the reflux adaptaded in microwave oven. Thermal decomposition analysis of the compound has been made by TG-DTG and DTA curves. Silica powders obtained and heated between 300 to 900 0 C in a oven were characterized by infrared vibrational spectroscopy, X-ray powder difraction and nitrogen adsorption isotherm (BET). The triethylammonium tris (oxalato) silicate (IV) thermal decomposition takes place at 300 0 C and the silica powder obtained is non cristalline with impurities that are eliminated with heating at 400 0 C. (author) [pt
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A Model for Thermal Decomposition of Hydrogen Peroxide
National Research Council Canada - National Science Library
Heister, S
2004-01-01
..., gas-phase decomposition kinetics, droplet dynamics, and control volume conservation laws. The code is adjustable for HP percent concentration for both main and secondary flows, massflow rates for both flows, and initial temperature of each...
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Thermal decomposition of ammonium hexachloroosmate
DEFF Research Database (Denmark)
Asanova, T I; Kantor, Innokenty; Asanov, I. P.
2016-01-01
Structural changes of (NH4)2[OsCl6] occurring during thermal decomposition in a reduction atmosphere have been studied in situ using combined energy-dispersive X-ray absorption spectroscopy (ED-XAFS) and powder X-ray diffraction (PXRD). According to PXRD, (NH4)2[OsCl6] transforms directly to meta...
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Thermal decomposition of potassium metaperiodate doped with trivalent ions
Energy Technology Data Exchange (ETDEWEB)
Muraleedharan, K., E-mail: kmuralika@gmail.com [Department of Chemistry, University of Calicut, Calicut, Kerala 673 635 (India); Kannan, M.P.; Gangadevi, T. [Department of Chemistry, University of Calicut, Calicut, Kerala 673 635 (India)
2010-04-20
The kinetics of isothermal decomposition of potassium metaperiodate (KIO{sub 4}), doped with phosphate and aluminium has been studied by thermogravimetry (TG). We introduced a custom-made thermobalance that is able to record weight decrease with time under pure isothermal conditions. The decomposition proceeds mainly through two stages: an acceleratory stages up to {alpha} = 0.50 and the decay stage beyond. The decomposition data for aluminium and phosphate doped KIO{sub 4} were found to be best described by the Prout-Tompkins equation. Separate kinetic analyses of the {alpha}-t data corresponding to the acceleratory region and decay region showed that the acceleratory stage gave the best fit with Prout-Tompkins equation itself whereas the decay stage fitted better to the contracting area equation. The rate of decomposition of phosphate doped KIO{sub 4} increases approximately linearly with an increase in the dopant concentration. In the case of aluminium doped KIO{sub 4}, the rate passes through a maximum with increase in the dopant concentration. The {alpha}-t data of pure and doped KIO{sub 4} were also subjected to isoconversional studies for the determination of activation energy values. Doping did not change the activation energy of the reaction. The results favour an electron-transfer mechanism for the isothermal decomposition of KIO{sub 4}, agreeing well with our earlier observations.
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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...
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Thermal decomposition study of Mn doped Fe3O4 nanoparticles
Malek, Tasmira J.; Chaki, S. H.; Tailor, J. P.; Deshpande, M. P.
2016-05-01
Fe3O4 is an excellent magnetic material among iron oxides. It has a cubic inverse spinel structure exhibiting distinguished electric and magnetic properties. In this paper the authors report the synthesis of Mn doped Fe3O4 nanoparticles by wet chemical reduction technique at ambient temperature and its thermal characterization. Ferric chloride hexa-hydrate (FeCl3•6H2O), manganese chloride tetra-hydrate (MnCl2•4H2O) and sodium boro-hydrate (NaBH4) were used for synthesis of Fe3O4 nanoparticles at ambient temperature. The elemental composition of the as-synthesized Mn doped Fe3O4 nanoparticles were determined by energy dispersive analysis of X-rays (EDAX) technique. Thermogravimetric (TG) and differential thermal analysis (DTA) were carried out on the Mn doped Fe3O4 nanoparticles in the temperature range of ambient to 1124 K. The thermo-curves revealed that the particles decompose by four steps. The kinetic parameters were evaluated using non-mechanistic equations for the thermal decomposition.
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Thermal decomposition of potassium bis-oxalatodiaqua- indate(III ...
Indian Academy of Sciences (India)
Unknown
32), temperature programmable thermal balance, with platinum crucible as container, is used for taking thermograms in air. The rate of heating is fixed at ... Thermal decomposition of pot. bis-oxalatodiaquaindate (III).H2O. 277. 3. Results and ...
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Synthesis and thermal decomposition study of dysprosium trifluoroacetate
DEFF Research Database (Denmark)
Opata, Y. A.; Grivel, J.-C.
2018-01-01
A study of the thermal decomposition process of dysprosium trifluoroacetate hydrate under flowing argon is presented. Thermogravimetry, differential thermal analysis, evolved gas analysis and ex-situ x-ray diffraction techniques have been employed in the investigation. Three main stages were...
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International Nuclear Information System (INIS)
Sotiriou, Georgios A.; Singh, Dilpreet; Zhang, Fang; Chalbot, Marie-Cecile G.; Spielman-Sun, Eleanor; Hoering, Lutz; Kavouras, Ilias G.; Lowry, Gregory V.; Wohlleben, Wendel; Demokritou, Philip
2016-01-01
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.
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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.
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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.
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De Waal, D.; Heyns, A. M.; Range, K.-J.
1989-06-01
Raman spectroscopy was used as a method in the kinetic investigation of the thermal decomposition of solid (NH 4) 2CrO 4. Time-dependent measurements of the intensity of the totally symmetric stretching CrO mode of (NH 4) 2CrO 4 have been made between 343 and 363 K. A short initial acceleratory period is observed at lower temperatures and the decomposition reaction decelerates after the maximum decomposition rate has been reached at all temperatures. These results can be interpreted in terms of the Avrami-Erofe'ev law 1 - (χ r) {1}/{2} = kt , where χr is the fraction of reactant at time t. At 358 K, k is equal to 1.76 ± 0.01 × 10 -3 sec -1 for microcrystals and for powdered samples. Activation energies of 97 ± 10 and 49 ± 0.9 kJ mole -1 have been calculated for microcrystalline and powdered samples, respectively.
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The non-isothermal kinetics of decomposition of manganese carbonate ore
Directory of Open Access Journals (Sweden)
Kenan Yıldız
2012-06-01
Full Text Available The non-isothermal kinetics of decomposition of manganese carbonate ore from Denizli Tavas region was studied. The ore decomposed according to a serie of reaction, MnCO3 ;#8594;(400-600°C MnO2 ;#8594;(;600 Mn2O3. By using of Kissenger equation, the activation energies for the decomposition of MnCO3 to MnO2 and the transformation of MnO2 to Mn2O3 were calculated as 185,7 kJ/mol and 217,3 kJ/mol, respectively.
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Directory of Open Access Journals (Sweden)
Jony Andrade
2008-01-01
Full Text Available The thermal decomposition of hydroxyl-terminated polybutadiene (HTPB/ammonium nitrate (AN based propellants, so called smokeless formulations, and raw materials were investigated by differential scanning calorimetry (DSC and thermogravimetry (TG. The thermoanalytical profile of different components and of propellant were evaluated and the Arrhenius parameters for the thermal decomposition of the propellant sample were determined by the Ozawa method. The kinetic parameters of the thermal decomposition of propellant samples were determined by DSC measurements. The values obtained for activation energy (Ea and pre-exponential factor were 163 kJ mol-1 and 1.94x10(6 min-1.
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Investigation of the thermal decomposition of some metal-substituted Keggin tungstophosphates
International Nuclear Information System (INIS)
Gamelas, J.A.; Couto, F.A.S.; Trovao, M.C.N.; Cavaleiro, A.M.V.; Cavaleiro, J.A.S.; Jesus, J.D.P. de
1999-01-01
The thermal decomposition of the tetrabutylammonium (TBA) salts (TBA) 4 H 3 [PW 11 O 39 ] and (TBA) 4 H x [PW 11 M(H 2 O)O 39 ]·nH 2 O, x = 3-(oxidation number of M), M = Mn(II), Co(II), Ni(II), Cu(II) or Fe(III), n = 0-3, has been studied by thermal analyses and the decomposition products identified by powder X-ray diffraction, FTIR and NMR spectroscopy. The organic cation started to decompose in the 150-200C range. The release of the metal M from the substituted polyoxoanions accompanied the initial degradation of the organic cations and [PW 12 O 40 ] 3- was formed as an intermediate at ca. 300C. For a comparison, the thermal decomposition of (TBA) 3 [PW 12 O 40 ] was also investigated. The thermal decomposition of the potassium salts of the lacunary and metal-substituted anions was also studied, but the formation of [PW 12 O 40 ] 3- was not observed. The temperature of decomposition of the [PW 11 M(H 2 O)O 39 ] (4+x)- anions was at least 150C higher for the potassium than for the tetrabutylammonium salts. This study exemplified that the thermal stability of some Keggin anions was dependent on the counter-cation present. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)
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Thermal decomposition of uranyl sulphate hydrate
International Nuclear Information System (INIS)
Sato, T.; Ozawa, F.; Ikoma, S.
1980-01-01
The thermal decomposition of uranyl sulphate hydrate (UO 2 SO 4 .3H 2 O) has been investigated by thermogravimetry, differential thermal analysis, X-ray diffraction and infrared spectrophotometry. As a result, it is concluded that uranyl sulphate hydrate decomposes thermally: UO 2 SO 4 .3H 2 O → UO 2 SO 4 .xH 2 O(2.5 = 2 SO 4 . 2H 2 O → UO 2 SO 4 .H 2 O → UO 2 SO 4 → α-UO 2 SO 4 → β-UO 2 SO 4 → U 3 O 8 . (author)
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Kinetics of the Thermal Degradation of Granulated Scrap Tyres: a Model-free Analysis
Directory of Open Access Journals (Sweden)
Félix A. LÓPEZ
2013-12-01
Full Text Available Pyrolysis is a technology with a promising future in the recycling of scrap tyres. This paper determines the thermal decomposition behaviour and kinetics of granulated scrap tyres (GST by examining the thermogravimetric/derivative thermogravimetric (TGA/DTG data obtained during their pyrolysis in an inert atmosphere at different heating rates. The model-free methods of Friedman, Flynn-Wall-Ozawa and Coats-Redfern were used to determine the reaction kinetics from the DTG data. The apparent activation energy and pre-exponential factor for the degradation of GST were calculated. A comparison with the results obtained by other authors was made.DOI: http://dx.doi.org/10.5755/j01.ms.19.4.2947
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Thermal decomposition of yttrium(III) valerate in argon
DEFF Research Database (Denmark)
Grivel, Jean-Claude; Yue, Zhao; Tang, Xiao
2014-01-01
The thermal decomposition of yttrium(III) valerate (Y(C4H9CO2)3) was studied in argon by means of thermogravimetry, differential thermal analysis, IR-spectroscopy, X-ray diffraction, in-situ synchrotron diffraction and hot-stage microscopy as well as room temperature optical microscopy. Melting...
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Decomposition kinetics of aminoborane in aqueous solutions
International Nuclear Information System (INIS)
Shvets, I.B.; Erusalimchik, I.G.
1984-01-01
Kinetics of aminoborane hydrolysis has been studied using the method of polarization galvanostatical curves on a platinum electrode in buffer solutions at pH 3; 5; 7. The supposition that the reaction of aminoborane hydrolysis is the reaction of the first order by aminoborane is proved. The rate constant of aminoborane decomposition in the solution with pH 5 is equal to: K=2.5x10 -5 s -1 and with pH 3 it equals K=1.12x10 -4 s -1
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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.
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Decomposition kinetics of plutonium hydride
Energy Technology Data Exchange (ETDEWEB)
Haschke, J.M.; Stakebake, J.L.
1979-01-01
Kinetic data for decomposition of PuH/sub 1/ /sub 95/ provides insight into a possible mechanism for the hydriding and dehydriding reactions of plutonium. The fact that the rate of the hydriding reaction, K/sub H/, is proportional to P/sup 1/2/ and the rate of the dehydriding process, K/sub D/, is inversely proportional to P/sup 1/2/ suggests that the forward and reverse reactions proceed by opposite paths of the same mechanism. The P/sup 1/2/ dependence of hydrogen solubility in metals is characteristic of the dissociative absorption of hydrogen; i.e., the reactive species is atomic hydrogen. It is reasonable to assume that the rates of the forward and reverse reactions are controlled by the surface concentration of atomic hydrogen, (H/sub s/), that K/sub H/ = c'(H/sub s/), and that K/sub D/ = c/(H/sub s/), where c' and c are proportionality constants. For this surface model, the pressure dependence of K/sub D/ is related to (H/sub s/) by the reaction (H/sub s/) reversible 1/2H/sub 2/(g) and by its equilibrium constant K/sub e/ = (H/sub 2/)/sup 1/2//(H/sub s/). In the pressure range of ideal gas behavior, (H/sub s/) = K/sub e//sup -1/(RT)/sup -1/2/ and the decomposition rate is given by K/sub D/ = cK/sub e/(RT)/sup -1/2/P/sup 1/2/. For an analogous treatment of the hydriding process with this model, it can be readily shown that K/sub H/ = c'K/sub e//sup -1/(RT)/sup -1/2/P/sup 1/2/. The inverse pressure dependence and direct temperature dependence of the decomposition rate are correctly predicted by this mechanism which is most consistent with the observed behavior of the Pu--H system.
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Model-free method for isothermal and non-isothermal decomposition kinetics analysis of PET sample
International Nuclear Information System (INIS)
Saha, B.; Maiti, A.K.; Ghoshal, A.K.
2006-01-01
Pyrolysis, one possible alternative to recover valuable products from waste plastics, has recently been the subject of renewed interest. In the present study, the isoconversion methods, i.e., Vyazovkin model-free approach is applied to study non-isothermal decomposition kinetics of waste PET samples using various temperature integral approximations such as Coats and Redfern, Gorbachev, and Agrawal and Sivasubramanian approximation and direct integration (recursive adaptive Simpson quadrature scheme) to analyze the decomposition kinetics. The results show that activation energy (E α ) is a weak but increasing function of conversion (α) in case of non-isothermal decomposition and strong and decreasing function of conversion in case of isothermal decomposition. This indicates possible existence of nucleation, nuclei growth and gas diffusion mechanism during non-isothermal pyrolysis and nucleation and gas diffusion mechanism during isothermal pyrolysis. Optimum E α dependencies on α obtained for non-isothermal data showed similar nature for all the types of temperature integral approximations
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Naya, Tomoki; Kohga, Makoto
2015-04-01
Ammonium nitrate (AN) has attracted much attention due to its clean burning nature as an oxidizer. However, an AN-based composite propellant has the disadvantages of low burning rate and poor ignitability. In this study, we added nitramine of cyclotrimethylene trinitramine (RDX) or cyclotetramethylene tetranitramine (HMX) as a high-energy material to AN propellants to overcome these disadvantages. The thermal decomposition and burning rate characteristics of the prepared propellants were examined as the ratio of AN and nitramine was varied. In the thermal decomposition process, AN/RDX propellants showed unique mass loss peaks in the lower temperature range that were not observed for AN or RDX propellants alone. AN and RDX decomposed continuously as an almost single oxidizer in the AN/RDX propellant. In contrast, AN/HMX propellants exhibited thermal decomposition characteristics similar to those of AN and HMX, which decomposed almost separately in the thermal decomposition of the AN/HMX propellant. The ignitability was improved and the burning rate increased by the addition of nitramine for both AN/RDX and AN/HMX propellants. The increased burning rates of AN/RDX propellants were greater than those of AN/HMX. The difference in the thermal decomposition and burning characteristics was caused by the interaction between AN and RDX.
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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.
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Thermal physics kinetic theory and thermodynamics
Singh, Devraj; Yadav, Raja Ram
2016-01-01
THERMAL PHYSICS: Kinetic Theory and Thermodynamics is designed for undergraduate course in Thermal Physics and Thermodynamics. The book provides thorough understanding of the fundamental principles of the concepts in Thermal Physics. The book begins with kinetic theory, then moves on liquefaction, transport phenomena, the zeroth, first, second and third laws, thermodynamics relations and thermal conduction. The book concluded with radiation phenomenon. KEY FEATURES: * Include exercises * Short Answer Type Questions * Long Answer Type Questions * Numerical Problems * Multiple Choice Questions
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Thermal decomposition of ammonium diuranate, uranyl nitrate hexahydrate and uranyl peroxide
International Nuclear Information System (INIS)
Yulianto, T.; Mutiara, E.
2011-01-01
The behaviors of three types of starting powder had been investigated during their thermal decomposition processes in nitrogen, air, and hydrogen. The powder types were the products of uranyl nitrate precipitation, i.e. ADU (ammonium diuranate), UNH (uranyl nitrate hexahydrate), and UPO (uranyl peroxide). The objective of the investigation was to find out the best atmosphere that would result in good quality powder in a thermal decomposition process with the lowest temperature and the shortest period of time in order to reduce the cost of UO 2 powder preparation. Before the thermal decomposition process was initiated, all powder types were characterized for their crystal structures. The investigation was conducted by TG-DTA instrument at temperature up to 800°C and the heating rate of 10°C/minute. The crystal structures were identified by X-Ray Diffractometer with Cu-Ka radiation. The specific surface area of the powder was also observed using BET method, especially for the powder that underwent the process in hydrogen heated up to 800°C. The Results showed that the process took place faster in hydrogen, and UNH required lower thermal decomposition temperature in relations with other types of powder. (author)
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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...
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Kinetics of Roasting Decomposition of the Rare Earth Elements by CaO and Coal
Directory of Open Access Journals (Sweden)
Shuai Yuan
2017-06-01
Full Text Available The roasting method of magnetic tailing mixed with CaO and coal was used to recycle the rare earth elements (REE in magnetic tailing. The phase transformation and decomposition process were researched during the roasting processes. The results showed that the decomposition processes of REE in magnetic tailing were divided into two steps. The first step from 380 to 431 °C mainly entailed the decomposition of bastnaesite (REFCO3. The second step from 605 to 716 °C mainly included the decomposition of monazite (REPO4. The decomposition products were primarily RE2O3, Ce0.75Nd0.25O1.875, CeO2, Ca5F(PO43, and CaF2. Adding CaO could reduce the decomposition temperature of REFCO3 and REPO4. Meanwhile, the decomposition effect of CaO on bastnaesite and monazite was significant. Besides, the effects of the roasting time, roasting temperature, and CaO addition level on the decomposition rate were studied. The optimum technological conditions were a roasting time of 60 min; roasting temperature of 750 °C; and CaO addition level of 20% (w/w. The maximum decomposition rate of REFCO3 and REPO4 was 99.87%. The roasting time and temperature were the major factors influencing the decomposition rate. The kinetics process of the decomposition of REFCO3 and REPO4 accorded with the interfacial reaction kinetics model. The reaction rate controlling steps were divided into two steps. The first step (at low temperature was controlled by a chemical reaction with an activation energy of 52.67 kJ/mol. The second step (at high temperature was controlled by diffusion with an activation energy of 8.5 kJ/mol.
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Non-isothermal kinetics of thermal degradation of chitosan
Directory of Open Access Journals (Sweden)
Georgieva Velyana
2012-08-01
Full Text Available Abstract Background Chitosan is the second most abundant nitrogen containing biopolymer in nature, obtained from the shells of crustaceans, particularly crabs, shrimp and lobsters, which are waste products of seafood processing industries. It has great potential application in the areas of biotechnology, biomedicine, food industries, and cosmetics. Chitosan is also capable of adsorbing a number of metal ions as its amino groups can serve as chelation sites. Grafted functional groups such as hydroxyl, carboxyl, sulfate, phosphate, and amino groups on the chitosan have been reported to be responsible for metal binding and sorption of dyes and pigments. The knowledge of their thermal stability and pyrolysis may help to better understand and plan their industrial processing. Results Thermogravimetric studies of chitosan in air atmosphere were carried out at six rates of linear increasing of the temperature. The kinetics and mechanism of the thermal decomposition reaction were evaluated from the TG data using recommended from ICTAC kinetics committee iso-conversional calculation procedure of Kissinger-Akahira-Sunose, as well as 27 mechanism functions. The comparison of the obtained results showed that they strongly depend on the selection of proper mechanism function for the process. Therefore, it is very important to determine the most probable mechanism function. In this respect the iso-conversional calculation procedure turned out to be the most appropriate. Conclusion Chitosan have excellent properties such as hydrophilicity, biocompatibility, biodegradability, antibacterial, non-toxicity, adsorption application. The thermal degradation of chitosan occurs in two stages. The most probable mechanism function for both stages is determined and it was best described by kinetic equations of n-th order (Fn mechanism. For the first stage, it was established that n is equal to 3.0 and for the second stage – to 1.0 respectively. The values of the
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The influence of temperature on the decomposition kinetics of peracetic acid in solutions
Kunigk, L.; Gomes, D.R.; Forte, F.; Vidal, K.P.; Gomes, L.F.; Sousa, P.F.
2001-01-01
Peracetic acid is a powerful sanitizer that has only recently been introduced in the Brazilian food industry. The main disadvantage of this sanitizer is its decomposition rate. The main purpose of this paper is to present results obtained in experiments carried out to study the decomposition kinetics of peracetic acid in aqueous solutions at 25, 35, 40 and 45 °C. The decompositon of peracetic acid is a first-order reaction. The decomposition rate constants are between 1.71x10-3 h -1 for 25 °C...
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Treatment of off-gas evolved from thermal decomposition of sludge waste
International Nuclear Information System (INIS)
Doo-Seong Hwang; Yun-Dong Choi; Gyeong-Hwan Jeong; Jei-Kwon Moon
2013-01-01
Korea Atomic Energy Research Institute (KAERI) started a decommissioning program of a uranium conversion plant. The treatment of the sludge waste, which was generated during the operation of the plant, is one of the most important tasks in the decommissioning program of the plant. The major compounds of sludge waste are nitrate salts and uranium. The sludge waste is denitrated by thermal decomposition. The treatment of off-gas evolved from the thermal decomposition of nitrate salts in the sludge waste is investigated. The nitrate salts in the sludge were decomposed in two steps: the first decomposition is due to the ammonium nitrate, and the second is due to the sodium and calcium nitrate and calcium carbonate. The components of off-gas from the decomposition of ammonium nitrate at low temperature are NH 3 , N 2 O, NO 2 , and NO. In addition, the components from the decomposition of sodium and calcium nitrate at high temperature are NO 2 and NO. Off-gas from the thermal decomposition is treated by the catalytic oxidation of ammonia and selective catalytic reduction (SCR). Ammonia is converted into nitrogen oxides through the oxidation catalyst and all nitrogen oxides are removed by SCR treatment besides nitrous oxide, which is greenhouse gas. An additional process is needed to remove nitrous oxide, and the feeding rate of ammonia in SCR should be controlled properly for evolved nitrogen oxides. (author)
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Thermal decomposition of 2-methylbenzoates of rare earth elements
International Nuclear Information System (INIS)
Brzyska, W.; Szubartowski, L.
1980-01-01
The conditions of thermal decomposition of La, Ce(3), Pr, Nd, Sm and Y 2-methylbenzoates were examined. On the basis of obtained results it was stated that hydrated 2-methylbenzoates were subjected to dehydration passing into anhydrated salts and then they decomposed into oxides. The activation energy of dehydration and decomposition reactions of lanthanons, La and Y 2-methylbenzoates was determined. (author)
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Kinetic analysis of thermally relativistic flow with dissipation
International Nuclear Information System (INIS)
Yano, Ryosuke; Suzuki, Kojiro
2011-01-01
Nonequilibrium flow of thermally relativistic matter with dissipation is considered in the framework of the relativistic kinetic theory. As an object of the analysis, the supersonic rarefied flow of thermally relativistic matter around the triangle prism is analyzed using the Anderson-Witting model. Obtained numerical results indicate that the flow field changes in accordance with the flow velocity and temperature of the uniform flow owing to both effects derived from the Lorentz contraction and thermally relativistic effects, even when the Mach number of the uniform flow is fixed. The profiles of the heat flux along the stagnation streamline can be approximated on the basis of the relativistic Navier-Stokes-Fourier (NSF) law except for a strong nonequilibrium regime such as the middle of the shock wave and the vicinity of the wall, whereas the profile of the heat flux behind the triangle prism cannot be approximated on the basis of the relativistic NSF law owing to rarefied effects via the expansion behind the triangle prism. Additionally, the heat flux via the gradient of the static pressure is non-negligible owing to thermally relativistic effects. The profile of the dynamic pressure is different from that approximated on the basis of the NSF law, which is obtained by the Eckart decomposition. Finally, variations of convections of the mass and momentum owing to the effects derived from the Lorentz contraction and thermally relativistic effects are numerically confirmed.
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Thermal decomposition of yttrium(III) propionate and butyrate
DEFF Research Database (Denmark)
Grivel, Jean-Claude
2013-01-01
The thermal decompositions of yttrium(III) propionate monohydrate (Y(C2H5CO2)3·H2O) and yttrium(III) butyrate dihydrate (Y(C3H7CO2)3·2H2O) were studied in argon by means of thermogravimetry, differential thermal analysis, IR-spectroscopy, X-ray diffraction and hot-stage microscopy. These two...
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Thermal decomposition studies of aqueous and nitric solutions of hydroxyurea
International Nuclear Information System (INIS)
Shekhar Kumar; Pranay Kumar Sinha; Kamachi Mudali, U.; Natarajan, R.
2012-01-01
Hydroxyurea and its derivatives are important nonsalt forming reductants in partitioning of uranium and plutonium in the nuclear fuel reprocessing operations. There is no experimental data available in open literature describing pressurization due to the thermal decomposition of aqueous and nitric solutions of hydroxyurea at elevated temperatures. Authors studied thermal decomposition of hydroxyurea-nitric acid system and resultant pressurization at various concentrations of nitric acid in an adiabatic calorimeter in closed-vent conditions. During these experiments, pressurization was observed. In this paper, results of these experiments have been discussed. (author)
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Radiation effects on thermal decomposition of inorganic solids
International Nuclear Information System (INIS)
Dedgaonkar, V.G.
1985-01-01
Radiation effects on the thermal decomposition characteristics of inorganic oxyanions like permanganates, nitrates, zeolites and particularly ammonium perchlorate (AP) have been highlighted.The last compound finds wide application as an oxidizer in solid rocket propellents and although several hundred papers have been published on it during the last 30-40 years, most of which from the point of view of understanding and controlling the decomposition behaviour, there are only a few reports available in this area following the radiation treatment. (author)
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Influence of nitrogen dioxide on the thermal decomposition of ammonium nitrate
Directory of Open Access Journals (Sweden)
Igor L. Kovalenko
2015-06-01
Full Text Available In this paper results of experimental studies of ammonium nitrate thermal decomposition in an open system under normal conditions and in NO2 atmosphere are presented. It is shown that nitrogen dioxide is the initiator of ammonium nitrate self-accelerating exothermic cyclic decomposition process. The insertion of NO2 from outside under the conditions of nonisothermal experiment reduces the characteristic temperature of the beginning of self-accelerating decomposition by 50...70 °C. Using method of isothermal exposures it is proved that thermal decomposition of ammonium nitrate in nitrogen dioxide atmosphere at 210 °C is autocatalytic (zero-order reaction. It was suggested that there is possibility of increasing the sensitivity and detonation characteristics of energy condensed systems based on ammonium nitrate by the insertion of additives which provide an earlier appearance of NO2 in the system.
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Yu, Hongbo; Liu, Fang; Ke, Ming; Zhang, Xiaoyu
2015-06-01
In this study, the effect of pretreatment with Echinodontium taxodii on thermal decomposition characteristics and kinetics of bamboo wastes was investigated by thermogravimetric analysis. The results showed fungal pretreatment can enhance the thermal degradation of bamboo. The negative effect of extractives in bamboo on the thermal decomposition can be decreased by the pretreatment. A modified three-parallel-reactions model based on isolated lignin was firstly proposed to study pyrolysis kinetics of bamboo lignocellulose. Kinetic analysis showed that with increasing pretreatment time fungal delignification was enhanced to transform the lignin component with high activation energy into that with low activation energy and raise the cellulose content in bamboo, making the thermal decomposition easier. These results demonstrated fungal pretreatment provided a potential way to improve thermal conversion efficiency of bamboo. Copyright © 2015 Elsevier Ltd. All rights reserved.
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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...
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Effect of Isomorphous Substitution on the Thermal Decomposition Mechanism of Hydrotalcites
Directory of Open Access Journals (Sweden)
Sergio Crosby
2014-10-01
Full Text Available Hydrotalcites have many important applications in catalysis, wastewater treatment, gene delivery and polymer stabilization, all depending on preparation history and treatment scenarios. In catalysis and polymer stabilization, thermal decomposition is of great importance. Hydrotalcites form easily with atmospheric carbon dioxide and often interfere with the study of other anion containing systems, particularly if formed at room temperature. The dehydroxylation and decomposition of carbonate occurs simultaneously, making it difficult to distinguish the dehydroxylation mechanisms directly. To date, the majority of work on understanding the decomposition mechanism has utilized hydrotalcite precipitated at room temperature. In this study, evolved gas analysis combined with thermal analysis has been used to show that CO2 contamination is problematic in materials being formed at RT that are poorly crystalline. This has led to some dispute as to the nature of the dehydroxylation mechanism. In this paper, data for the thermal decomposition of the chloride form of hydrotalcite are reported. In addition, carbonate-free hydrotalcites have been synthesized with different charge densities and at different growth temperatures. This combination of parameters has allowed a better understanding of the mechanism of dehydroxylation and the role that isomorphous substitution plays in these mechanisms to be delineated. In addition, the effect of anion type on thermal stability is also reported. A stepwise dehydroxylation model is proposed that is mediated by the level of aluminum substitution.
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Thermal decomposition of organic solvent with nitric acid in nuclear fuel reprocessing plants
Energy Technology Data Exchange (ETDEWEB)
Koike, Tadao; Nishio, Gunji; Takada, Junichi; Tukamoto, Michio; Watanabe, Kouji [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment; Miyata, Sadaichirou
1995-02-01
Since a thermal decomposition of organic solvent containing TBP (tributyl phosphate) with nitric acid and heavy metal nitrates is an exothermic reaction, it is possible to cause an explosive decomposition of TBP-complex materials formed by a nitration between the solvent and nitric acid, if the solvent involving TBP-complex is heated upto a thermal limit in an evaporator to concentrate a fuel liquid solution from the extraction process in the reprocessing plant. In JAERI, the demonstration test for explosive decomposition of TBP-complex by the nitration was performed to elucidate the safety margin of the evaporator in the event of hypothetical explosion under auspices of the Science and Technology Agency. The demonstration test was carried out by heating TBP/n-dodecane solvent mixed with nitric acid and uranium nitrate. In the test, the thermal decomposition behavior of the solvent was examined, and also a kinematic reaction constant and a heat formation of the TBP-complex decomposition were measured by the test. In the paper, a safety analysis of a model evaporator was conducted during accidental conditions under the explosive decomposition of the solvent. (author).
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Energy Technology Data Exchange (ETDEWEB)
Minier, L.; Behrens, R. [Sandia National Labs., Livermore, CA (United States). Combustion Research Facility; Burkey, T.J. [Univ. of Memphis, TN (United States). Chemistry Dept.
1997-01-01
The solid phase thermal reaction chemistry of NTO between 190 and 250 C is presently being evaluated by utilizing STMBMS, a technique that enables the authors to measure the vapor pressure of NTO and to explore the reaction mechanisms and chemical kinetics associated with the NTO thermal decomposition process. The vapor pressure of NTO is expressed as Log{sub 10} p(torr) = 12.5137 + 6,296.553(1/t{sub k}) and the {Delta}H{sub subl} = 28.71 {+-} 0.07 kcal/mol (120.01 {+-} 0.29 kJ/mol). The pyrolysis of NTO results in the formation of gaseous products and a condensed-phase residue. The identity of the major gaseous products and their origin from within the NTO molecules are determined based on the results from pyrolysis of NTO, NTO-3-{sup 13}C, NTO-1,2-{sup 15}N{sub 2} and NTO-{sup 2}H{sub 2}. Identification of the products show the major gaseous products to be N{sub 2}, CO{sub 2}, NO, HNCO, H{sub 2}O and some N{sub 2}O, CO, HCN and NH{sub 3}. The N{sub 2} is mostly derived from the N-1 and N-2 positions with some being from the N-4 and N-1 or N-2 positions. The CO{sub 2} is derived from both carbons in the NTO molecule in comparable amounts. The residue has an elemental formula of C{sub 2.1}H{sub .26}N{sub 2.9}O and FTIR analysis suggests that the residue is polyurea- and polycarbamate-like in nature. The temporal behaviors of the rates of formation of the gaseous products indicate that the overall thermal decomposition of NTO in the temperature range evaluated involves four major processes: (1) NTO sublimation; (2) an apparent solid-solid phase transition between 190 and 195 C; (3) a decomposition regime induced by the presence of exogenous H{sub 2}O at the onset of decomposition; and (4) a decomposition regime that occurs at the onset of decomposition and continues until the depletion of NTO. Decomposition pathways that are consistent with the data are presented.
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The influence of temperature on the decomposition kinetics of peracetic acid in solutions
Directory of Open Access Journals (Sweden)
Kunigk L.
2001-01-01
Full Text Available Peracetic acid is a powerful sanitizer that has only recently been introduced in the Brazilian food industry. The main disadvantage of this sanitizer is its decomposition rate. The main purpose of this paper is to present results obtained in experiments carried out to study the decomposition kinetics of peracetic acid in aqueous solutions at 25, 35, 40 and 45 °C. The decompositon of peracetic acid is a first-order reaction. The decomposition rate constants are between 1.71x10-3 h -1 for 25 °C and 9.64x10-3 h-1 for 45 °C. The decomposition rate constant is affected by temperature according to the Arrhenius equation, and the activation energy for the decomposition of peracetic acid in aqueous solutions prepared from the commercial formulation used in this work is 66.20 kJ/mol.
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International Nuclear Information System (INIS)
Adamopoulou, Theodora; Papadaki, Maria I.; Kounalakis, Manolis; Vazquez-Carreto, Victor; Pineda-Solano, Alba; Wang, Qingsheng; Mannan, M.Sam
2013-01-01
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 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 −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
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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.
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Organic and inorganic decomposition products from the thermal desorption of atmospheric particles
Williams, Brent J.; Zhang, Yaping; Zuo, Xiaochen; Martinez, Raul E.; Walker, Michael J.; Kreisberg, Nathan M.; Goldstein, Allen H.; Docherty, Kenneth S.; Jimenez, Jose L.
2016-04-01
Atmospheric aerosol composition is often analyzed using thermal desorption techniques to evaporate samples and deliver organic or inorganic molecules to various designs of detectors for identification and quantification. The organic aerosol (OA) fraction is composed of thousands of individual compounds, some with nitrogen- and sulfur-containing functionality and, often contains oligomeric material, much of which may be susceptible to decomposition upon heating. Here we analyze thermal decomposition products as measured by a thermal desorption aerosol gas chromatograph (TAG) capable of separating thermal decomposition products from thermally stable molecules. The TAG impacts particles onto a collection and thermal desorption (CTD) cell, and upon completion of sample collection, heats and transfers the sample in a helium flow up to 310 °C. Desorbed molecules are refocused at the head of a gas chromatography column that is held at 45 °C and any volatile decomposition products pass directly through the column and into an electron impact quadrupole mass spectrometer. Analysis of the sample introduction (thermal decomposition) period reveals contributions of NO+ (m/z 30), NO2+ (m/z 46), SO+ (m/z 48), and SO2+ (m/z 64), derived from either inorganic or organic particle-phase nitrate and sulfate. CO2+ (m/z 44) makes up a major component of the decomposition signal, along with smaller contributions from other organic components that vary with the type of aerosol contributing to the signal (e.g., m/z 53, 82 observed here for isoprene-derived secondary OA). All of these ions are important for ambient aerosol analyzed with the aerosol mass spectrometer (AMS), suggesting similarity of the thermal desorption processes in both instruments. Ambient observations of these decomposition products compared to organic, nitrate, and sulfate mass concentrations measured by an AMS reveal good correlation, with improved correlations for OA when compared to the AMS oxygenated OA (OOA
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Kinetics of methanol decomposition on Cu/ZnO/ZrO2 catalysts
International Nuclear Information System (INIS)
Grabowski, R.; Kozlowska, A.
2004-01-01
Interaction of methanol with Cu/ZnO/ZrO 2 (with different copper content) has been investigated by gravimetric and TPD methods. The TPD measurements of methanol adsorption on these catalysis show that it forms the complexes of two types. The first complex (I) decomposes at low temperature (453 K) yielding H 2 and CO 2 and second (II) decomposes at temperature (573 K) giving CO and H 2 . In the process of decomposition of the complex (I) takes part water which is adsorbed on the surface of the catalyst and the decomposition of the complex (II) occurs without participation of adsorbed water. Gravimetric measurements of methanol and that an increase of copper content leads to the changes in the kinetics of methanol adsorption and its decomposition. On the basis of gravimetric measurements a model of methanol adsorption and decomposition on Cu/ZnO/ZrO 2 catalyst has been proposed and the rate constants of methanol adsorption (k a ) and decomposition with and without participation of water (k 1 and k 2 ) have been determined. (author)
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Thermal decomposition of hydrotalcite with chromate, molybdate or sulphate in the interlayer
Energy Technology Data Exchange (ETDEWEB)
Frost, Ray L. [Inorganic Materials Research Program, School of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane Queensland 4001 (Australia)]. E-mail: r.frost@qut.edu.au; Musumeci, Anthony W. [Inorganic Materials Research Program, School of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane Queensland 4001 (Australia); Bostrom, Thor [Inorganic Materials Research Program, School of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane Queensland 4001 (Australia); Adebajo, Moses O. [Inorganic Materials Research Program, School of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane Queensland 4001 (Australia); Weier, Matt L. [Inorganic Materials Research Program, School of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane Queensland 4001 (Australia); Martens, Wayde [Inorganic Materials Research Program, School of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane Queensland 4001 (Australia)
2005-05-15
The thermal decomposition of hydrotalcites with chromate, molybdate and sulphate in the interlayer has been studied using thermogravimetric analysis coupled to a mass spectrometer measuring the gas evolution. X-ray diffraction shows the hydrotalcites have a d(0 0 3) spacing of 7.98 A with very small differences in the d-spacing between the three hydrotalcites. XRD was also used to determine the products of the thermal decomposition. For the sulphate-hydrotalcite decomposition the products were MgO and a spinel MgAl{sub 2}O{sub 4}, for the chromate interlayered hydrotalcite MgO, Cr{sub 2}O{sub 3} and spinel. For the molybdate interlayered hydrotalcite the products were MgO, spinel and MgMoO{sub 4}. EDX analyses enabled the formula of the hydrotalcites to be determined. Two processes are observed in the thermal decomposition namely dehydration and dehydroxylation and for the case of the sulphate interlayered hydrotalcite, a third process is the loss of sulphate. Both the dehydration and dehydroxylation take place in three steps each for each of the hydrotalcites.
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Shanableh, A
2005-01-01
The main objective of this study was to develop generalized first-order kinetic models to represent hydrothermal decomposition and oxidation of biosolids within a wide range of temperatures (200-450 degrees C). A lumping approach was used in which oxidation of the various organic ingredients was characterized by the chemical oxygen demand (COD), and decomposition was characterized by the particulate (i.e., nonfilterable) chemical oxygen demand (PCOD). Using the Arrhenius equation (k = k(o)e(-Ea/RT)), activation energy (Ea) levels were derived from 42 continuous-flow hydrothermal treatment experiments conducted at temperatures in the range of 200-450 degrees C. Using predetermined values for k(o) in the Arrhenius equation, the activation energies of the various organic ingredients were separated into 42 values for oxidation and a similar number for decomposition. The activation energy values were then classified into levels representing the relative ease at which the organic ingredients of the biosolids were oxidized or decomposed. The resulting simple first-order kinetic models adequately represented, within the experimental data range, hydrothermal decomposition of the organic particles as measured by PCOD and oxidation of the organic content as measured by COD. The modeling approach presented in the paper provide a simple and general framework suitable for assessing the relative reaction rates of the various organic ingredients of biosolids.
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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 H 2 O, NH 3 , N 2 O, NO, NO 2 and HNO 3 , while in nitrogen, H 2 O, NH 3 , NO and HNO 3 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.
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Influence of nitrogen dioxide on the thermal decomposition of ammonium nitrate
Igor L. Kovalenko
2015-01-01
In this paper results of experimental studies of ammonium nitrate thermal decomposition in an open system under normal conditions and in NO2 atmosphere are presented. It is shown that nitrogen dioxide is the initiator of ammonium nitrate self-accelerating exothermic cyclic decomposition process. The insertion of NO2 from outside under the conditions of nonisothermal experiment reduces the characteristic temperature of the beginning of self-accelerating decomposition by 50...70 °C. Using metho...
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Study of non-catalytic thermal decomposition of triglyceride at hydroprocessing condition
International Nuclear Information System (INIS)
Palanisamy, Shanmugam; Gevert, Borje S.
2016-01-01
Highlights: • Thermolysis of triglycerides occurs above 300 °C and cracking intensify above 350 °C. • Decomposition of carboxylic group observed, and β-H abstraction gives radical. • Product contains aldehyde, ketonic, saturated/unsaturated, cyclic, glycerol group. • Gasoline fraction contains lighter, cyclic and unsaturated hydrocarbons. • Residues contain ester, dimer and carboxylic groups. - Abstract: Non-catalytic thermal decomposition of triglyceride is studied between 300 and 410 °C at 0.1 and 5 MPa in the presence of H 2 or inert gas. This test is carried in tubular reactor filled with inert material (borosilicate glass pellet). The qualitative and analytical results showed that n-alkanes and alkenes with oxygenated olefins were primary products, consistent with thermal cracking to lighter hydrocarbons. The resulting outlet fuel gas obtained mainly from the radical reaction and had high concentration of CO, ethylene and methane. The decomposition forms a large number of radical compounds containing acids, aldehydes, ketones, aliphatic and aromatic hydrocarbon groups. Lighter fraction contains mostly naphthenic group, and heavy fraction contains straight chain paraffinic hydrocarbons. When H 2 partial pressure raised, the cracking of heavy fractions is low, and products contain low concentration of the lighter and gasoline fractions. Here, the thermal decomposition of triglyceride yields lighter fractions due to cracking, decarboxylation and decarbonylation.
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Thermal decomposition of rhenium (5) complexes with 1,2,4-triazole
International Nuclear Information System (INIS)
Amindzhanov, A.A.; Gagieva, S.Ch.; Kotegov, K.V.
1991-01-01
Processes of thermal decomposition of rhenium (5) complexes with 1,2,4-triazole were studied. Thermolysis products were identified on the basis of data of the element analysis, IR spectra, conductometry and other methods. It is ascertained that at the first stage of thermolysis of hydroxyl-containing monomer complexes removal of water molecules occurs, and at the second one - dimerization process with formation of Re-O-Re group. It is shown that the nature of halide ion practically does not affect the temperature of the start of intensive thermal decomposition of the complexes
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Biomass pyrolysis: Thermal decomposition mechanisms of furfural and benzaldehyde
Vasiliou, AnGayle K.; Kim, Jong Hyun; Ormond, Thomas K.; Piech, Krzysztof M.; Urness, Kimberly N.; Scheer, Adam M.; Robichaud, David J.; Mukarakate, Calvin; Nimlos, Mark R.; Daily, John W.; Guan, Qi; Carstensen, Hans-Heinrich; Ellison, G. Barney
2013-09-01
The thermal decompositions of furfural and benzaldehyde have been studied in a heated microtubular flow reactor. The pyrolysis experiments were carried out by passing a dilute mixture of the aromatic aldehydes (roughly 0.1%-1%) entrained in a stream of buffer gas (either He or Ar) through a pulsed, heated SiC reactor that is 2-3 cm long and 1 mm in diameter. Typical pressures in the reactor are 75-150 Torr with the SiC tube wall temperature in the range of 1200-1800 K. Characteristic residence times in the reactor are 100-200 μsec after which the gas mixture emerges as a skimmed molecular beam at a pressure of approximately 10 μTorr. Products were detected using matrix infrared absorption spectroscopy, 118.2 nm (10.487 eV) photoionization mass spectroscopy and resonance enhanced multiphoton ionization. The initial steps in the thermal decomposition of furfural and benzaldehyde have been identified. Furfural undergoes unimolecular decomposition to furan + CO: C4H3O-CHO (+ M) → CO + C4H4O. Sequential decomposition of furan leads to the production of HC≡CH, CH2CO, CH3C≡CH, CO, HCCCH2, and H atoms. In contrast, benzaldehyde resists decomposition until higher temperatures when it fragments to phenyl radical plus H atoms and CO: C6H5CHO (+ M) → C6H5CO + H → C6H5 + CO + H. The H atoms trigger a chain reaction by attacking C6H5CHO: H + C6H5CHO → [C6H6CHO]* → C6H6 + CO + H. The net result is the decomposition of benzaldehyde to produce benzene and CO.
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1.6. The kinetics of hydrochloric acid decomposition of argillite of Chashma-Sang Deposit
International Nuclear Information System (INIS)
Mirsaidov, U.M.; Mirzoev, D.Kh.; Boboev, Kh.E.
2016-01-01
Present article of book is devoted to kinetics of hydrochloric acid decomposition of argillite of Chashma-Sang Deposit. It was defined that with temperature increasing the extraction rate of Al_2O_3 and Fe_2O_3 increases. The dependence of extraction rate of Al_2O_3 and Fe_2O_3 on process duration at hydrochloric acid decomposition of argillite was studied. The activation energy of the process was defined.
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The correlation between elongation at break and thermal decomposition of aged EPDM cable polymer
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.
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Direct observation of thermal disorder and decomposition of black phosphorus
Yoo, Seung Jo; Kim, Heejin; Lee, Ji-Hyun; Kim, Jin-Gyu
2018-02-01
Theoretical research has been devoted to reveal the properties of black phosphorus as a two-dimensional nanomaterial, but little attention has been paid for the experimental characterization. In this study, the thermal disorder and decomposition of black phosphorus were examined using in situ heating transmission electron microscopy experiments. We observed that the breaking of crystallographic symmetry begins at 380 °C under vacuum condition, followed by the phosphorus evaporates after long-term heating at 400 °C. This decomposition process can be initiated by the surficial vacancy and proceeds toward both interlayer ([010]) and intralayer ([001]) directions. The results on the thermal behavior of black phosphorus provide useful guidance for thin film deposition and fabrication processes with black phosphorus.
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The coke drum thermal kinetic effects
Energy Technology Data Exchange (ETDEWEB)
Aldescu, Maria M.; Romero, Sim; Larson, Mel [KBC Advanced Technologies plc, Surrey (United Kingdom)
2012-07-01
The coke drum thermal kinetic dynamics fundamentally affect the coker unit yields as well as the coke product properties and unit reliability. In the drum the thermal cracking and polymerization or condensation reactions take place in a semi-batch environment. Understanding the fundamentals of the foaming kinetics that occur in the coke drums is key to avoiding a foam-over that could result in a unit shutdown for several months. Although the most dynamic changes with time occur during drum filling, other dynamics of the coker process will be discussed as well. KBC has contributed towards uncovering and modelling the complexities of heavy oil thermal dynamics. (author)
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Decomposition of aluminosilicate ores of Afghanistan by hydrochloric acid
International Nuclear Information System (INIS)
Mamatov, E.D.; Khomidi, A.K.
2015-01-01
Present article is devoted to decomposition of aluminosilicate ores of Afghanistan by hydrochloric acid. The physicochemical properties of initial aluminosilicate ores were studied by means of X-ray phase, differential-thermal analysis methods. The chemical and mineral composition of aluminosilicate ores was considered. The kinetics of acid decomposition of aluminosilicate ores composed of two stages was studied as well. The flowsheets of complex processing of aluminium comprising ores by means of chloric and acid methods were proposed.
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Lee, Junggil; Kim, Youngdeuk; Kim, Wooseung
2012-01-01
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
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Institute of Scientific and Technical Information of China (English)
王刚; 李爱民
2008-01-01
Thermal decomposition of polylactic acid (PLA) was studied in the presence of pine wood sawdust (PS), walnut shell (WS), corncob (CC) in order to understand the pyrolytic behavior of these components occurring in waste. A thermogravimetric analyzer (TGA) was applied for monitoring the mass loss profiles under heating rate of 10℃·min-1. Results obtained from this comprehensive investigation indicated that PLA was decomposed in the temperature range 300-372℃, whereas the thermal degradation temperature of biomass is 183-462℃. The difference of mass loss (△W) between experimental and theoretical ones, calculated as algebraic sums of those from each separated component, is about 17% 46% at 300-400℃. These experimental results indicated a significant syner-gistic effect during PLA and biomass copyrolysis. Moreover, a kinetic analysis was performed to fit thermogravimetric data, the global processes being considered as one to two consecutive reactions. A reasonable fit to the experimental data was obtained for all materials and their blends.
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Thermal degradation and kinetic study for different waste/rejected plastic materials
International Nuclear Information System (INIS)
Rana, Srujal; Parikh, Jigisha Kamal; Mohanty, Pravakar
2013-01-01
A kinetic analysis based on thermal decomposition of rejected polypropylene, plastic film and plastic pellets collected from different industrial outlet has been carried out. Non-isothermal experiments using different heating rates of 5, 10, 20, 30, 40 and 50 .deg. C min"−"1 have been performed from ambient to 700 .deg. C in a thermo-balance with the objective of determining the kinetic parameters. The values of activation energy and frequency factor were found to be in the range of 107-322 kJ/mol, 85-331 kJ/mol, 140-375 kJ/mol and 3.49E+07-4.74E+22 min⌃(-1), 3.52E+06-2.88E+22min⌃(-1), 7.28E+13-1.17E+25 min⌃(-1) for rejected polypropylene, plastic film and plastic pellets, respectively, by Coats-Redfern and Ozawa methods including different models. Kissinger method, a model free analysis is also adopted to find the kinetic parameters. Activation energy and frequency factor were found to be 108 kJ/mol, 98 kJ/mol, 132 kJ/mol and 6.89E+03, 2.12E+02, 8.06E+05 min⌃(-1) for rejected polypropylene, plastic film and plastic pellets, respectively, by using the Kissinger method
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Hernández, Ana Belén; Okonta, Felix; Freeman, Ntuli
2017-07-01
Thermochemical valorisation processes that allow energy to be recovered from sewage sludge, such as pyrolysis and gasification, have demonstrated great potential as convenient alternatives to conventional sewage sludge disposal technologies. Moreover, these processes may benefit from CO 2 recycling. Today, the scaling up of these technologies requires an advanced knowledge of the reactivity of sewage sludge and the characteristics of the products, specific to the thermochemical process. In this study the behaviour of sewage sludge during thermochemical conversion, under different atmospheres (N 2 , CO 2 and air), was studied, using TGA-FTIR, in order to understand the effects of different atmospheric gases on the kinetics of degradation and on the gaseous products. The different steps observed during the solid degradation were related with the production of different gaseous compounds. A higher oxidative degree of the atmosphere surrounding the sample resulted in higher reaction rates and a shift of the degradation mechanisms to lower temperatures, especially for the mechanisms taking place at temperatures above 400 °C. Finally, a multiple first-order reaction model was proposed to compare the kinetic parameters obtained under different atmospheres. Overall, the highest activation energies were obtained for combustion. This work proves that CO 2 , an intermediate oxidative atmosphere between N 2 and air, results in an intermediate behaviour (intermediate peaks in the derivative thermogravimetric curves and intermediate activation energies) during the thermochemical decomposition of sewage sludge. Overall, it can be concluded that the kinetics of these different processes require a different approach for their scaling up and specific consideration of their characteristic reaction temperatures and rates should be evaluated. Copyright © 2017 Elsevier Ltd. All rights reserved.
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Energy Technology Data Exchange (ETDEWEB)
Pinto, Rui M., E-mail: ruipinto@fct.unl.pt [CFA, Centro de Fisica Atomica, Departamento de Fisica, Faculdade de Ciencias e Tecnologia, FCT, Universidade Nova de Lisboa, 2829-516 Caparica (Portugal); Dias, Antonio A.; Costa, Maria L. [CFA, Centro de Fisica Atomica, Departamento de Fisica, Faculdade de Ciencias e Tecnologia, FCT, Universidade Nova de Lisboa, 2829-516 Caparica (Portugal)
2011-03-18
Graphical abstract: Gas-phase UV photoelectron spectrum of the thermal decomposition of 5-aminotetrazole (5ATZ), obtained at 245 {sup o}C, and mechanism underlying the thermal dissociation of 2H-5ATZ. Research highlights: {yields} Electronic structure of 5ATZ studied by photoelectron spectroscopy. {yields} Gas-phase 5-ATZ exists mainly as the 2H-tautomer. {yields} Thermal decomposition of 5ATZ gives N{sub 2}, NH{sub 2}CN, HN{sub 3} and HCN, at 245 {sup o}C. {yields} HCN can be originated from a carbene intermediate. - Abstract: The electronic properties and thermal decomposition of 5-aminotetrazole (5ATZ) are investigated using UV photoelectron spectroscopy (UVPES) and theoretical calculations. Simulated spectra of both 1H- and 2H-5ATZ, based on electron propagator methods, are produced in order to study the relative gas-phase tautomer population. The thermal decomposition results are rationalized in terms of intrinsic reaction coordinate (IRC) calculations. 5ATZ yields a HOMO ionization energy of 9.44 {+-} 0.04 eV and the gas-phase 5ATZ assumes mainly the 2H-form. The thermal decomposition of 5ATZ leads to the formation of N{sub 2}, HN{sub 3} and NH{sub 2}CN as the primary products, and HCN from the decomposition of a intermediate CH{sub 3}N{sub 3} compound. The reaction barriers for the formation of HN{sub 3} and N{sub 2} from 2H-5ATZ are predicted to be {approx}228 and {approx}150 kJ/mol, at the G2(MP2) level, respectively. The formation of HCN and HNNH from the thermal decomposition of a CH{sub 3}N{sub 3} carbene intermediate is also investigated.
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Energy Technology Data Exchange (ETDEWEB)
Liu, Jin-jian [School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094 (China); Yancheng Teachers College, Yancheng 224002 (China); Liu, Zu-Liang, E-mail: liuzl@mail.njust.edu.cn [School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094 (China); Cheng, Jian [School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094 (China); Yancheng Teachers College, Yancheng 224002 (China); Fang, Dong, E-mail: fangdong106@163.com [Yancheng Teachers College, Yancheng 224002 (China)
2013-04-15
An energetic lead(II) coordination polymer based on the ligand ANPyO has been synthesized and its crystal structure has been got. The polymer was characterized by FT-IR spectroscopy, elemental analysis, DSC and TG-DTG technologies. Thermal analysis shows that there are one endothermic process and two exothermic decomposition stages in the temperature range of 50–600 °C with final residues 57.09%. The non-isothermal kinetic has also been studied on the main exothermic decomposition using the Kissinger's and Ozawa–Doyle's methods, the apparent activation energy is calculated as 195.2 KJ/mol. Furthermore, DSC measurements show that the polymer has significant catalytic effect on the thermal decomposition of ammonium perchlorate. - Graphical abstract: An energetic lead(II) coordination polymer of ANPyO has been synthesized, structurally characterized and properties tested. Highlights: ► We have synthesized and characterized an energetic lead(II) coordination polymer. ► We have measured its molecular structure and thermal decomposition. ► It has significant catalytic effect on thermal decomposition of AP.
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Cobos, C J; Sölter, L; Tellbach, E; Troe, J
2014-06-07
The thermal decomposition reactions of CF3CF2H and CF3CFHCF3 have been studied in shock waves by monitoring the appearance of CF2 radicals. Temperatures in the range 1400-2000 K and Ar bath gas concentrations in the range (2-10) × 10(-5) mol cm(-3) were employed. It is shown that the reactions are initiated by C-C bond fission and not by HF elimination. Differing conclusions in the literature about the primary decomposition products, such as deduced from experiments at very low pressures, are attributed to unimolecular falloff effects. By increasing the initial reactant concentrations in Ar from 60 to 1000 ppm, a retardation of CF2 formation was observed while the final CF2 yields remained close to two CF2 per C2F5H or three CF2 per C3F7H decomposed. This is explained by secondary bimolecular reactions which lead to comparably stable transient species like CF3H, releasing CF2 at a slower rate. Quantum-chemical calculations and kinetic modeling help to identify the reaction pathways and provide estimates of rate constants for a series of primary and secondary reactions in the decomposition mechanism.
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International Nuclear Information System (INIS)
Yang, Qi; Chen, Sanping; Xie, Gang; Gao, Shengli
2011-01-01
Highlights: ► A new energetic compound Cu(Mtta) 2 (NO 3 ) 2 has been synthesized and structural characterized. ► Sensitivity tests reveal that the compound is insensitive to mechanical stimuli. ► Cu(Mtta) 2 (NO 3 ) 2 accelerates the decomposition of Ammonium perchlorate (AP), which is the key component of composite solid propellant. - Abstract: An energetic coordination compound Cu(Mtta) 2 (NO 3 ) 2 has been synthesized by using 1-methyltetrazole (Mtta) as ligand and its structure has been characterized by X-ray single crystal diffraction. The central copper (II) cation was coordinated by four O atoms from two Mtta ligands and two N atoms from two NO 3 − anions to form a six-coordinated and distorted octahedral structure. 2D superamolecular layer structure was formed by the extensive intermolecular hydrogen bonds between Mtta ligands and NO 3 − anions. Thermal decomposition process of the compound was predicted based on DSC and TG-DTG analyses results. The kinetic parameters of the first exothermic process of the compound were studied by the Kissinger's and Ozawa–Doyle's methods. Sensitivity tests revealed that the compound was insensitive to mechanical stimuli. In addition, compound was explored as additive to promote the thermal decomposition of ammonium perchlorate (AP) by differential scanning calorimetry.
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Xingyan Huang; Cornelis F. De Hoop; Jiulong Xie; Chung-Yun Hse; Jinqiu Qi; Yuzhu Chen; Feng Li
2017-01-01
The thermal decomposition characteristics of microwave liquefied rape straw residues with respect to liquefaction condition and pyrolysis conversion were investigated using a thermogravimetric (TG) analyzer at the heating rates of 5, 20, 50 °C min-1. The hemicellulose decomposition peak was absent at the derivative thermogravimetric analysis (DTG...
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Thermal unimolecular decomposition of methanol. Zum thermischen unimolekularen Zerfall von Methanol
Energy Technology Data Exchange (ETDEWEB)
Spindler, K
1979-01-01
The thermal unimolecular decomposition of methanol and that of acetone (1B) were investigated experimentally after reflected shockwaves, by following up the OH and CH/sub 3/ absorption or the CH/sub 3/ and acetone absorption respectively. A computer simulation of the decomposition of methanol and the subsequent reactions was done. This gave velocity constants for some reactions, which are different from those that are found in the literature. The experimental investigation of the decomposition of acetone, from comparison of the results with the data in the literature, shows that the observations of CH/sub 3/ absorption are very suitable for obtaining velocity constants for decomposition reactions, where CH/sub 3/ radicals are formed in the first stage.
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Fructose decomposition kinetics in organic acids-enriched high temperature liquid water
Energy Technology Data Exchange (ETDEWEB)
Li, Yinghua; Lu, Xiuyang; Yuan, Lei; Liu, Xin [Department of Chemical and Biochemical Engineering, Zhejiang University, Zheda Road 38, Hangzhou 310027, Zhejiang (China)
2009-09-15
Biomass continues to be an important candidate as a renewable resource for energy, chemicals, and feedstock. Decomposition of biomass in high temperature liquid water is a promising technique for producing industrially important chemicals such as 5-hydroxymethylfurfural (5-HMF), furfural, levulinic acid with high efficiency. Hexose, which is the hydrolysis product of cellulose, will be one of the most important starting chemicals in the coming society that is highly dependent on biomass. Taking fructose as a model compound, its decomposition kinetics in organic acids-enriched high temperature liquid water was studied in the temperature range from 180 C to 220 C under the pressure of 10 MPa to further improve reaction rate and selectivity of the decomposition reactions. The results showed that the reaction rate is greatly enhanced with the addition of organic acids, especially formic acid. The effects of temperature, residence time, organic acids and their concentrations on the conversion of fructose and yield of 5-HMF were investigated. The evaluated apparent activation energies of fructose decomposition are 126.8 {+-} 3.3 kJ mol{sup -1} without any catalyst, 112.0 {+-} 13.7 kJ mol{sup -1} catalyzed with formic acid, and 125.6 {+-} 3.8 kJ mol{sup -1} catalyzed with acetic acid, respectively, which shows no significant difference. (author)
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Decomposition of thermally unstable substances in film evaporators
Energy Technology Data Exchange (ETDEWEB)
Matz, G
1982-10-01
It is widely known that film evaporators are considered to permit really gentle evaporation of heat-sensitive substances. Nevertheless, decomposition of such substance still occurs to an extent depending upon the design and operation of the evaporator. In the following a distinction is made between evaporators with films not generated mechanically, namely the long tube evaporator (lTE) or climbing film evaporator, the falling film evaporator (FFE) and the multiple phase helical tube (MPT) or helical coil evaporators (TFE). Figs 1 and 2 illustrate the mode of operation. A theory of the decomposition of thermally unstable substances in these evaporators is briefly outlined and compared with measurements. Such a theory cannot be developed without any experimental checks; on the other hand, meausrements urgently need a theoretical basis if only to establish what actually has to be measured. All experiments are made with a system of readily adjustable decomposability, namely with aqueous solutions of saccharose; the thermal inversion of this compound can be controlled by addition of various amounts or concentrations of hydrochloric acid. In the absence of any catalysis by hydrochloric acid, the decomposition rates within in the temperature interval studied (60-130/sup 0/C) are so low that the experiments would take much too long and determination of the concentration differences (generally by polarimetric methods) would be very complicated. Such slight effects would also be very unfavourable for comparison with theory. (orig.)
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Thermal decomposition and reaction of confined explosives
International Nuclear Information System (INIS)
Catalano, E.; McGuire, R.; Lee, E.; Wrenn, E.; Ornellas, D.; Walton, J.
1976-01-01
Some new experiments designed to accurately determine the time interval required to produce a reactive event in confined explosives subjected to temperatures which will cause decomposition are described. Geometry and boundary conditions were both well defined so that these experiments on the rapid thermal decomposition of HE are amenable to predictive modelling. Experiments have been carried out on TNT, TATB and on two plastic-bonded HMX-based high explosives, LX-04 and LX-10. When the results of these experiments are plotted as the logarithm of the time to explosion versus 1/T K (Arrhenius plot), the curves produced are remarkably linear. This is in contradiction to the results obtained by an iterative solution of the Laplace equation for a system with a first order rate heat source. Such calculations produce plots which display considerable curvature. The experiments have also shown that the time to explosion is strongly influenced by the void volume in the containment vessel. Results of the experiments with calculations based on the heat flow equations coupled with first-order models of chemical decomposition are compared. The comparisons demonstrate the need for a more realistic reaction model
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Effect of high heating rate on thermal decomposition behaviour of ...
Indian Academy of Sciences (India)
the thermal decomposition behaviour of the aforementioned powder at high heating rates was taken into considera- ... does not change the process of releasing hydrogen from titanium hydride ... from titanium hydride in a sequence of steps.
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Directory of Open Access Journals (Sweden)
K. V. Dobrego
2015-01-01
Full Text Available Employing dolomite in the capacity of a sorbent for generator gas purification is of considerable interest nowadays, as it is the impurity of generator gas that causes the major problem for creating cheep and effective co-generator plants. Designing gas purification systems employs simple but physically adequate macrokinetic models of dolomite thermal decomposition. The paper analyzes peculiarities of several contemporaneous models of dolomite and calcite thermal decomposition and infers on reasonable practicality for creating compact engineering dolomite-decomposition macrokinetic models and universal techniques of these models parameter reconstruction for specific dolomite samples. Such technics can be founded on thermogravimetric data and standard approximation error minimizing algorithms.The author assumes that CO2 evacuation from the reaction zone within the particle may proceed by diffusion mechanism and/or by the Darcy filtration and indicates that functional dependence of the thermal-decomposition rate from the particle sizes and the temperature differs for the specified mechanisms. The paper formulates four macrokinetic models whose correspondence verification is grounded on the experimental data. The author concludes that further work in this direction should proceed with the dolomite samples investigation and selecting the best approximation model describing experimental data in wide range of temperatures, warming up rates and the particle sizes.
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Effect of high heating rate on thermal decomposition behaviour of ...
Indian Academy of Sciences (India)
Effect of high heating rate on thermal decomposition behaviour of titanium hydride ... hydride powder, while switching it from internal diffusion to chemical reaction. ... TiH phase and oxides form on the powder surface, controlling the process.
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Thermal decomposition of anhydrous zinc and cadmium salicylates
International Nuclear Information System (INIS)
Kharitonov, Yu.Ya.; Tujebakhova, Z.K.
1984-01-01
On the basis of studying thermograms, thermogravigrams, IR absorption spectra, X-rayograms of anhydrous znc and cadmium salicylate complexes of the M(HSal) 2 composition, (where M=Zn, Cd; HSal is an anion of once deprotonated salicyclic acid H 2 Sal) and products of their thermal transformations, the processes are characterized of stage-by-stage thermal decomposition of these compounds under continuous heating in the air from room temperature to approximately 1000 deg C. It is shown that the Cd(HSal) 2 pyrolysis proceeds with the formation of CdSal at 170-250 deg C and CdO - at 320-460 deg C
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Thermal decomposition and isomerization of cis-permethrin and beta-cypermethrin in the solid phase.
González Audino, Paola; Licastro, Susana A; Zerba, Eduardo
2002-02-01
The stability to heart of cis-permethrin and beta-cypermethrin in the solid phase was studied and the decomposition products identified. Samples heated at 210 degrees C in an oven in the dark showed that, in the absence of potassium chlorate (the salt present in smoke-generating formulations of these pyrethroids), cis-permethrin was not isomerized, although in the presence of that salt, decomposition was greater and thermal isomerization occurred. Other salts of the type KXO3 or NaXO3, with X being halogen or nitrogen, also led to a considerable thermal isomerization. Heating the insecticides in solution in the presence of potassium chlorate did not produce isomerization in any of the solvents assayed. Salt-catalysed thermal cis-trans isomerization was also found for other pyrethroids derived from permethrinic or deltamethrinic acid but not for those derived from chrysanthemic acid. The main thermal degradation processes of cis-permethrin and beta-cypermethrin decomposition when potassium chlorate was present were cyclopropane isomerization, ester cleavage and subsequent oxidation of the resulting products. Permethrinic acid, 3-phenoxybenzyle chloride, alcohol, aldehyde and acid were identified in both cases, as well as 3-phenoxybenzyl cyanide from beta-cypermethrin. A similar decomposition pattern occurred after combustion of pyrethroid fumigant formulations.
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Thermal decomposition pathways of hydroxylamine: theoretical investigation on the initial steps.
Wang, Qingsheng; Wei, Chunyang; Pérez, Lisa M; Rogers, William J; Hall, Michael B; Mannan, M Sam
2010-09-02
Hydroxylamine (NH(2)OH) is an unstable compound at room temperature, and it has been involved in two tragic industrial incidents. Although experimental studies have been carried out to study the thermal stability of hydroxylamine, the detailed decomposition mechanism is still in debate. In this work, several density functional and ab initio methods were used in conjunction with several basis sets to investigate the initial thermal decomposition steps of hydroxylamine, including both unimolecular and bimolecular reaction pathways. The theoretical investigation shows that simple bond dissociations and unimolecular reactions are unlikely to occur. The energetically favorable initial step of decomposition pathways was determined as a bimolecular isomerization of hydroxylamine into ammonia oxide with an activation barrier of approximately 25 kcal/mol at the MPW1K level of theory. Because hydroxylamine is available only in aqueous solutions, solvent effects on the initial decomposition pathways were also studied using water cluster methods and the polarizable continuum model (PCM). In water, the activation barrier of the bimolecular isomerization reaction decreases to approximately 16 kcal/mol. The results indicate that the bimolecular isomerization pathway of hydroxylamine is more favorable in aqueous solutions. However, the bimolecular nature of this reaction means that more dilute aqueous solution will be more stable.
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Modeling N2O Reduction and Decomposition in a Circulating Fluidized bed Boiler
DEFF Research Database (Denmark)
Johnsson, Jan Erik; Åmand, Lars-Erik; Dam-Johansen, Kim
1996-01-01
The N2O concentration was measured in a circulating fluidized bed boiler of commercial size. Kinetics for N2O reduction by char and catalytic reduction and decomposition over bed material from the combustor were determined in a laboratory fixed bed reactor. The destruction rate of N2O in the comb......The N2O concentration was measured in a circulating fluidized bed boiler of commercial size. Kinetics for N2O reduction by char and catalytic reduction and decomposition over bed material from the combustor were determined in a laboratory fixed bed reactor. The destruction rate of N2O...... in the combustion chamber and the cyclone was calculated taking three mechanisms into account: Reduction by char, catalytic decomposition over bed material and thermal decomposition. The calculated destruction rate was in good agreement with the measured destruction of N2O injected at different levels in the boiler...
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The correlation between elongation at break and thermal decomposition of aged EPDM cable polymer
International Nuclear Information System (INIS)
Šarac, T.; Devaux, J.; Quiévy, N.; Gusarov, A.; Konstantinović, M.J.
2017-01-01
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. - Highlights: • EPDM is aged in a wide range of dose rates and temperatures. • Tensile and thermogravimetry test were performed. • Mechanical parameters are strongly affected by irradiation dose and temperature. • Direct link between the mechanical and physicochemical properties is provided. • Thermal and radiation mediated oxidation degradation is considered to be important.
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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.
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Kinetics of hydrogen evolution in the thermal dissociation of the hydride ZrNiH /SUB 2.8/
International Nuclear Information System (INIS)
Chernavskii, P.A.; Lunin, V.V.
1985-01-01
The kinetics of hydrogen evolution in the thermal decomposition of ZrNiH /SUB 2.8/ has been studied. The kinetic curve has two rate maxima. It is presumed that the second maximum is related to the phenomenon of critical inhibition that accompanies the phase transition. Apparent activation energies were determined for hydrogen evolution in argon and argon-ethylene atmospheres. The apparent energy increases in the argon-ethylene mixture. On the basis of the activation energy measurements it is presumed that the rate-determining step in hydrogen evolution is either the formation of hydrogen molecules from atoms on the surface of the lateral diffusion of atomic hydrogen. In the region of hydrogen concentration in the hydride corresponding to the phase transition, the rate-determining step is hydrogen diffusion in the hydride
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Prepared by Thermal Hydro-decomposition
Prasoetsopha, N.; Pinitsoontorn, S.; Kamwanna, T.; Kurosaki, K.; Ohishi, Y.; Muta, H.; Yamanaka, S.
2014-06-01
The polycrystalline samples of Ca3Co4- x Ga x O9+ δ (0 ≤ x ≤ 0.15) were prepared by a simple thermal hydro-decomposition method. The high density ceramics were fabricated using a spark plasma sintering technique. The crystal structure of calcined powders was characterized by x-ray diffraction. The single phase of Ca3Co4- x Ga x O9+ δ was obtained. The scanning electron micrograph illustrated the grain alignment perpendicular to the direction of the pressure in the sintering process. The evidence from x-ray absorption near edge spectra were used to confirm the oxidation state of the Ga dopant. The thermoelectric properties of the misfit-layered of Ca3Co4- x Ga x O9+ δ were investigated. Seebeck coefficient tended to decrease with increasing Ga content due to the hole-doping effect. The electrical resistivity and thermal conductivity were monotonically decreased with increasing Ga content. The Ga doping of x = 0.15 showed the highest power factor of 3.99 × 10-4 W/mK2 at 1,023 K and the lowest thermal conductivity of 1.45 W/mK at 1,073 K. This resulted in the highest ZT of 0.29 at 1,073 K. From the optical absorption spectra, the electronic structure near the Fermi level show no significant change with Ga doping.
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Directory of Open Access Journals (Sweden)
Batakliev Todor
2014-06-01
Full Text Available Catalytic ozone decomposition is of great significance because ozone is a toxic substance commonly found or generated in human environments (aircraft cabins, offices with photocopiers, laser printers, sterilizers. Considerable work has been done on ozone decomposition reported in the literature. This review provides a comprehensive summary of the literature, concentrating on analysis of the physico-chemical properties, synthesis and catalytic decomposition of ozone. This is supplemented by a review on kinetics and catalyst characterization which ties together the previously reported results. Noble metals and oxides of transition metals have been found to be the most active substances for ozone decomposition. The high price of precious metals stimulated the use of metal oxide catalysts and particularly the catalysts based on manganese oxide. It has been determined that the kinetics of ozone decomposition is of first order importance. A mechanism of the reaction of catalytic ozone decomposition is discussed, based on detailed spectroscopic investigations of the catalytic surface, showing the existence of peroxide and superoxide surface intermediates
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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.
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Application of isotopic substitution for studing thermal decomposition of silico-12-tungstic acid
International Nuclear Information System (INIS)
Khakhinov, V.V.; Pinchuk, I.N.; Tumurova, L.V.; Mokhosoev, M.V.
1987-01-01
Using the methods of thermal analysis and isotopic substitution, the mechanism of dehydration and decomposition of silico-12-tungstic acid hydrate is studied. It is found that H-D exchange leads to elevation of temperature of heteropoly acid decomposition. The observed isotopic effect shows that proton transfer is the limiting stage of the reaction
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Decomposition of pre calcined aluminium silicate ores of Afghanistan by hydrochloric acid
International Nuclear Information System (INIS)
Khomidi, A.K.; Mamatov, E.D.
2015-01-01
Present article is devoted to decomposition of pre calcined aluminium silicate ores of Afghanistan by hydrochloric acid. The physicochemical properties of initial aluminium silicate ores were studied by means of X-ray phase, differential thermal and silicate analysis. The chemical composition of aluminium containing ores was determined. The optimal conditions of interaction of initial and pre calcined siallites with hydrochloric acid were defined. The kinetics of acid decomposition of aluminium silicate ores was studied as well.
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International Nuclear Information System (INIS)
Iwasaki, Toshiyuki; Kato, Shigeru; Yamasaki, Akihiro; Ito, Takuya; Suzuki, Seiichi; Kojima, Toshinori; Kodera, Yoichi; Hatta, Akimichi; Kikuzato, Masahiro
2015-01-01
Thermal decomposition experiments of woody wastes contaminated with radioactive materials were conducted using an externally-heated horizontal kiln in the work area for segregation of disaster wastes at Hirono Town, Futaba County, Fukushima Prefecture. Radioactivity was not detected in gaseous products of thermal decomposition at 923 K and 1123 K after passage through a trap filled with activated carbon. The contents of radioactive cesium ( 134 Cs and 137 Cs) were measured in the solid and liquid products of the thermal decomposition experiments and in the residues in the kiln after all of the experiments. Although a trace amount of radioactive cesium was found in the washing trap during the start-up period of operation at 923 K, most of the cesium remained in the char, including the residues in the kiln. These results suggest that most of the radioactive cesium is trapped in char particles and is not emitted in gaseous form. (author)
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International Nuclear Information System (INIS)
Mirsaidov, U.M.; Kurbonov, A.S.; Mamatov, E.D.
2015-01-01
Present article is devoted to kinetics of nitric acid decomposition of calcined borosilicate raw material of Ak-Arkhar Deposit. The dependence of nitric acid decomposition of calcined boric raw material for extraction of boron oxide on temperature (20-100 deg C) and process duration (15-60 minutes) was defined. It was defined that at temperature increasing the extraction rate of boron oxide increases from 20.8 to 78.6%.
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Monika; Dhar, Prodyut; Katiyar, Vimal
2017-11-01
Cellulose nanocrystals (CNC) are fabricated from filter paper (as cellulosic source) by acid hydrolysis using different acids such as sulphuric (H 2 SO 4 ), phosphoric (H 3 PO 4 ), hydrochloric (HCl) and nitric (HNO 3 ) acid. The resulting acid derived CNC are melt mixed with Polylactic acid (PLA) using extruder at 180°C. Thermogravimetric (TGA) result shows that increase in 10% and 50% weight loss (T 10 , T 50 ) temperature for PLA-CNC film fabricated with HNO 3 , H 3 PO 4 and HCl derived CNC have improved thermal stability in comparison to H 2 SO 4 -CNC. Nonisothermal kinetic studies are carried out with modified-Coats-Redfern (C-R), Ozawa-Flynn-Wall (OFW) and Kissinger method to predict the kinetic and thermodynamic parameters. Subsequently prediction of these parameter leads to the proposal of thermal induced degradation mechanism of nanocomposites using Criado method. The distribution of E a calculated from OFW model are (PLA-H 3 PO 4 -CNC: 125-139 kJmol -1 ), (PLA-HNO 3 -CNC: 126-145 kJmol -1 ), (PLA-H 2 SO 4 -CNC: 102-123 kJmol -1 ) and (PLA-HCl-CNC: 140-182 kJmol -1 ). This difference among E a for the decomposition of PLA-CNC bionanocomposite is probably due to various acids used in this study. The E a calculated by these two methods are found in consonance with that observed from Kissinger method. Further, hyphenated TG-Fourier transform infrared spectroscopy (FTIR) result shows that gaseous products such as CO 2 , CO, lactide, aldehydes and other compounds are given off during the thermal degradation of PLA-CNC nanocomposite. Copyright © 2017 Elsevier B.V. All rights reserved.
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International Nuclear Information System (INIS)
Ramesh, Thimmasandra Narayan
2010-01-01
The isothermal decomposition of cobalt hydroxide and cobalt hydroxynitrate at different intervals of temperature leads to the formation of Co 3 O 4 . The phase evolution during the decomposition process was monitored using powder X-ray diffraction. The transformation of cobalt hydroxide to cobalt oxide occurs via three phase mixture while cobalt hydroxynitrate to cobalt oxide occurs through a two phase mixture. The nature of the sample and its preparation method controls the decomposition mechanism. The comparison of topotactical relationship between the precursors to the decomposed product has been reported in relation to polytypism. - Graphical abstract: Isothermal thermal decomposition studies of cobalt hydroxide and cobalt hydroxynitrate at different intervals of temperature show the metastable phase formed prior to Co 3 O 4 phase.
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International Nuclear Information System (INIS)
Lu, K.-T.; Chen, T.-C.; Hu, K.-H.
2009-01-01
The benzoyl peroxide (BPO) is widely used in the chemical industry. Many catastrophes have been caused by its thermal instability or reactive incompatibility in storage or thermal decomposition reaction. Thus, its hazard characteristics have to be clearly identified. First of all, the differential scanning calorimeter (DSC) is used to measure the heat of decomposition reaction, which can contribute to understanding the reaction characteristics of benzoyl peroxide. The accelerating rate calorimeter (ARC) is used to measure the rates of temperature and pressure rises of decomposition reaction, and then the kinetics parameters are estimated. Furthermore, the MIKE 3 apparatus and the 20-l-Apparatus are used to measure and analyze the dust explosion characteristics of benzoyl peroxide under room temperature and atmospheric pressure. Finally, Semenov's thermal explosion theory is applied to investigate the critical runaway condition and the stability criterion of decomposition reaction, and to build the relationship of critical temperature, convective heat transfer coefficient, heat transfer surface area and ambient temperature. These results contribute to improving the safety in the reaction, transportation and storage processes of benzoyl peroxide
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Solid-state reaction kinetics of neodymium doped magnesium hydrogen phosphate system
Gupta, Rashmi; Slathia, Goldy; Bamzai, K. K.
2018-05-01
Neodymium doped magnesium hydrogen phosphate (NdMHP) crystals were grown by using gel encapsulation technique. Structural characterization of the grown crystals has been carried out by single crystal X-ray diffraction (XRD) and it revealed that NdMHP crystals crystallize in orthorhombic crystal system with space group Pbca. Kinetics of the decomposition of the grown crystals has been studied by non-isothermal analysis. The estimation of decomposition temperatures and weight loss has been made from the thermogravimetric/differential thermo analytical (TG/DTA) in conjuncture with DSC studies. The various steps involved in the thermal decomposition of the material have been analysed using Horowitz-Metzger, Coats-Redfern and Piloyan-Novikova equations for evaluating various kinetic parameters.
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Effect of mechanical activation on structure and thermal decomposition of aluminum sulfate
International Nuclear Information System (INIS)
Ghasri-Khouzani, M.; Meratian, M.; Panjepour, M.
2009-01-01
The thermal decompositions of both non-activated and mechanically activated aluminum sulfates were studied by thermogravimetry (TG). The structural disorder, the specific surface area (SSA) and the morphology of mechanically activated aluminum sulfates were analyzed by X-ray diffraction (XRD), laser particle-size analyzer, and scanning electron microscopy (SEM), respectively. Thermal analyses results indicated that the initial temperature of thermal decomposition (T i ) in TG curves for mechanically activated aluminum sulfates decreased gradually with increasing the milling time. It was also found that the SSA of mechanically activated aluminum sulfates remained almost constant after a certain milling time, and lattice strains (ε) rose but the crystallite sizes (D) decreased with increasing the milling time. These results showed that the decrease of T i in TG curves of mechanically activated aluminum sulfates was mainly caused by the increase of lattice distortions and decrease of the crystallite sizes with increasing the milling time
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Solid-phase thermal decomposition of 2,4-dinitroimidazole (2,4-DNI)
Energy Technology Data Exchange (ETDEWEB)
Minier, L.; Behrens, R. Jr. [Rome Astronomical Observatory (Italy). Space Physics Research Center; Bulusu, S. [Army Armament Research and Development Command, Dover, NJ (United States). Energetic Materials Div.
1996-12-31
The solid-phase thermal decomposition of the insensitive energetic nitroaromatic heterocycle 2,4-dinitroimidazole (2,4-DNI: mp 265--274C) is studied utilizing simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS) between 200 and 247C. The pyrolysis products have been identified using perdeuterated and {sup 15}N-labeled isotopomers. The products consist of low molecular-weight gases and a thermally stable solid residue. The major gaseous products are NO, CO{sub 2}, CO, N{sub 2}, HNCO and H{sub 2}O. Minor gaseous products are HCN, C{sub 2}N{sub 2}, NO{sub 2}, C{sub 3}H{sub 4}N{sub 2}, C{sub 3}H{sub 3}N{sub 3}O and NH{sub 3}. The elemental formula of the residue is C{sub 2}HN{sub 2}O and FTIR analysis suggests that it is polyurea- and polycarbamate-like in nature. Rates of formation of the gaseous products and their respective quantities have been determined for a typical isothermal decomposition experiment at 235C. The temporal behaviors of the gas formation rates indicate that the overall decomposition is characterized by a sequence of four events; (1) an early decomposition period induced by impurities and water, (2) an induction period where C0{sub 2} and NO are the primary products formed at relatively constant rates, (3) an autoacceleratory period that peaks when the sample is depleted and (4) a final period in which the residue decomposes. Arrhenius parameters for the induction period are E{sub a} = 46.9 {plus_minus} 0.7 kcal/mol and Log(A) = 16.3 {plus_minus} 0.3. Decomposition pathways that are consistent with the data are presented.
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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.
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Isoconversional kinetics of thermally stimulated processes
Vyazovkin, Sergey
2015-01-01
The use of isoconversional kinetic methods for analysis of thermogravimetric and calorimetric data on thermally stimulated processes is quickly growing in popularity. The purpose of this book is to create the first comprehensive resource on the theory and applications of isoconversional methodology. The book introduces the reader to the kinetics of physical and chemical condensed phase processes that occur as a result of changing temperature and discusses how isoconversional analysis can provide important kinetic insights into them. The book will help the readers to develop a better understanding of the methodology, and promote its efficient usage and successful development.
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Thermal decomposition of uranylnitrate by the Spray-Dryer process
International Nuclear Information System (INIS)
Wildhagen, G.R.S.; Silva, G.C. da
1988-01-01
The proposal of this work consist in the thermal decomposition of uranyl nitrate solutions by the Spray-Dryer process aiming the production of highly reactive fluidized UO 3 , adequate for the use in posterior of reduction to UO 2 and hydrofluorination to UF 4 , in a fluidized bed for the obtention of UF 6 in the cicle of nuclear fuels. (author) [pt
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Wu, Qiujie; Tan, Liu; Xu, Sen; Liu, Dabin; Min, Li
2018-04-01
Numerous accidents of emulsion explosive (EE) are attributed to uncontrolled thermal decomposition of ammonium nitrate emulsion (ANE, the intermediate of EE) and EE in large scale. In order to study the thermal decomposition characteristics of ANE and EE in different scales, a large-scale test of modified vented pipe test (MVPT), and two laboratory-scale tests of differential scanning calorimeter (DSC) and accelerating rate calorimeter (ARC) were applied in the present study. The scale effect and water effect both play an important role in the thermal stability of ANE and EE. The measured decomposition temperatures of ANE and EE in MVPT are 146°C and 144°C, respectively, much lower than those in DSC and ARC. As the size of the same sample in DSC, ARC, and MVPT successively increases, the onset temperatures decrease. In the same test, the measured onset temperature value of ANE is higher than that of EE. The water composition of the sample stabilizes the sample. The large-scale test of MVPT can provide information for the real-life operations. The large-scale operations have more risks, and continuous overheating should be avoided.
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Aramini, Matteo; Niskanen, Johannes; Cavallari, Chiara; Pontiroli, Daniele; Musazay, Abdurrahman; Krisch, Michael; Hakala, Mikko; Huotari, Simo
2016-02-21
We report the microscopic view of the thermal structural stability of the magnesium intercalated fullerene polymer Mg2C60. With the application of X-ray Raman spectroscopy and X-ray diffraction, we study in detail the decomposition pathways of the polymer system upon annealing at temperatures between 300 and 700 °C. We show that there are at least two energy scales involved in the decomposition reaction. Intermolecular carbon bonds, which are responsible for the formation of a 2D fullerene polymer, are broken with a relatively modest thermal energy, while the long-range order of the original polymer remains intact. With an increased thermal energy, the crystal structure in turn is found to undergo a transition to a novel intercalated cubic phase that is stable up to the highest temperature studied here. The local structure surrounding magnesium ions gets severely modified close to, possibly at, the phase transition. We used density functional theory based calculations to study the thermodynamic and kinetic aspects of the collapse of the fullerene network, and to explain the intermediate steps as well as the reaction pathways in the break-up of this peculiar C60 intermolecular bonding architecture.
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Mechanistic Aspects of the Thermal Decomposition of Dicyclopentadienyl Titanium(IV) Dibenzyl
Boekel, C.P.; Teuben, J.H.; Liefde Meijer, H.J. de
1975-01-01
The thermal decomposition of dicyclopentadienyltitanium(IV) dibenzyl in the solid state and in hydrocarbon solvents has been investigated. The compound decomposes via intermolecular abstraction of hydrogen atoms from the cyclopentadienyl rings with quantitative formation of toluene. The reaction was
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Directory of Open Access Journals (Sweden)
Gumerov Vladislav M.
2015-01-01
Full Text Available Experimental studies determining periods of suppression of thermal decomposition reaction of forest combustible materials was carried out by high-speed, cross-correlation cameras and panoramic techniques PIV and IPI under influence of water steam. Conditions and characteristics of reaction termination of thermal decomposition of forest combustible materials under reaction with steam cloud were defined.
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Thermal decomposition of dolomite under CO2: insights from TGA and in situ XRD analysis.
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.
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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.
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International Nuclear Information System (INIS)
Cavaignac, A.L.O.; Lima, R.J.C.; Façanha Filho, P.F.; Moreno, A.J.D.; Freire, P.T.C.
2016-01-01
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.
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Thermal Decomposition of Radiation-Damaged Polystyrene
International Nuclear Information System (INIS)
J Abrefah, J.; Klinger, G.S.
2000-01-01
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 polystyrene. The differences were in the
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International Nuclear Information System (INIS)
Mirsaidov, U.M.; Kurbonov, A.S.; Mamatov, E.D.
2015-01-01
Present article is devoted to kinetics of hydrochloric-acid decomposition of calcined concentrate of boron raw material of Ak-Arkhar Deposit. The experimental data of dependence of hydrochloric-acid decomposition of calcined boron raw material for boron oxide extraction on temperature (20-80 deg C) and process duration (15-60 min) were considered. It was defined that at temperature increasing the boron oxide extraction from borosilicate raw material increases from 24.1 till 86.8%. The constants of decomposition rate of boron raw material were calculated.
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International Nuclear Information System (INIS)
Gubanov, Alexander I.; Dedova, Elena S.; Plyusnin, Pavel E.; Filatov, Eugeny Y.; Kardash, Tatyana Y.; Korenev, Sergey V.; Kulkov, Sergey N.
2014-01-01
Highlights: • Synthesis of ZrW 2 O 8 using hydrothermal method. • On hydrothermal synthesis optimal conc. of HCl in the reaction mixture is 2.3 M. • Thermal decomposition of ZrW 2 O 7 ((OH) 1.5 ,Cl 0.5 )·2H 2 O begins are 200 °S. • Amorphous intermediate crystallizes into cubic single-phase ZrW 2 O 8 above 550 °S. • ZrW 2 O 8 destructed at temperatures above 700 °S. - Abstract: This article discusses some peculiarities of the synthesis of ZrW 2 O 8 (1) using thermal decomposition of the precursor ZrW 2 O 7 ((OH) 1.5 ,Cl 0.5 )·2H 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
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Preparation of lanthanum sulfide nanoparticles by thermal decomposition of lanthanum complex
Institute of Scientific and Technical Information of China (English)
LI Peisen; LI Huanyong; JIE Wanqi
2011-01-01
γ-La2S3 nanoparticles were successfully prepared by thermal decomposition of lanthanum complex La(Et2S2CN)3·phen at low temperature. The obtained sample was characterized by the X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and element analysis. The decomposition mechanism of lanthanum complex was studied by thermogravimetric analyses (TGA). The results showed that the obtained samples were cubic phase particles with uniform sizes among 10-30 nm and γ-La2S3 was prepared by decomposition of La(Et2S2CN)3 phen via La4(Et2S2CN)3 as an intermediate product. The band gap of γ-La2S3 was 2.97 eV, which was bigger than bulk crystal because of pronounced quantum confinement effect.
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The thermal decomposition of copper(II) oxalate revisited
International Nuclear Information System (INIS)
Lamprecht, Emmanuel; Watkins, Gareth M.; Brown, Michael E.
2006-01-01
DSC, TG and TG-FT-IR, and XRPD have been used to examine the effects of supposedly inert atmospheres of argon and nitrogen on the mechanism of the thermal decomposition of copper(II) oxalate. The DSC curves in pure argon at 10 deg. C min -1 show a broad endotherm with onset at about 280 deg. C and maximum at about 295 deg. C. In mixtures of argon and nitrogen, as the proportion of argon gas is decreased, the endothermic character of the decomposition decreases until, when nitrogen is the main component, the decomposition exhibits a complex broad exothermic character. XRPD studies showed that, regardless of the proportions of nitrogen and argon, the DSC residues consisted of mainly copper metal with small amounts of copper(I) oxide (cuprite) and, under some conditions, traces of copper(II) oxide (tenorite). Various explanations for this behaviour are discussed and a possible answer lies in the disproportionation of CO 2 (g) to form small quantities of O 2 (g) or monatomic oxygen. The possibility exists that the exothermicity in nitrogen could be explained by reaction of the nitrogen with atomic oxygen to form N 2 O(g), but this product could not be detected using TG-FT-IR
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The thermal decomposition of copper(II) oxalate revisited
Energy Technology Data Exchange (ETDEWEB)
Lamprecht, Emmanuel [Chemistry Department, Rhodes University, Grahamstown 6140 (South Africa); Watkins, Gareth M. [Chemistry Department, Rhodes University, Grahamstown 6140 (South Africa); Brown, Michael E. [Chemistry Department, Rhodes University, Grahamstown 6140 (South Africa)]. E-mail: m.brown@ru.ac.za
2006-07-01
DSC, TG and TG-FT-IR, and XRPD have been used to examine the effects of supposedly inert atmospheres of argon and nitrogen on the mechanism of the thermal decomposition of copper(II) oxalate. The DSC curves in pure argon at 10 deg. C min{sup -1} show a broad endotherm with onset at about 280 deg. C and maximum at about 295 deg. C. In mixtures of argon and nitrogen, as the proportion of argon gas is decreased, the endothermic character of the decomposition decreases until, when nitrogen is the main component, the decomposition exhibits a complex broad exothermic character. XRPD studies showed that, regardless of the proportions of nitrogen and argon, the DSC residues consisted of mainly copper metal with small amounts of copper(I) oxide (cuprite) and, under some conditions, traces of copper(II) oxide (tenorite). Various explanations for this behaviour are discussed and a possible answer lies in the disproportionation of CO{sub 2}(g) to form small quantities of O{sub 2}(g) or monatomic oxygen. The possibility exists that the exothermicity in nitrogen could be explained by reaction of the nitrogen with atomic oxygen to form N{sub 2}O(g), but this product could not be detected using TG-FT-IR.
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Non-isothermal crystallization kinetics and thermal behaviour of ...
Indian Academy of Sciences (India)
Administrator
The thermal behaviour and crystallization kinetics of PA12/SEBS-g-MA blends .... was determined using Perkin Elmer Pyris 1 TGA. ..... such as difference in the thermal conductivity of the .... glasses (Columbus: American Ceramics Society) p 166.
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Adamopoulou, Theodora; Papadaki, Maria I; Kounalakis, Manolis; Vazquez-Carreto, Victor; Pineda-Solano, Alba; Wang, Qingsheng; Mannan, M Sam
2013-06-15
Thermal decomposition of hydroxylamine, NH2OH, 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(-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. Copyright © 2013 Elsevier B.V. All rights reserved.
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Thermal decomposition of cesium-ethylene-ternary graphite intercalation compounds
International Nuclear Information System (INIS)
Matsumoto, R.; Oishi, Y.; Arii, T.
2010-01-01
In this paper, the thermal decomposition of air-stable Cs-ethylene-ternary graphite intercalation compounds (GICs) is discussed. The air stability of Cs-GICs is improved remarkably after the absorption of ethylene into their interlayer nanospace, because the ethylene molecules oligomerize and block the movement of Cs atoms. In addition, the evaporation of Cs atoms from the Cs-ethylene-ternary GICs is observed above 400 o C under a N 2 atmosphere of 100 Pa by ion attachment mass spectrometry. Although the results indicate that Cs-ethylene-ternary GICs remain stable up to approximately 400 o C, their thermal stability is not very high as compared to that of Cs-GICs.
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Energy Technology Data Exchange (ETDEWEB)
Sharma, J.K. [Department of Chemistry, Deen Dayal Upadhyay Gorakhpur University, Gorakhpur (India); Srivastava, Pratibha, E-mail: author.pratibhas1980@gmail.com [Department of Chemistry, Deen Dayal Upadhyay Gorakhpur University, Gorakhpur (India); Singh, Gurdip [Department of Chemistry, Deen Dayal Upadhyay Gorakhpur University, Gorakhpur (India); Akhtar, M. Shaheer [New & Renewable Energy Material Development Center (NewREC), Chonbuk National University, Jeonbuk (Korea, Republic of); Ameen, S. [Energy Materials & Surface Science Laboratory, Solar Energy Research Center, School of Chemical Engineering, Chonbuk National University, Jeonju 561-756 (Korea, Republic of)
2015-03-15
Graphical abstract: - Highlights: • Co{sub 3}O{sub 4} NPs were synthesized from the leaves extract of plant Calotropis gigantea. • Green synthesis of Co{sub 3}O{sub 4} NPs is a cost effective and eco-friendly route. • Faster thermal decomposition of AP occurred in presence of the green synthesized Co{sub 3}O{sub 4} NPs. • A high burning rate of CSP was observed. • Green synthesized Co{sub 3}O{sub 4} NPs displays the good electrocatalytic activity to reduction of I{sub 3}{sup −} to I{sup −} ions. - Abstract: In this paper, we report on the green synthesis of cobalt oxide nanoparticles (Co{sub 3}O{sub 4} NPs) using leaves extract of plant Calotropis gigantea and characterize by X-ray diffraction (XRD), UV–vis spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDX). The green synthesized Co{sub 3}O{sub 4} NPs showed excellent catalytic effect on the thermal decomposition of ammonium perchlorate (AP) and burning rate of composite solid propellants (CSPs). Kinetics of slow and rapid thermal decomposition has been investigated by isoconversional and ignition delay methods, respectively. Moreover, the electrocatalytic performance of green synthesized Co{sub 3}O{sub 4} NPs in dye-sensitized solar cells (DSSC) has also been evaluated. The cyclic voltametry measurement shows good electrocatalytic activity of Co{sub 3}O{sub 4} NPs toward the reduction of I{sub 3}{sup −} to I{sup −} ions.
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Mechanism of thermal decomposition of K{sub 2}FeO{sub 4} and BaFeO{sub 4}: A review
Energy Technology Data Exchange (ETDEWEB)
Sharma, Virender K., E-mail: vsharma@sph.tamhsc.edu [Texas A& M University, Department of Environmental and Occupational Health, School of Public Health (United States); Machala, Libor [Palacky University, Regional Centre of Advanced Technologies and Materials, Departments of Experimental Physics and Physical Chemistry, Faculty of Science (Czech Republic)
2016-12-15
This paper presents thermal decomposition of potassium ferrate(VI) (K{sub 2}FeO{sub 4}) and barium ferrate(VI) (BaFeO{sub 4}) in air and nitrogen atmosphere. Mössbauer spectroscopy and nuclear forward scattering (NFS) synchrotron radiation approaches are reviewed to advance understanding of electron-transfer processes involved in reduction of ferrate(VI) to Fe(III) phases. Direct evidences of Fe {sup V} and Fe {sup IV} as intermediate iron species using the applied techniques are given. Thermal decomposition of K{sub 2}FeO{sub 4} involved Fe {sup V}, Fe {sup IV}, and K{sub 3}FeO{sub 3} as intermediate species while BaFeO{sub 3} (i.e. Fe {sup IV}) was the only intermediate species during the decomposition of BaFeO{sub 4}. Nature of ferrite species, formed as final Fe(III) species, of thermal decomposition of K{sub 2}FeO{sub 4} and BaFeO{sub 4} under different conditions are evaluated. Steps of the mechanisms of thermal decomposition of ferrate(VI), which reasonably explained experimental observations of applied approaches in conjunction with thermal and surface techniques, are summarized.
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Czech Academy of Sciences Publication Activity Database
Asadi, Z.; Asadi, M.; Zeinali, A.; Ranjkeshshorkaei, M.; Fejfarová, Karla; Eigner, Václav; Dušek, Michal; Dehnokhalaji, A.
2014-01-01
Roč. 126, č. 6 (2014), s. 1673-1683 ISSN 0974-3626 R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : uranyl schiff base complexes * kinetic study * kinetics of thermal decomposition * X-ray crystallography * cyclic voltammetry Subject RIV: CA - Inorganic Chemistry Impact factor: 1.191, year: 2014
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Energy Technology Data Exchange (ETDEWEB)
Pivesso, Paulo Roberto; Galvao, Luzia Patricia Fernandes de Carvalho; Fernandes Junior, Valter Jose; Coutinho, Ana Carla S.L.S. [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil); Souza, Antonio Gouveia de [Universidade Federal da Paraiba (UFPB), Joao Pessoa, PB (Brazil)
2004-07-01
The modern gasoline contains in your composition insatured hydrocarbons that can be degraded by the action of the air, heat and substances presenting catalytic activity. The presence of air and heat promote oxidation reactions and polymerization, which promote the gum formation, that is a product with diverse characteristics. The petroleum and l the automobile industries have been investing in researches to lessen the gum undesirable effects. Nowadays, several products are added to the gasoline, for example, the surfactant additives, with the purpose to reduce the formation of deposits in the engine. This work evaluated the influence of a polyester amine addictive, used as the main active component in Brazilian gasoline. The gums were generated evaporating the gasolines according to the ASTM D 381 method. Two types of gum were obtained; the Common Washed Gum (White Sample) and the Additive based Washed Gum (Additive Sample). Both samples were characterized for thermal analysis and submitted for a kinetic study using the model-free method proposed by Vyazovkin. This approach was applied to the final stage of the gums decomposition, supplying the corresponding relative kinetic parameters, such as energy of activation and conversion (author)
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Programming Enhancements for Low Temperature Thermal Decomposition Workstation
International Nuclear Information System (INIS)
Igou, R.E.
1998-01-01
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
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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.
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Ozone disintegration kinetics in the reactor for tyres decomposition
International Nuclear Information System (INIS)
Golota, V.I.; Manujlenko, O.V.; Taran, G.V.; Pis'menetskij, A.S.; Zamuriev, A.A.
2010-01-01
The results of theoretical and experimental research of ozone disintegration kinetics in the chemical reactor which is developed for decomposition of tyres in the ozone-air environment are presented. Analytical expression for dependence of ozone concentration in the reactor from time and from parameters of the task, such as volume speed of ozone-air mixture feed on a reactor input, concentration of ozone on the input to the reactor, volume speed of output of the used mixture, reactor size, and square of its internal surface is obtained. It is shown that at the same speed of ozone-air mixture pro rolling through the reactor, with growth of ozone concentration on the input, value of stationary concentration in the reactor grows, remaining always less than concentration on the input. It is also shown that at the same ozone concentration on the input, with growth of speed of ozone-air mixture pro rolling through the reactor, value of stationary ozone concentration in the reactor also grows, remaining always less than ozone concentration on the input. The ozone disintegration kinetics in the reactor in a wide range of speed of ozone-air mixture pro rolling through the reactor (0.15, 0.30, 0.45, 0.60 m3/hour) and various ozone concentration on the input (5, 10, 15, 20 g/m3) is experimentally studied. It is shown that experimental results with good accuracy coincide with the theoretical. Direct experiment showed the essential influence of the internal surface of the reactor on the ozone disintegration kinetics.
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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 quantitativ...
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Czech Academy of Sciences Publication Activity Database
Asadi, Z.; Zeinali, A.; Dušek, Michal; Eigner, Václav
2014-01-01
Roč. 46, č. 12 (2014), s. 718-729 ISSN 0538-8066 R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : uranyl * Schiff base * kinetics * anticancer activity Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.517, year: 2014
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Synthesis, thermal decomposition and sensitivity study of CsDNBF
Energy Technology Data Exchange (ETDEWEB)
Wang, Shaozong; Zhang, Tonglai; Yang, Li; Zhang, Jianguo; Sun, Yuanhua [State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081 (China)
2007-02-15
CsDNBF (cesium 7-hydroxy-4,6-dinitro-5,7-dihydrobenzofuroxanide) was synthesized from the sodium salt of DNBF and cesium nitrate. The thermal decomposition process has been investigated and the results show that the solid residues at 240 C are RCOOCs, CsNCO, RNO{sub 2} and CsNO{sub 3}. The sensitivity results demonstrate that CsDNBF has better properties than KDNBF, which has been widely used. (Abstract Copyright [2007], Wiley Periodicals, Inc.)
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Kinetics of Platinum-Catalyzed Decomposition of Hydrogen Peroxide
Vetter, Tiffany A.; Colombo, D. Philip, Jr.
2003-07-01
CIBA Vision Corporation markets a contact lens cleaning system that consists of an AOSEPT disinfectant solution and an AOSEPT lens cup. The disinfectant is a buffered 3.0% m/v hydrogen peroxide solution and the cup includes a platinum-coated AOSEPT disc. The hydrogen peroxide disinfects by killing bacteria, fungi, and viruses found on the contact lenses. Because the concentration of hydrogen peroxide needed to disinfect is irritating to eyes, the hydrogen peroxide needs to be neutralized, or decomposed, before the contact lenses can be used again. A general chemistry experiment is described where the kinetics of the catalyzed decomposition of the hydrogen peroxide are studied by measuring the amount of oxygen generated as a function of time. The order of the reaction with respect to the hydrogen peroxide, the rate constant, and the energy of activation are determined. The integrated rate law is used to determine the time required to decompose the hydrogen peroxide to a concentration that is safe for eyes.
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High-purity Cu nanocrystal synthesis by a dynamic decomposition method
Jian, Xian; Cao, Yu; Chen, Guozhang; Wang, Chao; Tang, Hui; Yin, Liangjun; Luan, Chunhong; Liang, Yinglin; Jiang, Jing; Wu, Sixin; Zeng, Qing; Wang, Fei; Zhang, Chengui
2014-12-01
Cu nanocrystals are applied extensively in several fields, particularly in the microelectron, sensor, and catalysis. The catalytic behavior of Cu nanocrystals depends mainly on the structure and particle size. In this work, formation of high-purity Cu nanocrystals is studied using a common chemical vapor deposition precursor of cupric tartrate. This process is investigated through a combined experimental and computational approach. The decomposition kinetics is researched via differential scanning calorimetry and thermogravimetric analysis using Flynn-Wall-Ozawa, Kissinger, and Starink methods. The growth was found to be influenced by the factors of reaction temperature, protective gas, and time. And microstructural and thermal characterizations were performed by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and differential scanning calorimetry. Decomposition of cupric tartrate at different temperatures was simulated by density functional theory calculations under the generalized gradient approximation. High crystalline Cu nanocrystals without floccules were obtained from thermal decomposition of cupric tartrate at 271°C for 8 h under Ar. This general approach paves a way to controllable synthesis of Cu nanocrystals with high purity.
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Ag nanoparticles hosted in monolithic mesoporous silica by thermal decomposition method
International Nuclear Information System (INIS)
Chen Wei; Zhang Junying
2003-01-01
Ag nanoparticles were obtained by thermal decomposition of silver nitrate within pores of mesoporous silica. Microstructure of this composite was examined by X-ray diffraction and high-resolution transmission electron microscopy. Optical measurements for the nanocomposite show that Ag particle doping leads to a large red shift of the absorption edge
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International Nuclear Information System (INIS)
De Dobbelaere, Christopher; Mullens, Jules; Hardy, An; Van Bael, Marlies K.
2011-01-01
Highlights: → A totally water based glycolato-Ti(IV) precursor is presented and characterized. → The precursors' thermal decomposition profile depends on the ligand to metal ratio. → Titanium is coordinated in an unidentate fashion by the glycolate anion. → Smooth and uniform TiO 2 films can be prepared from the precursor solution. - Abstract: A new aqueous solution-gel precursor based on water soluble glycolato(-peroxo)-Ti(IV) complexes is developed for the preparation of TiO 2 films. With regard to the decomposition of complexes towards oxide formation, it is important to gain insight in the chemical transformations inside the precursor during thermal treatment. Therefore, the thermo-oxidative decomposition pathway of a gel obtained by slow evaporation of the precursor solution is described based on hyphenated thermogravimetric analysis with Fourier transform infrared spectroscopy (TGA-FTIR) and mass spectrometry (TGA-MS). Pure glycolic acid is used as a reference system for this study. By varying the molar glycolic acid to Ti(IV) ratio, the thermal decomposition of the gel can be drastically shortened and the profile's course changed. Gel structure and chemical changes in the gel upon heating are also studied by means of off-line FTIR. A unidentate coordination of the titanium(IV) ion by the carboxylate group of the glycolato ligands and the involvement of the hydroxyl group is confirmed. Phase formation at certain points in the thermal decomposition is studied by X-ray diffraction and Raman spectroscopy. Finally, it is proven that the new precursor is a valuable candidate for the deposition of low carbon containing solution-gel films which can ultimately be converted into smooth and uniform TiO 2 films.
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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.
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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.
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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.
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Periodic and stochastic thermal modulation of protein folding kinetics.
Platkov, Max; Gruebele, Martin
2014-07-21
Chemical reactions are usually observed either by relaxation of a bulk sample after applying a sudden external perturbation, or by intrinsic fluctuations of a few molecules. Here we show that the two ideas can be combined to measure protein folding kinetics, either by periodic thermal modulation, or by creating artificial thermal noise that greatly exceeds natural thermal fluctuations. We study the folding reaction of the enzyme phosphoglycerate kinase driven by periodic temperature waveforms. As the temperature waveform unfolds and refolds the protein, its fluorescence color changes due to FRET (Förster resonant Energy Transfer) of two donor/acceptor fluorophores labeling the protein. We adapt a simple model of periodically driven kinetics that nicely fits the data at all temperatures and driving frequencies: The phase shifts of the periodic donor and acceptor fluorescence signals as a function of driving frequency reveal reaction rates. We also drive the reaction with stochastic temperature waveforms that produce thermal fluctuations much greater than natural fluctuations in the bulk. Such artificial thermal noise allows the recovery of weak underlying signals due to protein folding kinetics. This opens up the possibility for future detection of a stochastic resonance for protein folding subject to noise with controllable amplitude.
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Directory of Open Access Journals (Sweden)
González-Ibarra A.A.
2016-01-01
Full Text Available This work examines the role of NaOH and Ca(OH2 on the hydrothermal decomposition of industrial jarosite deposited by a Mexican company in a tailings dam. The industrial jarosite is mainly composed by natrojarosite and contains 150 g Ag/t, showing a narrow particle size distribution, as revealed by XRD, fire assay, SEM-EDS and laser-diffraction analysis. The effect of the pH, when using NaOH or Ca(OH2 as alkalinizing agent was studied by carrying out decomposition experiments at different pH values and 60°C in a homogeneous size particle system (pH = 8, 9, 10 and 11 and in a heterogeneous size particle system (pH = 11. Also, the kinetic study of the process and the controlling step of the decomposition reaction when NaOH and Ca(OH2 are used was determined by fitting the data obtained to the shrinking core model for spherical particles of constant size. These results, supported by chemical (EDS, morphological (SEM and mapping of elements (EDS analysis of a partially reacted jarosite particle allowed to conclude that when NaOH is used, the process kinetics is controlled by the chemical reaction and when Ca(OH2 is used, the rate determining step is changed to a diffusion control through a layer of solid products.
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International Nuclear Information System (INIS)
Zhang, Yifu; Meng, Changgong
2016-01-01
Fe_3O_4 and Co_3O_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_3O_4 and Co_3O_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_3O_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_3O_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_3O_4 and Co_3O_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_3O_4 and Co_3O_4 microspheres were successfully synthesized. • The T_c of AP with 1, 2, 4 and 8 wt% of Fe_3O_4 microspheres was decreased by 58, 80, 102 and 129 °C. • The T_c of AP with 1, 2, 4 and 8 wt% of Co_3O_4 microspheres was decreased by 55, 74, 112 and 131 °C. • The thermal decomposition process of AP was detected by TG-IR.
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International Nuclear Information System (INIS)
Nishio, Gunji; Watanabe, Kouji; Koike, Tadao; Miyato, Teijiro.
1996-12-01
For analyzing a cause of the Tomsk-7 accident at Russian reprocessing plant, it is necessary to determine reaction-rate constant and reaction heat for a thermal decomposition of TBP/kerosine containing unstable reactive hydrocarbons with nitric acid. In JAERI, the rate constant and reaction heat were obtained from data measured with a differential thermal analyzer (DTA) for unstable hydrocarbons such as n-butanol, n-butyl nitrate, aromatic hydrocarbons, and cyclic compounds. The safety evaluation of Tomsk tank ruptured by the reaction was carried out by heat balance calculations between heat generation and heat loss in the tank using these rate constants and reaction heats. Consequently, it is clear that the cause of the tank rupture would be due to an exothermic reaction of aromatic hydrocarbons in kerosine made by petroleum with the concentrated nitric acid of 14.2N. (author)
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Directory of Open Access Journals (Sweden)
Zun Maria
2014-12-01
Full Text Available In this study, the stability of 10% hydrogen peroxide aqueous and non-aqueous solutions with the addition of 6% (w/w of urea was evaluated. The solutions were stored at 20°C, 30°C and 40°C, and the decomposition of hydrogen peroxide proceeded according to first-order kinetics. With the addition of the urea in the solutions, the decomposition rate constant increased and the activation energy decreased. The temperature of storage also affected the decomposition of substance, however, 10% hydrogen peroxide solutions prepared in PEG-300, and stabilized with the addition of 6% (w/w of urea had the best constancy.
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Non-isothermal degradation and evaluation of kinetic parameters of some Schiff base metal complexes
International Nuclear Information System (INIS)
Mishra, A.P.; Soni, Monika
2008-01-01
Thermal decomposition of VO (II)-methyl isobutyl ketone-nicotinamide, VO (II)-2-furfurylidine-3,4-dichloroaniline, Co(II)-4-dimethyl amino benzylidine-3-chloro-4-fluoroaniline, VO(II)-2-pyridine carboxylidine-4-aminobenzoic acid complexes have been carried out by thermogravimetric method. The TG curves of complexes were recorded at a uniform rate of 20 deg C/min in nitrogen. The thermogram of the three VO(II) complexes exhibit single stage decomposition whereas the Co(II) complex shows a double stage decomposition. Various kinetic parameters i. e., energy of activation (E), entropy (AS) and frequency factor (Z) have been evaluated by using Coats-Redfern and Piloyan-Novikova equations and their comparable values are reported. The order of thermal stability of first decomposition stage is as: 4=2>1>3. (author)
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Energy Technology Data Exchange (ETDEWEB)
De Dobbelaere, Christopher, E-mail: christopher.dedobbelaere@uhasselt.be [Hasselt University, Institute for Materials Research, Inorganic and Physical Chemistry, Agoralaan Building D, B-3590 Diepenbeek (Belgium); Mullens, Jules, E-mail: jules.mullens@uhasselt.be [Hasselt University, Institute for Materials Research, Inorganic and Physical Chemistry, Agoralaan Building D, B-3590 Diepenbeek (Belgium); Hardy, An, E-mail: an.hardy@uhasselt.be [Hasselt University, Institute for Materials Research, Inorganic and Physical Chemistry, Agoralaan Building D, B-3590 Diepenbeek (Belgium); IMEC vzw, Division IMOMEC, Agoralaan Building D, B-3590 Diepenbeek (Belgium); Van Bael, Marlies K., E-mail: marlies.vanbael@uhasselt.be [Hasselt University, Institute for Materials Research, Inorganic and Physical Chemistry, Agoralaan Building D, B-3590 Diepenbeek (Belgium); IMEC vzw, Division IMOMEC, Agoralaan Building D, B-3590 Diepenbeek (Belgium)
2011-06-10
Highlights: {yields} A totally water based glycolato-Ti(IV) precursor is presented and characterized. {yields} The precursors' thermal decomposition profile depends on the ligand to metal ratio. {yields} Titanium is coordinated in an unidentate fashion by the glycolate anion. {yields} Smooth and uniform TiO{sub 2} films can be prepared from the precursor solution. - Abstract: A new aqueous solution-gel precursor based on water soluble glycolato(-peroxo)-Ti(IV) complexes is developed for the preparation of TiO{sub 2} films. With regard to the decomposition of complexes towards oxide formation, it is important to gain insight in the chemical transformations inside the precursor during thermal treatment. Therefore, the thermo-oxidative decomposition pathway of a gel obtained by slow evaporation of the precursor solution is described based on hyphenated thermogravimetric analysis with Fourier transform infrared spectroscopy (TGA-FTIR) and mass spectrometry (TGA-MS). Pure glycolic acid is used as a reference system for this study. By varying the molar glycolic acid to Ti(IV) ratio, the thermal decomposition of the gel can be drastically shortened and the profile's course changed. Gel structure and chemical changes in the gel upon heating are also studied by means of off-line FTIR. A unidentate coordination of the titanium(IV) ion by the carboxylate group of the glycolato ligands and the involvement of the hydroxyl group is confirmed. Phase formation at certain points in the thermal decomposition is studied by X-ray diffraction and Raman spectroscopy. Finally, it is proven that the new precursor is a valuable candidate for the deposition of low carbon containing solution-gel films which can ultimately be converted into smooth and uniform TiO{sub 2} films.
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DECOMPOSITION STUDY OF CALCIUM CARBONATE IN COCKLE SHELL
Directory of Open Access Journals (Sweden)
MUSTAKIMAH MOHAMED
2012-02-01
Full Text Available Calcium oxide (CaO is recognized as an efficient carbon dioxide (CO2 adsorbent and separation of CO2 from gas stream using CaO based adsorbent is widely applied in gas purification process especially at high temperature reaction. CaO is normally been produced via thermal decomposition of calcium carbonate (CaCO3 sources such as limestone which is obtained through mining and quarrying limestone hill. Yet, this study able to exploit the vast availability of waste resources in Malaysia which is cockle shell, as the potential biomass resources for CaCO3 and CaO. In addition, effect of particle size towards decomposition process is put under study using four particle sizes which are 0.125-0.25 mm, 0.25-0.5 mm, 1-2 mm, and 2-4 mm. Decomposition reactivity is conducted using Thermal Gravimetric Analyzer (TGA at heating rate of 20°C/minutes in inert (Nitrogen atmosphere. Chemical property analysis using x-ray fluorescence (XRF, shows cockle shell is made up of 97% Calcium (Ca element and CaO is produced after decomposition is conducted, as been analyzed by x-ray diffusivity (XRD analyzer. Besides, smallest particle size exhibits the highest decomposition rate and the process was observed to follow first order kinetics. Activation energy, E, of the process was found to vary from 179.38 to 232.67 kJ/mol. From Arrhenius plot, E increased when the particle size is larger. To conclude, cockle shell is a promising source for CaO and based on four different particles sizes used, sample at 0.125-0.25 mm offers the highest decomposition rate.
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International Nuclear Information System (INIS)
Kishore, P.N.R.; Jeevanandam, P.
2012-01-01
Highlights: ► Silica-iron oxide core–shell nanoparticles have been synthesized by a novel thermal decomposition approach. ► The silica-iron oxide core–shell nanoparticles are superparamagnetic at room temperature. ► The silica-iron oxide core–shell nanoparticles serve as good photocatalyst for the degradation of Rhodamine B. - Abstract: A simple thermal decomposition approach for the synthesis of magnetic nanoparticles consisting of silica as core and iron oxide nanoparticles as shell has been reported. The iron oxide nanoparticles were deposited on the silica spheres (mean diameter = 244 ± 13 nm) by the thermal decomposition of iron (III) acetylacetonate, in diphenyl ether, in the presence of SiO 2 . The core–shell nanoparticles were characterized by X-ray diffraction, infrared spectroscopy, field emission-scanning electron microscopy coupled with energy dispersive X-ray analysis, transmission electron microscopy, diffuse reflectance spectroscopy, and magnetic measurements. The results confirm the presence of iron oxide nanoparticles on the silica core. The core–shell nanoparticles are superparamagnetic at room temperature indicating the presence of iron oxide nanoparticles on silica. The core–shell nanoparticles have been demonstrated as good photocatalyst for the degradation of Rhodamine B.
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Nitrated graphene oxide and its catalytic activity in thermal decomposition of ammonium perchlorate
Energy Technology Data Exchange (ETDEWEB)
Zhang, Wenwen; Luo, Qingping; Duan, Xiaohui [State Key Laboratory Cultivation Base for Nonmetal Composites and Functional Materials, Southwest University of Science and Technology, Mianyang 621010 (China); Zhou, Yong [Eco-materials and Renewable Energy Research Center (ERERC), School of Physics, National Lab of Solid State Microstructure, ERERC, Nanjing University, Nanjing 210093 (China); Pei, Chonghua, E-mail: peichonghua@swust.edu.cn [State Key Laboratory Cultivation Base for Nonmetal Composites and Functional Materials, Southwest University of Science and Technology, Mianyang 621010 (China)
2014-02-01
Highlights: • The NGO was synthesized by nitrifying homemade GO. • The N content of resulted NGO is up to 1.45 wt.%. • The NGO can facilitate the decomposition of AP and release much heat. - Abstract: Nitrated graphene oxide (NGO) was synthesized by nitrifying homemade GO with nitro-sulfuric acid. Fourier transform infrared spectroscopy (FTIR), laser Raman spectroscopy, CP/MAS {sup 13}C NMR spectra and X-ray photoelectron spectroscopy (XPS) were used to characterize the structure of NGO. The thickness and the compositions of GO and NGO were analyzed by atomic force microscopy (AFM) and elemental analysis (EA), respectively. The catalytic effect of the NGO for the thermal decomposition of ammonium perchlorate (AP) was investigated by differential scanning calorimetry (DSC). Adding 10% of NGO to AP decreases the decomposition temperature by 106 °C and increases the apparent decomposition heat from 875 to 3236 J/g.
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Nitrated graphene oxide and its catalytic activity in thermal decomposition of ammonium perchlorate
International Nuclear Information System (INIS)
Zhang, Wenwen; Luo, Qingping; Duan, Xiaohui; Zhou, Yong; Pei, Chonghua
2014-01-01
Highlights: • The NGO was synthesized by nitrifying homemade GO. • The N content of resulted NGO is up to 1.45 wt.%. • The NGO can facilitate the decomposition of AP and release much heat. - Abstract: Nitrated graphene oxide (NGO) was synthesized by nitrifying homemade GO with nitro-sulfuric acid. Fourier transform infrared spectroscopy (FTIR), laser Raman spectroscopy, CP/MAS 13 C NMR spectra and X-ray photoelectron spectroscopy (XPS) were used to characterize the structure of NGO. The thickness and the compositions of GO and NGO were analyzed by atomic force microscopy (AFM) and elemental analysis (EA), respectively. The catalytic effect of the NGO for the thermal decomposition of ammonium perchlorate (AP) was investigated by differential scanning calorimetry (DSC). Adding 10% of NGO to AP decreases the decomposition temperature by 106 °C and increases the apparent decomposition heat from 875 to 3236 J/g
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Thermal decomposition of biphenyl (1963); Decomposition thermique du biphenyle (1963)
Energy Technology Data Exchange (ETDEWEB)
Clerc, M [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires
1962-06-15
The rates of formation of the decomposition products of biphenyl; hydrogen, methane, ethane, ethylene, as well as triphenyl have been measured in the vapour and liquid phases at 460 deg. C. The study of the decomposition products of biphenyl at different temperatures between 400 and 460 deg. C has provided values of the activation energies of the reactions yielding the main products of pyrolysis in the vapour phase. Product and Activation energy: Hydrogen 73 {+-} 2 kCal/Mole; Benzene 76 {+-} 2 kCal/Mole; Meta-triphenyl 53 {+-} 2 kCal/Mole; Biphenyl decomposition 64 {+-} 2 kCal/Mole; The rate of disappearance of biphenyl is only very approximately first order. These results show the major role played at the start of the decomposition by organic impurities which are not detectable by conventional physico-chemical analysis methods and the presence of which accelerates noticeably the decomposition rate. It was possible to eliminate these impurities by zone-melting carried out until the initial gradient of the formation curves for the products became constant. The composition of the high-molecular weight products (over 250) was deduced from the mean molecular weight and the dosage of the aromatic C - H bonds by infrared spectrophotometry. As a result the existence in tars of hydrogenated tetra, penta and hexaphenyl has been demonstrated. (author) [French] Les vitesses de formation des produits de decomposition du biphenyle: hydrogene, methane, ethane, ethylene, ainsi que des triphenyles, ont ete mesurees en phase vapeur et en phase liquide a 460 deg. C. L'etude des produits de decomposition du biphenyle a differentes temperatures comprises entre 400 et 460 deg. C, a fourni les valeurs des energies d'activation des reactions conduisant aux principaux produits de la pyrolyse en phase vapeur. Produit et Energie d'activation: Hydrogene 73 {+-} 2 kcal/Mole; Benzene 76 {+-} 2 kcal/Mole; Metatriphenyle, 53 {+-} 2 kcal/Mole; Decomposition du biphenyle 64 {+-} 2 kcal/Mole; La
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Catalytic effects of inorganic acids on the decomposition of ammonium nitrate.
Sun, Jinhua; Sun, Zhanhui; Wang, Qingsong; Ding, Hui; Wang, Tong; Jiang, Chuansheng
2005-12-09
In order to evaluate the catalytic effects of inorganic acids on the decomposition of ammonium nitrate (AN), the heat releases of decomposition or reaction of pure AN and its mixtures with inorganic acids were analyzed by a heat flux calorimeter C80. Through the experiments, the different reaction mechanisms of AN and its mixtures were analyzed. The chemical reaction kinetic parameters such as reaction order, activation energy and frequency factor were calculated with the C80 experimental results for different samples. Based on these parameters and the thermal runaway models (Semenov and Frank-Kamenestkii model), the self-accelerating decomposition temperatures (SADTs) of AN and its mixtures were calculated and compared. The results show that the mixtures of AN with acid are more unsteady than pure AN. The AN decomposition reaction is catalyzed by acid. The calculated SADTs of AN mixtures with acid are much lower than that of pure AN.
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Thermal decomposition of nitrate salts liquid waste for the lagoon sludge treatment
International Nuclear Information System (INIS)
Hwang, D. S.; Oh, J. H.; Kim, Y. K.; Lee, K. Y.; Choi, Y. D.; Hwang, S. T.; Park, J. H.
2004-01-01
This study investigated the thermal decomposition property of nitrate salts liquid waste which is produced in a series of the processes for the sludge treatment. Thermal decomposition property was analyzed by TG/DTA and XRD. Most ammonium nitrate in the nitrate salts liquid waste was decomposed at 250 .deg. C and calcium nitrate was decomposed and converted into calcium oxide at 550 .deg. C. Sodium nitrate was decomposed at 700 .deg. C and converted into sodium oxide which reacts with water easily. But sodium oxide was able to convert into a stable compound by adding alumina. Therefore, nitrate salts liquid waste can be treated by two steps as follows. First, ammonium nitrate is decomposed at 250 .deg. C. Second, alumina is added in residual solid sodium nitrate and calcium nitrate and these are decomposed at 900 .deg. C. Final residue consists of calcium oxide and Na 2 O.Al 2 O 3 and can be stored stably
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International Nuclear Information System (INIS)
Dantas, J.M.; Abrao, A.
1981-04-01
A contribution to the characterization of several uranium compounds obtained at the IPEN' Uranium Pilot Plant is given. Particularly, samples of ammonium diuranate (ADU) and uranium oxides were studied. The main objective was to know the stoichiometry of the ADU and the oxides resulting from its thermal transformation. ADU samples were prepared by batchwise precipitation, stationary dewatering into stove and batchwise thermal decomposition, or, alternatively, continuous precipitation, continuous filtration, continuous drying and continuous thermal decomposition inside a temperature gradient electrical furnace. All ADU were precipitated using NH 3 gas from uranul sulfate or uranyl nitrate solutions. The thermal decomposition of ADU and uranium oxides were studied in an air atmosphere by thermogravimetry (TG) and differential scanning calorimetry (DSC). Any correlation between the parameters of precipitation, drying, calcination and the hystory of the obtaintion of the several uraniumm compounds and their initial and final composition was looked for. Heating program was established to have the U 3 O 8 oxide as the final product. Intermediary phases were tentatively identified. Temperatures at which occurred the absorption water elimination, crystallization water elimination, evolution or oxidation of NH 3 , decomposition of NO -3 ion and oxygen evolution and the exo- and endothermic process for each sample were identified. (Author) [pt
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International Nuclear Information System (INIS)
Frost, Ray L.; Wain, Daria; Martens, Wayde N.; Locke, Ashley C.; Martinez-Frias, Jesus; Rull, Fernando
2007-01-01
Two evaporite minerals from the El Jaroso Ravine, Spain have been analysed by thermogravimetry coupled with an evolved gas mass spectrometer. X-ray diffraction results proved the evaporite minerals were a mixture of sulphates including the minerals magnesiocopiapite, coquimbite and possibly alunogen. Thermal decomposition of the unoxidised samples showed steps at 52, 99 and 143 deg. C confirmed by mass spectrometric results and attributed to adsorbed water, interstitial water and chemically bonded water. This evaporite mineral rock showed two higher temperature decomposition steps at 555 and 599 deg. C with mass losses of 19.6 and 7.8%. Slightly different temperatures for the thermal decomposition of the oxadada sample were observed at 52, 64.5 and 100 deg. C. Two higher temperature mass loss steps at 560.5 and 651 deg. C were observed for the oxidised sample. By comparison of the thermal analysis patterns of halotrichite and jarosite it can be shown that the El Jaroso samples are mineral sulphates and not halotrichite or jarosite
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Energy Technology Data Exchange (ETDEWEB)
Frost, Ray L. [Inorganic Materials Research Program, School of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001 (Australia)]. E-mail: r.frost@qut.edu.au; Wain, Daria [Inorganic Materials Research Program, School of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001 (Australia); Martens, Wayde N. [Inorganic Materials Research Program, School of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001 (Australia); Locke, Ashley C. [Inorganic Materials Research Program, School of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001 (Australia); Martinez-Frias, Jesus [Inorganic Materials Research Program, School of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001 (Australia); Cristalografia y Mineralogia, Unidad Asociada al Centro de Astrobiologia INTA-CSIC, Universidad de Valladolid, 47006 Valladolid (Spain); Rull, Fernando [Inorganic Materials Research Program, School of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001 (Australia); Cristalografia y Mineralogia, Unidad Asociada al Centro de Astrobiologia INTA-CSIC, Universidad de Valladolid, 47006 Valladolid (Spain)
2007-08-25
Two evaporite minerals from the El Jaroso Ravine, Spain have been analysed by thermogravimetry coupled with an evolved gas mass spectrometer. X-ray diffraction results proved the evaporite minerals were a mixture of sulphates including the minerals magnesiocopiapite, coquimbite and possibly alunogen. Thermal decomposition of the unoxidised samples showed steps at 52, 99 and 143 deg. C confirmed by mass spectrometric results and attributed to adsorbed water, interstitial water and chemically bonded water. This evaporite mineral rock showed two higher temperature decomposition steps at 555 and 599 deg. C with mass losses of 19.6 and 7.8%. Slightly different temperatures for the thermal decomposition of the oxadada sample were observed at 52, 64.5 and 100 deg. C. Two higher temperature mass loss steps at 560.5 and 651 deg. C were observed for the oxidised sample. By comparison of the thermal analysis patterns of halotrichite and jarosite it can be shown that the El Jaroso samples are mineral sulphates and not halotrichite or jarosite.
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In-situ EXAFS study on the thermal decomposition of TiH2
International Nuclear Information System (INIS)
Zhou Yingli; Wu Min; An Pengfei; Zheng Lirong; Chu Shengqi; Zhang Jing; Hu Tiandou
2014-01-01
Thermal decomposition behaviors of TiH 2 powder under a flowing helium atmosphere and in a low vacuum condition have been studied using an in situ EXAFS technique. By an EXAFS analysis containing the multiple scattering paths including H atoms, the changes of the hydrogen stoichiometric ratio and the phase transformation sequence are obtained. The results demonstrate that the initial decomposition temperature is dependent on experimental conditions, which occurs, respectively, at about 300 and 400 °C in a low vacuum condition and under a flowing helium atmosphere. During the decomposition process of TiH 2 in a low vacuum condition, the sample experiences a phase change process: δ(TiH 2 ) → δ (TiH x ) → δ(TiH x )+ β(TiH x ) → δ(TiH x )+ β(TiH x ) + α(Ti) → β(TiH x ) + α(Ti) → α(Ti) + β(Ti). This study offers a way to detect the structural information of hydrogen. A detailed discussion about the decomposition process of TiH 2 is given in this paper. (authors)
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Analysis of Siderite Thermal Decomposition by Differential Scanning Calorimetry
Bell, M. S.; Lin, I.-C.; McKay, D. S.
2000-01-01
Characterization of carbonate devolitilization has important implications for atmospheric interactions and climatic effects related to large meteorite impacts in platform sediments. On a smaller scale, meteorites contain carbonates which have witnessed shock metamorphic events and may record pressure/temperature histories of impact(s). ALH84001 meteorite contains zoned Ca-Mg-Fe-carbonates which formed on Mars. Magnetite crystals are found in the rims and cores of these carbonates and some are associated with void spaces leading to the suggestion by Brearley et al. that the crystals were produced by thermal decomposition of the carbonate at high temperature, possibly by incipient shock melting or devolitilization. Golden et al. recently synthesized spherical Mg-Fe-Ca-carbonates from solution under mild hydrothermal conditions that have similar carbonate compositional zoning to those of ALH84001. They have shown experimental evidence that the carbonate-sulfide-magnetite assemblage in ALH84001 can result from a multistep inorganic process involving heating possibly due to shock events. Experimental shock studies on calcium carbonate prove its stability to approx. 60 GPa, well in excess of the approx. 45 GPa peak pressures indicated by other shock features in ALH84001. In addition, Raman spectroscopy of carbonate globules in ALH84001 indicates no presence of CaO and MgO. Such oxide phases should be found associated with the magnetites in voids if these magnetites are high temperature shock products, the voids resulting from devolitilization of CO2 from calcium or magnesium carbonate. However, if the starting material was siderite (FeCO3), thermal breakdown of the ALH84001 carbonate at 470 C would produce iron oxide + CO2. As no documentation of shock effects in siderite exists, we have begun shock experiments to determine whether or not magnetite is produced by the decomposition of siderite within the < 45GPa pressure window and by the resultant thermal pulse to approx
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Thermal and high pressure inactivation kinetics of blueberry peroxidase.
Terefe, Netsanet Shiferaw; Delon, Antoine; Versteeg, Cornelis
2017-10-01
This study for the first time investigated the stability and inactivation kinetics of blueberry peroxidase in model systems (McIlvaine buffer, pH=3.6, the typical pH of blueberry juice) during thermal (40-80°C) and combined high pressure-thermal processing (0.1-690MPa, 30-90°C). At 70-80°C, the thermal inactivation kinetics was best described by a biphasic model with ∼61% labile and ∼39% stable fractions at temperature between 70 and 75°C. High pressure inhibited the inactivation of the enzyme with no inactivation at pressures as high as 690MPa and temperatures less than 50°C. The inactivation kinetics of the enzyme at 60-70°C, and pressures higher than 500MPa was best described by a first order biphasic model with ∼25% labile fraction and 75% stable fraction. The activation energy values at atmospheric pressure were 548.6kJ/mol and 324.5kJ/mol respectively for the stable and the labile fractions. Crown Copyright © 2017. Published by Elsevier Ltd. All rights reserved.
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Pyrolysis of Waste Castor Seed Cake: A Thermo-Kinetics Study
Directory of Open Access Journals (Sweden)
Abdullahi Muhammad Sokoto
2018-03-01
Full Text Available Biomass pyrolysis is a thermo-chemical conversion process that is of both industrial and ecological importance. The efficient chemical transformation of waste biomass to numerous products via pyrolysis reactions depends on process kinetic rates; hence the need for kinetic models to best design and operate the pyrolysis. Also, for an efficient design of an environmentally sustainable pyrolysis process of a specific lignocellulosic waste, a proper understanding of its thermo-kinetic behavior is imperative. Thus, pyrolysis kinetics of castor seed de-oiled cake (Ricinus communis using thermogravimetric technique was studied. The decomposition of the cake was carried out in a nitrogen atmosphere with a flow rate of 100mL min-1 from ambient temperature to 900 °C. The results of the thermal profile showed moisture removal and devolatilization stages, and maximum decomposition of the cake occurred at a temperature of 200-400 °C. The kinetic parameters such as apparent activation energy, pre-exponential factor, and order of reaction were determined using Friedman (FD, Kissinger-Akahira-Sunose (KAS, and Flynn-Wall-Ozawa (FWO kinetic models. The average apparent activation energy values of 124.61, 126.95 and 129.80 kJmol-1 were calculated from the slopes of the respective models. The apparent activation energy values obtained depends on conversion, which is an evidence of multi-step kinetic process during the pyrolytic decomposition of the cake. The kinetic data would be of immense benefit to model, design and develop a suitable thermo-chemical system for the conversion of waste de-oil cake to energy carrier.
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Shin, Seungha
pertaining to thermal energy transport and conversion are further explored by directly addressing the nonequilibria in phonon and molecular vibration. Enhancement of the laser cooling performance in molecular gas is examined by nonequilibrium interaction kinetics between molecules and photons. Thermal energy transport across interfaces and junctions is also studied, and decomposition of thermal interfacial resistance, atomic restructuring, and phonon wave features are addressed.
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Mechanistic Aspects of the Thermal Decomposition of Dicyclopentadienyltitanium(IV)diaryl Compounds
Boekel, C.P.; Teuben, J.H.; Liefde Meijer, H.J. de
1975-01-01
The thermal decomposition of a number of compounds Cp2TiR2 (R = aryl) was studied in the solid state and in various solvents. A first-order reaction was observed and activation energies of 20-30 kcal mol-1 were found depending on the nature of R. The activation energy for Cp2Ti(C6H5)2 (20-22 kcal
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Directory of Open Access Journals (Sweden)
Mohamad Irfan Fathurrohman
2015-07-01
Full Text Available The vulcanization kinetics of Ethylene-propylene diene monomer (EPDM rubber thermal insulation was studied by using rheometer under isothermal condition at different temperatures. The rheometry analysis was used to determining the cure kinetic parameters and predicting the cure time of EPDM thermal insulation. The experimental results revealed that the curing curves of EPDM thermal insulation were marching and the optimum curing time decreased with increasing the temperature. The kinetic parameters were determined from the autocatalytic model showed close fitting with the experimental results, indicating suitability of autocatalytic model in characterizing the cure kinetics. The activation energy was determined from the autocatalytic model is 46.3661 kJ mol-1. The cure time were predicted from autocatalytic model and the obtained kinetic parameter by using the relationship among degree of conversion, cure temperature, and cure time. The predictions of cure time provide information for the actual curing characteristic of EPDM thermal insulation. The mechanical properties of EPDM thermal insulation with different vulcanization temperatures showed the same hardness, tensile strength and modulus at 300%, except at temperature 70 °C, while the elongation at breaking point decreased with increasing temperature of vulcanization. © 2015 BCREC UNDIP. All rights reservedReceived: 8th April 2014; Revised: 7th January 2015; Accepted: 16th January 2015How to Cite: Fathurrohman, M.I., Maspanger, D.R., Sutrisno, S. (2015. Vulcanization Kinetics and Mechanical Properties of Ethylene Propylene Diene Monomer Thermal Insulation. Bulletin of Chemi-cal Reaction Engineering & Catalysis, 10 (2, 104-110. (doi:10.9767/bcrec.10.2.6682.104-110Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.2.6682.104-110
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Energy Technology Data Exchange (ETDEWEB)
Kumar, Dinesh; Kapoor, I.P.S. [Department of Chemistry, DDU Gorakhpur University, Gorakhpur 273 009 (India); Singh, Gurdip, E-mail: gsingh4us@yahoo.com [Department of Chemistry, DDU Gorakhpur University, Gorakhpur 273 009 (India); Froehlich, Roland [Institut fuer Organische Chemie, Universitaet Muenster, D-48149 Muenster (Germany)
2012-10-10
Graphical abstract: Nickel and copper nitrate complexes with 2,2 Prime -bipyridine, nitrate and water ligands have been prepared and characterized by single crystal X-ray diffraction, FT-IR and CHN analyses. Thermolysis was performed by using TG, DTA and ignition delay measurements. The kinetics of thermolysis were also evaluated. Highlights: Black-Right-Pointing-Pointer Preparation and characterization of Ni and Cu nitrate complexes have been reported. Black-Right-Pointing-Pointer Thermolysis has been carried out using TG-DTA and ignition delay measurements. Black-Right-Pointing-Pointer Their thermal decomposition pathways have been proposed. Black-Right-Pointing-Pointer Oxides residues as end product of thermolysis were revealed by XRD patterns. Black-Right-Pointing-Pointer Kinetics of their isothermal decomposition was evaluated. - Abstract: Nickel and copper nitrate complexes with 2,2 Prime -bipyridine (bipy) as a N donor and nitrate and water as oxygen donor ligands of the general formula [M(NO{sub 3})(C{sub 10}H{sub 8}N{sub 2})(H{sub 2}O){sub 3}](NO{sub 3}), where M = Ni and Cu, have been obtained from the corresponding metal nitrate salts. These complexes were characterized by X-ray crystallography, FT-IR, and CHN analysis. Both the complexes have been found to be six coordinated. Their thermal decomposition behaviour was investigated by TG, DTA, and ignition delay measurements. TG-DTA examinations of these complexes revealed multistep thermal decomposition. The corresponding metal oxide residues obtained after thermolysis were identified from their X-ray diffraction patterns (XRD). Kinetics of isothermal decomposition of the complexes was established from both the model-fitting as well as isoconversional methods.
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Thermal decomposition behaviors of magnesium borohydride doped with metal fluoride additives
International Nuclear Information System (INIS)
Zhang, Z.G.; Wang, H.; Liu, J.W.; Zhu, M.
2013-01-01
Highlights: • The decomposition proceeded through several distinct steps. • The mixed materials show a dramatically low initial hydrogen release temperature. • The additives react with the Mg–B–H compounds rather than acting as catalysts. • The reaction process was studied using an in situ TEM. - Abstract: The thermal decomposition behaviors of Magnesium borohydride [Mg(BH 4 ) 2 ] and metal fluoride doped mixtures were studied by temperature programmed desorption measurement/mass spectrometry (TPD/MS), differential scanning calorimetry (DSC) and in situ transmission electron microscope (TEM) observations. The decomposition and release of hydrogen proceeded through several distinct steps, including two polymorphic transitions, ionic Mg(BH 4 ) 2 melting with solid Mg–B–H amorphous phase formation and Mg–B–H decomposition. The addition of additives such as CaF 2 , ZnF 2 and TiF 3 resulted in a decrease in the hydrogen release temperature. ZnF 2 and TiF 3 reduced the initial hydrogen release temperature to ca. 50 °C. However, hydrogen release during the transformation from γ-Mg(BH 4 ) 2 to the amorphous Mg–B–H compounds at ca. 300 °C was only 4.5 wt.% in contrast to 9.8 wt.% for the direct decomposition of pure Mg(BH 4 ) 2 . TEM observations confirmed that ZnF 2 and TiF 3 reacted with amorphous Mg–B–H compounds rather than acting as catalysts
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DEFF Research Database (Denmark)
Wallington, T.J.; Sehested, J.; Nielsen, O.J.
1994-01-01
A pulse radiolysis technique has been used to measure a rate constant of (6.6 +/- 1.3) x 10(-12) cm3 molecule-1 s-1 for the association reaction between CF3C(O)O2 radicals and NO2 at 295 K and one atmosphere total pressure of SF6 diluent. A FTIR/smog chamber system was used to study the thermal...... decomposition CF3C(O)O2NO2. The rate of decomposition of CF3C(O)O2NO2 was independent of the total pressure of N2 diluent over the range 100-700 Torr and was fit by the expression k-1 = (1.9(-1.5)+7.6) x 10(16) exp[(-14000 +/- 480)/T] s-1. Implications for the atmospheric chemistry of CFC replacements...
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Thermal studies on unirradiated and γ-irradiated polymer of allyl diglycol carbonate
International Nuclear Information System (INIS)
Kalsi, P.C.; Pandey, A.K.; Iyer, R.H.; Singh Mudher, K.D.
1995-01-01
The thermal decomposition of unirradiated and γ-irradiated (5.93-15.5 MRad dose range) allyl diglycol carbonate polymer (trade name, CR-39) was studied by thermogravimetry (TG) and differential thermal analysis (DTA). These studies indicate four main decomposition steps in CR-39 polymer in air. Assessment of the influence of radiation dose on the above range shows that while the 5.93 MRad γ-irradiated polymer CR-39 degrades in three steps, the 15.5 MRad γ-irradiated polymer degrades in only two steps. The kinetics of the different stages of degradation were also evaluated from the TG curves. Irradiation enhances the decomposition rate and the effect increases further with increasing radiation dose. The activation energy values calculated for all the decomposition stages decrease on irradiation
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Thermal Dehydration Kinetics of Gypsum and Borogypsum under Non-isothermal Conditions
Institute of Scientific and Technical Information of China (English)
I.Y.Elbeyli; S.Piskin
2004-01-01
Thermal dehydration of gypsum and borogypsum was investigated under nonisothermal conditions in air by using simultaneous thermogravimetric-differential thermal analyzer. Nonisothermal experiments were carried out at various linear heating rates. Kinetics of dehydration in the temperature range of 373-503 K were evaluated from the DTA (differential thermal analysis)-TGA (thermogravimetric analysis) data by means of Coats-Redfern,Kissinger and Doyle Equations. Values of the activation energy and the pre-exponential factor of the dehydration were calculated. The results of thermal experiments and kinetic parameters indicated that borogypsum is similar to gypsum from dehydration mechanism point of view although it consists of boron and small amount of alkali metal oxides.
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Thermal decomposition of chromite spinel with chlorite admixture
Energy Technology Data Exchange (ETDEWEB)
Sanchez-Ramos, S. [Department of Analytical Chemistry, Faculty of Chemistry, University of Valencia, C/Doctor Moliner 50, 46100-Burjassot, Valencia (Spain); Escuela Superior de Ceramica, C/Ceramista A. Blat 22, 46940 Manises, Valencia (Spain); Domenech-Carbo, A. [Department of Analytical Chemistry, Faculty of Chemistry, University of Valencia, C/Doctor Moliner 50, 46100-Burjassot, Valencia (Spain); Gimeno-Adelantado, J.V. [Department of Analytical Chemistry, Faculty of Chemistry, University of Valencia, C/Doctor Moliner 50, 46100-Burjassot, Valencia (Spain)], E-mail: jose.v.gimeno@uv.es; Peris-Vicente, J.; Valle-Algarra, F.M. [Department of Analytical Chemistry, Faculty of Chemistry, University of Valencia, C/Doctor Moliner 50, 46100-Burjassot, Valencia (Spain)
2008-09-30
The behaviour of minerals in a South African chromite ore during the increasing of the temperature has been studied. Firstly, the changes produced during the ignition process have been examined by means of thermal and differential analysis (TGA-DTA) until 1200 deg. C. The characterization of the initial mineral and those obtained after heating at several temperatures in room atmosphere has been performed by X-ray diffraction (XRD). Moreover, voltammetric analyses have allowed to determine the variation of the iron oxidation degree in the studied materials. Light microscopy was applied to find more information about the different phases by their colour. During the heating, a wide range of complex exothermic and endothermic transformations take place. Decomposition compounds were identified, which were produced by heat decomposition, loss of structural water, element substitutions and oxygen absorptions and desorptions, caused mainly by the variation of the iron oxidation degree. The spinels of the chromite ore decompose in other spinels, with a partial change of the iron oxidation degree. From nearly 800 deg. C, chrome oxide (Cr{sub 2}O{sub 3}) comes off from the chromite forming another phase, and almost at 1000 deg. C, a slow decrease of weight was detected, caused among others to the formation of a magnetite phase. Simultaneously, the silicates undergo strong modifications, including decompositions and incorporation of iron (II) in their structure and producing other silicates stable at high temperatures, which modify the behaviour of the pure spinels. Moreover, at 1200 deg. C these silicates decompose to cristobalite (SiO{sub 2})
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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.
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Blagodatskaya, Еvgenia; Blagodatsky, Sergey; Khomyakov, Nikita; Myachina, Olga; Kuzyakov, Yakov
2016-02-01
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 (14C-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.
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Kinetic Parameters of Thermal Degradation of Polymers
Institute of Scientific and Technical Information of China (English)
朱新生; 程嘉祺
2003-01-01
The derivative expressions between activation energy (E) and the temperature at the maximum mass loss rate(Tmax) and between activation energy (E) and exponent (N) were deduced in the light of Arrhenius theory. It was found that the increase of activation energy results in the decrease of exponent and the increase of Tmax. The kinetic parameters were involved in the analysis of the thermal degradation of several polymers. The degradation kinetics of these polymers well complied with the prediction of the derivative expressions for the polymer degradation with single mechanism dominated.
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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 (Cr 2 O 3 ) and magnesiochromite (MgCr 2 O 4 ) 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.
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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.
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Alias, R.; Hamid, N. H.; Jaapar, J.; Musa, M.; Alwi, H.; Halim, K. H. Ku
2018-03-01
Thermal behavior and decomposition kinetics of shredded oil palm empty fruit bunches (SOPEFB) were investigated in this study by using thermogravimetric analysis (TGA). The SOPEFB were analyzed under conditions of temperature 30 °C to 900 °C with nitrogen gas flow at 50 ml/min. The SOPEFB were embedded with cobalt (II) nitrate solution with concentration 5%, 10%, 15% and 20%. The TG/DTG curves shows the degradation behavior of SOPEFB following with char production for each heating rate and each concentration of cobalt catalyst. Thermal degradation occurred in three phases, water drying phase, decomposition of hemicellulose and cellulose phase, and lignin decomposition phase. The kinetic equation with relevant parameters described the activation energy required for thermal degradation at the temperature regions of 200 °C to 350 °C. Activation energy (E) for different heating rate with SOPEFB embedded with different concentration of cobalt catalyst showing that the lowest E required was at SOPEFB with 20% concentration of cobalt catalyst..
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Thermal Decomposition of Sodium Hydrogen Carbonate and Textural Features of Its Calcines
Czech Academy of Sciences Publication Activity Database
Hartman, Miloslav; Svoboda, Karel; Pohořelý, Michael; Šyc, Michal
2013-01-01
Roč. 52, č. 31 (2013), s. 10619-10626 ISSN 0888-5885 R&D Projects: GA MŠk(CZ) 7C11009 Grant - others:RFCS(XE) RFCR-CT-2010-00009 Institutional support: RVO:67985858 Keywords : thermal decomposition * sodium hydrogen carbonate * sodium bicarbonate Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.235, year: 2013
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Three-dimensional coupled kinetics/thermal- hydraulic benchmark TRIGA experiments
International Nuclear Information System (INIS)
Feltus, Madeline Anne; Miller, William Scott
2000-01-01
This research project provides separate effects tests in order to benchmark neutron kinetics models coupled with thermal-hydraulic (T/H) models used in best-estimate codes such as the Nuclear Regulatory Commission's (NRC) RELAP and TRAC code series and industrial codes such as RETRAN. Before this research project was initiated, no adequate experimental data existed for reactivity initiated transients that could be used to assess coupled three-dimensional (3D) kinetics and 3D T/H codes which have been, or are being developed around the world. Using various Test Reactor Isotope General Atomic (TRIGA) reactor core configurations at the Penn State Breazeale Reactor (PSBR), it is possible to determine the level of neutronics modeling required to describe kinetics and T/H feedback interactions. This research demonstrates that the small compact PSBR TRIGA core does not necessarily behave as a point kinetics reactor, but that this TRIGA can provide actual test results for 3D kinetics code benchmark efforts. This research focused on developing in-reactor tests that exhibited 3D neutronics effects coupled with 3D T/H feedback. A variety of pulses were used to evaluate the level of kinetics modeling needed for prompt temperature feedback in the fuel. Ramps and square waves were used to evaluate the detail of modeling needed for the delayed T/H feedback of the coolant. A stepped ramp was performed to evaluate and verify the derived thermal constants for the specific PSBR TRIGA core loading pattern. As part of the analytical benchmark research, the STAR 3D kinetics code (, STAR: Space and time analysis of reactors, Version 5, Level 3, Users Guide, Yankee Atomic Electric Company, YEAC 1758, Bolton, MA) was used to model the transient experiments. The STAR models were coupled with the one-dimensional (1D) WIGL and LRA and 3D COBRA (, COBRA IIIC: A digital computer program for steady-state and transient thermal-hydraulic analysis of rod bundle nuclear fuel elements, Battelle
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Segregation and precipitation in iron-chromium alloys during thermal ageing and irradiation
International Nuclear Information System (INIS)
Senninger, O.
2013-01-01
Iron-Chromium alloys have a peculiar thermodynamic and diffusion behavior which is due to their magnetic properties. The alloy decomposition under thermal ageing has been studied in this thesis. An atomistic kinetic model has been performed in this aim in which we have modeled in details the chemical species thermodynamic and diffusion properties. In particular, the evolution of elements diffusion properties which the ferro-paramagnetic transition has been introduced in the model. Simulated decompositions have been compared with experiments for a large range of concentrations and temperatures. A good agreement between simulations and experiments was observed and these comparisons have highlighted the ferro to paramagnetic transition key role in the concentrated alloys kinetic decomposition. This study has also evidenced that the elements diffusion at phases interfaces is responsible for the alloy decomposition kinetic in long lasting.We have also started a study of the alloy radiation induced segregation. For that purpose, atomistic kinetic model has been performed modeling defects migration through a perfect planar sink. It have been shown, I agreement with former studies, that chromium tends to segregate in the vicinity of sinks at low temperatures and deplete at high temperature. (author) [fr
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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.
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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......, an intermediate stage involving a RE2O(C2H5CO2)4 composition was evidenced in the case of the Eu- and Sm-propionates. For all compounds, further decomposition of RE2O2CO3 into the corresponding sesquioxides (RE2O3) is accompanied by the release of CO2. The thermal decomposition of Dy- and Tb-propionates occurs...
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Spectral and thermal investigation of tetrabenzoylacetonatobenzoylacetonediuranyl
International Nuclear Information System (INIS)
Kostyuk, N.N.; Dik, T.A.; Klavsut', G.N.; Umrejko, D.S.
1989-01-01
Uranium(6) compound with benzoylacetone (NBA) of [(UO 2 ) 2 (NBA)(BA) 4 ] composition was prepared by the method of electrochemical synthesis in oxidizing medium. Spectral and thermal investigation (data of IR, Raman spectra, TG, DTA) was conducted to show that four NBA molecules entered the compound as acidoligands and one NBA molecule (being a bridge) - as neutral ligand in keto-form. Mechanism of thermal decomposition was suggested and kinetic parameters of thermolysis of examined substance were calculated
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Using decomposition kinetics to model the removal of mine water pollutants in constructed wetlands
Energy Technology Data Exchange (ETDEWEB)
Tarutis, W J; Unz, R F [Pennsylvania State University, University Park, PA (United States)
1994-01-01
Although numerous mathematical models have been used to describe decomposition, few, if any, have been used to model the removal of pollutants in constructed wetlands. A steady state method based on decomposition kinetics and reaction stoichiometry has been developed which simulates the removal of ferrous iron entering wetlands constructed for mine drainage treatment. Input variables for the model include organic matter concentration, reaction rate coefficient, porosity and dry density, and hydraulic detection time. Application of the model assumes complete anaerobic conditions within the entire substrate profile, constant temperature, no additional organic matter input, and subsurface flow only. For these ideal conditions, model simulations indicate that wetlands constructed with readily decomposable substrates rich in organic carbon are initially capable of removing far greater amounts of iron than wetlands built with less biodegradable substrates. However, after three to five years of operation this difference becomes negligible. For acceptable long-term treatment performance, therefore, periodic additions of decomposable organic matter will be required.
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International Nuclear Information System (INIS)
Wang Ji; Wei Min; Rao Guoying; Evans, D.G.; Duan Xue
2004-01-01
The sodium salt of hexasulfated β-cyclodextrin has been synthesized and intercalated into a magnesium-aluminum layered double hydroxide by ion exchange. The structure, composition and thermal decomposition behavior of the intercalated material have been studied by variable temperature X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), inductively coupled plasma emission spectroscopy (ICP), and thermal analysis (TG-DTA) and a model for the structure has been proposed. The thermal stability of the intercalated sulfated β-cyclodextrin is significantly enhanced compared with the pure form before intercalation
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Wang, Ji; Wei, Min; Rao, Guoying; Evans, David G.; Duan, Xue
2004-01-01
The sodium salt of hexasulfated β-cyclodextrin has been synthesized and intercalated into a magnesium-aluminum layered double hydroxide by ion exchange. The structure, composition and thermal decomposition behavior of the intercalated material have been studied by variable temperature X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), inductively coupled plasma emission spectroscopy (ICP), and thermal analysis (TG-DTA) and a model for the structure has been proposed. The thermal stability of the intercalated sulfated β-cyclodextrin is significantly enhanced compared with the pure form before intercalation.
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International Nuclear Information System (INIS)
Faradzhev, N.S.; Perry, C.C.; Kusmierek, D.O.; Fairbrother, D.H.; Madey, T.E.
2004-01-01
The kinetics of decomposition and subsequent chemistry of adsorbed CF 2 Cl 2 , activated by low-energy electron irradiation, have been examined and compared with CCl 4 . These molecules have been adsorbed alone and coadsorbed with water ice films of different thicknesses on metal surfaces (Ru; Au) at low temperatures (25 K; 100 K). The studies have been performed with temperature programmed desorption (TPD), reflection absorption infrared spectroscopy (RAIRS), and x-ray photoelectron spectroscopy (XPS). TPD data reveal the efficient decomposition of both halocarbon molecules under electron bombardment, which proceeds via dissociative electron attachment (DEA) of low-energy secondary electrons. The rates of CF 2 Cl 2 and CCl 4 dissociation increase in an H 2 O (D 2 O) environment (2-3x), but the increase is smaller than that reported in recent literature. The highest initial cross sections for halocarbon decomposition coadsorbed with H 2 O, using 180 eV incident electrons, are measured (using TPD) to be 1.0±0.2x10 -15 cm 2 for CF 2 Cl 2 and 2.5±0.2x10 -15 cm 2 for CCl 4 . RAIRS and XPS studies confirm the decomposition of halocarbon molecules codeposited with water molecules, and provide insights into the irradiation products. Electron-induced generation of Cl - and F - anions in the halocarbon/water films and production of H 3 O + , CO 2 , and intermediate compounds COF 2 (for CF 2 Cl 2 ) and COCl 2 , C 2 Cl 4 (for CCl 4 ) under electron irradiation have been detected using XPS, TPD, and RAIRS. The products and the decomposition kinetics are similar to those observed in our recent experiments involving x-ray photons as the source of ionizing irradiation
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Ventura, Isaac Aguilar
2013-05-31
Multiwalled carbon nanotube-enriched epoxy polymers were prepared by solvent evaporation based on a commercially available epoxy system and functionalized multiwalled carbon nanotubes (COOH-MWCNTs). Three weight ratio configurations (0.05, 0.5, and 1.0 wt %) of COOH-MWCNTs were considered and compared with neat epoxy and ethanol-treated epoxy to investigate the effects of nano enrichment and processing. Here, the thermal properties of the epoxy polymers, including curing kinetics, thermal conductivity, and degradation kinetics were studied. Introducing the MWCNTs increased the curing activation energy as revealed by differential scanning calorimetry. The final thermal conductivity of the 0.5 and 1.0 wt % MWCNT-enriched epoxy samples measured by laser flash technique increased by up to 15% compared with the neat material. The activation energy of the degradation process, investigated by thermogravimetric analysis, was found to increase with increasing CNT content, suggesting that the addition of MWCNTs improved the thermal stability of the epoxy polymers. © 2013 Wiley Periodicals, Inc.
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Optimization and kinetics decomposition of monazite using NaOH
International Nuclear Information System (INIS)
MV Purwani; Suyanti; Deddy Husnurrofiq
2015-01-01
Decomposition of monazite with NaOH has been done. Decomposition performed at high temperature on furnace. The parameters studied were the comparison NaOH / monazite, temperature and time decomposition. From the research decomposition for 100 grams of monazite with NaOH, it can be concluded that the greater the ratio of NaOH / monazite, the greater the conversion. In the temperature influences decomposition 400 - 700°C, the greater the reaction rate constant with increasing temperature greater decomposition. Comparison NaOH / monazite optimum was 1.5 and the optimum time of 3 hours. Relations ratio NaOH / monazite with conversion (x) following the polynomial equation y = 0.1579x 2 – 0.2855x + 0.8301 (y = conversion and x = ratio of NaOH/monazite). Decomposition reaction of monazite with NaOH was second orde reaction, the relationship between temperature (T) with a reaction rate constant (k), k = 6.106.e - 1006.8 /T or ln k = - 1006.8/T + 6.106, frequency factor A = 448.541, activation energy E = 8.371 kJ/mol. (author)
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International Nuclear Information System (INIS)
Syed, M.; Khan, A.M.; Khan, R.A.
2016-01-01
This study investigates the decomposition of clofibric acid (CLF) by different advanced oxidation processes (AOPs), such as UV (254 nm), VUV (185 nm), UV / TiO/sub 2/ and VUV / TiO/sub 2/. The removal efficiencies of applied AOPs were compared in the presence and absence of dissolved oxygen. The removal efficiency of the studied AOPs towards degradation of CLF were found in the order of VUV / TiO/sub 2/ + O/sub 2/ > VUV/TiO/sub 2/ + N/sub 2/ > VUV alone > UV / TiO/sub 2/ + O/sub 2/ > UV / TiO/sub 2/ +N/sub 2/ > UV alone. The decomposition kinetics of CLF was found to follow pseudo-first order rate law. VUV / TiO2 process was found to be most cheap and effective one for decomposition of CLF as compared to other applied AOPs in terms of electrical energy per order. Degradation products resulting from the degradation processes were also investigated using UPLC-MS /MS, accordingly degradation pathway was proposed. (author)
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Patterned magnetite films prepared via soft lithography and thermal decomposition
International Nuclear Information System (INIS)
An Lijuan; Li, Zhaoqiang; Li Wei; Nie Yaru; Chen Zhimin; Wang Yanping; Yang Bai
2006-01-01
A method for the fabrication of patterned magnetite (Fe 3 O 4 ) films is presented. We first prepared an ordered 2D array of Fe(acac) 3 through a selective deposition technique on patterned self-assembled monolayers. Using thermal decomposition at elevated temperature (300 o C), we transformed the patterned Fe(acac) 3 into patterned Fe 3 O 4 films in a short reaction time. These patterned films have been confirmed by using optical photographs, field emission scanning electron microscopy and atomic force microscopy
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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.
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The platinum catalysed decomposition of hydrazine in acidic media
International Nuclear Information System (INIS)
Ananiev, A.V.; Tananaev, I.G.; Brossard, Ph.; Broudic, J.C.
2000-01-01
Kinetic study of the hydrazine decomposition in the solutions of HClO 4 , H 2 SO 4 and HNO 3 in the presence of Pt/SiO 2 catalyst has been undertaken. It was shown that the kinetics of the hydrazine catalytic decomposition in HClO 4 and H 2 SO 4 are identical. The process is determined by the heterogeneous catalytic auto-decomposition of N 2 H 4 on the catalyst's surface. The platinum catalysed hydrazine decomposition in the nitric acid solutions is a complex process, including heterogeneous catalytic auto-decomposition of N 2 H 4 , reaction of hydrazine with catalytically generated nitrous acid and the catalytic oxidation of hydrazine by nitric acid. The kinetic parameters of these reactions have been determined. The contribution of each reaction in the total process is determined by the liquid phase composition and by the temperature. (authors)
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Energy Technology Data Exchange (ETDEWEB)
Rodriguez, R.; Udaquiola, S. [Univ. Nacional de San Juan, San Juan (Argentina). Lab. Tec. Amb., Inst. de Ing. Qca; Gauthier, D; Flamant, G. [PROMES-CNRS, Font-Romeu Odeillo (France); Mazza, G. [Univ. Nacional Del Comahue, Neuquen (Argentina). Dept. de Quimica; Martinez, O. [Univ. Nacional de la Plata, La Plata (Argentina). CINDECA-CONICET
2007-07-01
In thermochemical conversion processes that produce energy, the kinetics of waste decomposition must be considered. The rate of mass loss due to thermal decomposition determines the available fuel on the fire triangle of heat, fuel and oxygen. Heating rates in thermobalance experiments are low, and are often used to study the primary reactions in the decomposition of solids since their cracking is negligible. Thermogravimetry is an option for determining the decomposition profile of a solid in terms of its temperature versus the kinetics of its decomposition. This paper presented the thermal analysis and results of a study that used thermogravimetric analyses on dry samples of sewage sludge from San Juan, Argentina in an inert and oxidative atmosphere. Three peaks were observed in all differential thermogravimetric curves during the organic matter decomposition. In order to explain the experimental data, various reaction schemes were set up. The first two schemes considered 3 fractions decomposing in parallel during pyrolysis, with oxidative pyrolysis of all fractions during combustion or only two. The third scheme considered the decomposition of 2 fractions only but with dissymmetrical behavior during the whole pyrolysis and combustion phenomenon. It was concluded that the simulations were a good agreement with the experimental data for the first 2 schemes only, and overall, the fit was better with the second scheme. 11 refs., 4 figs.
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Directory of Open Access Journals (Sweden)
Shusen Zhao
2010-01-01
Full Text Available Nanometer cobalt ferrite (CoFe2O4 was synthesized by polyol-medium solvothermal method and characterized by X-ray diffraction (XRD, transmission electron microscopy (TEM, and selected area electron diffraction (SAED. Further, the catalytic activity and kinetic parameters of CoFe2O4 nanocrystallites on the thermal decomposition behavior of ammonium perchlorate (AP have been investigated by thermogravimetry and differential scanning calorimetry analysis (TG-DSC. The results imply that the catalytic performance of CoFe2O4 nanocrystallites is significant and the decrease in the activation energy and the increase in the rate constant for AP further confirm the enhancement in catalytic activity of CoFe2O4 nanocrystallites. A mechanism based on an proton transfer process has also been proposed for AP in the presence of CoFe2O4 nanocrystallites.
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Skrdla, Peter J; Robertson, Rebecca T
2005-06-02
Many solid-state reactions and phase transformations performed under isothermal conditions give rise to asymmetric, sigmoidally shaped conversion-time (x-t) profiles. The mathematical treatment of such curves, as well as their physical interpretation, is often challenging. In this work, the functional form of a Maxwell-Boltzmann (M-B) distribution is used to describe the distribution of activation energies for the reagent solids, which, when coupled with an integrated first-order rate expression, yields a novel semiempirical equation that may offer better success in the modeling of solid-state kinetics. In this approach, the Arrhenius equation is used to relate the distribution of activation energies to a corresponding distribution of rate constants for the individual molecules in the reagent solids. This distribution of molecular rate constants is then correlated to the (observable) reaction time in the derivation of the model equation. In addition to providing a versatile treatment for asymmetric, sigmoidal reaction curves, another key advantage of our equation over other models is that the start time of conversion is uniquely defined at t = 0. We demonstrate the ability of our simple, two-parameter equation to successfully model the experimental x-t data for the polymorphic transformation of a pharmaceutical compound under crystallization slurry (i.e., heterogeneous) conditions. Additionally, we use a modification of this equation to model the kinetics of a historically significant, homogeneous solid-state reaction: the thermal decomposition of AgMnO4 crystals. The potential broad applicability of our statistical (i.e., dispersive) kinetic approach makes it a potentially attractive alternative to existing models/approaches.
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Thermal conductivity of group-IV semiconductors from a kinetic-collective model.
de Tomas, C; Cantarero, A; Lopeandia, A F; Alvarez, F X
2014-09-08
The thermal conductivity of group-IV semiconductors (silicon, germanium, diamond and grey tin) with several isotopic compositions has been calculated from a kinetic-collective model. From this approach, significantly different to Callaway-like models in its physical interpretation, the thermal conductivity expression accounts for a transition from a kinetic (individual phonon transport) to a collective (hydrodynamic phonon transport) behaviour of the phonon field. Within the model, we confirm the theoretical proportionality between the phonon-phonon relaxation times of the group-IV semiconductors. This proportionality depends on some materials properties and it allows us to predict the thermal conductivity of the whole group of materials without the need to fit each material individually. The predictions on thermal conductivities are in good agreement with experimental data over a wide temperature range.
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Thermal conductivity of group-IV semiconductors from a kinetic-collective model
de Tomas, C.; Cantarero, A.; Lopeandia, A. F.; Alvarez, F. X.
2014-01-01
The thermal conductivity of group-IV semiconductors (silicon, germanium, diamond and grey tin) with several isotopic compositions has been calculated from a kinetic-collective model. From this approach, significantly different to Callaway-like models in its physical interpretation, the thermal conductivity expression accounts for a transition from a kinetic (individual phonon transport) to a collective (hydrodynamic phonon transport) behaviour of the phonon field. Within the model, we confirm the theoretical proportionality between the phonon–phonon relaxation times of the group-IV semiconductors. This proportionality depends on some materials properties and it allows us to predict the thermal conductivity of the whole group of materials without the need to fit each material individually. The predictions on thermal conductivities are in good agreement with experimental data over a wide temperature range. PMID:25197256
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International Nuclear Information System (INIS)
He, Xuan-yu; Wang, Jun; Ramdani, Noureddine; Liu, Wen-bin; Liu, Li-jia; Yang, Lei
2013-01-01
Graphical abstract: - Highlights: • A novel diamine-based benzoxazine monomer containing aryl ether and bulky fluorene groups (BEF-p) is synthesized. • Kinetic parameters can be calculated by Starink-LSR method and direct LSR method. • Cure reaction could be successfully described with the autocatalytic model. • The poly(BEF-p) exhibits high T g and superior thermal stability. • Aryl ether linkages had little influence on the thermal stability. - Abstract: A novel diamine-based benzoxazine monomer containing aryl ether and bulky fluorene groups (BEF-p) was prepared from the reaction of 9,9-bis-[4-(p-aminophenoxy)-phenyl]fluorene with paraformaldehyde and phenol. The chemical structure of monomer was confirmed by Fourier-transform infrared (FTIR) and 1 H and 13 C nuclear magnetic resonance spectroscopy ( 1 H and 13 C NMR). The polymerization behavior of monomer was analyzed by differential scanning calorimetry (DSC) and FTIR. The curing kinetics was studied by non-isothermal DSC, and the kinetic parameters were determined. The autocatalytic model based on two kinetic methods (Starink-LSR method and direct LSR method) showed good agreement with experimental results. The thermal and mechanical properties of poly(BEF-p) were evaluated with DSC, dynamic mechanical thermal analysis (DMTA), and thermogravimetric analysis (TGA). The results showed that the cured polymer exhibited higher glass transition temperature (T g ) and better thermal stability compared with diaminodiphenylmethane-based benzoxazine(P-ddm), and was slightly lower than those of fluorene diamine-phenol-based polybenzoxazine (poly(BF-p))
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International Nuclear Information System (INIS)
Srimachai, Taranee; Anantawaraskul, Siripon
2010-01-01
Full text: Thermal degradation behavior during polymer pyrolysis can typically be described using three apparent kinetic parameters (i.e., pre-exponential factor, activation energy, and reaction order). Several efficient techniques have been developed to estimate these apparent kinetic parameters for simple thermal degradation behavior (i.e., single apparent pyrolysis reaction). Unfortunately, these techniques cannot be directly extended to the case of polymer pyrolysis with complex thermal degradation behavior (i.e., multiple concurrent reactions forming single or multiple DTG peaks). In this work, we proposed a deconvolution method to determine the number of apparent reactions and estimate three apparent kinetic parameters and contribution of each reaction for polymer pyrolysis with complex thermal degradation behavior. The proposed technique was validated with the model and experimental pyrolysis data of several polymer blends with known compositions. The results showed that (1) the number of reaction and (2) three apparent kinetic parameters and contribution of each reaction can be estimated reasonably. The simulated DTG curves with estimated parameters also agree well with experimental DTG curves. (author)
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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.
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Energy Technology Data Exchange (ETDEWEB)
Zhang Lin [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Institute of Polymers, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Li Fan, E-mail: lfan@ncu.edu.cn [Institute of Polymers, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Chen Yiwang, E-mail: ywchen@ncu.edu.cn [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Institute of Polymers, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Wang Xiaofeng [Institute of Polymers, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China)
2011-08-15
In this paper, a new and simple approach for in-situ preparation of transparent ZnO/poly(metyl methacrylate) (ZnO/PMMA) nanocomposite films was developed. Poly(methyl methacrylate)-co-poly(zinc methacrylate acetate) (PMMA-co-PZnMAAc) copolymer was synthesized via free-radical polymerization between methyl methacrylate (MMA) and zinc methacrylate acetate (ZnMAAc), where asymmetric ZnMAAc with only one terminal double bond (C=C) was applied to act as the precursor for ZnO nanocrystals and could avoid cross-link. Subsequently, transparent ZnO/PMMA nanocomposite films were obtained by in-situ thermal decomposition. Scanning electron microscope (SEM) image revealed that ZnO nanocrystals were homogeneously dispersed in PMMA matrix. With thermal decomposition time increasing, the absorption intensity in UV region and photoluminescence intensity of ZnO/PMMA nanocomposite films enhanced. However, the optical properties diminished when the thermal decomposition temperature increased. The TGA measurement displayed ZnO/PMMA nanocomposite films prepared by the in-situ synthesis method possessed better thermal stability compared with those prepared by the physical blending method and pristine PMMA films. - Highlights: > ZnO/PMMA hybrid films were prepared via free-radical polymerization and in-situ thermal decomposition. > ZnO NCs are homogeneously dispersed in the PMMA matrix and these films have good optical properties. > Thermal stability of these films is improved compared with those of physically blending ones.
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International Nuclear Information System (INIS)
Zhang Lin; Li Fan; Chen Yiwang; Wang Xiaofeng
2011-01-01
In this paper, a new and simple approach for in-situ preparation of transparent ZnO/poly(metyl methacrylate) (ZnO/PMMA) nanocomposite films was developed. Poly(methyl methacrylate)-co-poly(zinc methacrylate acetate) (PMMA-co-PZnMAAc) copolymer was synthesized via free-radical polymerization between methyl methacrylate (MMA) and zinc methacrylate acetate (ZnMAAc), where asymmetric ZnMAAc with only one terminal double bond (C=C) was applied to act as the precursor for ZnO nanocrystals and could avoid cross-link. Subsequently, transparent ZnO/PMMA nanocomposite films were obtained by in-situ thermal decomposition. Scanning electron microscope (SEM) image revealed that ZnO nanocrystals were homogeneously dispersed in PMMA matrix. With thermal decomposition time increasing, the absorption intensity in UV region and photoluminescence intensity of ZnO/PMMA nanocomposite films enhanced. However, the optical properties diminished when the thermal decomposition temperature increased. The TGA measurement displayed ZnO/PMMA nanocomposite films prepared by the in-situ synthesis method possessed better thermal stability compared with those prepared by the physical blending method and pristine PMMA films. - Highlights: → ZnO/PMMA hybrid films were prepared via free-radical polymerization and in-situ thermal decomposition. → ZnO NCs are homogeneously dispersed in the PMMA matrix and these films have good optical properties. → Thermal stability of these films is improved compared with those of physically blending ones.
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Simões, P. N.; Pedroso, L. M.; Portugal, A. A.; Campos, J. L.
2000-01-01
The thermal decomposition of solid mixtures of 2-oxy-4,6-dinitramine-s-triazine (DNAM) and phase stabilized ammonium nitrate (PSAN) at different mass ratios has been studied. Simultaneous thermal analysis (DSC/TG) and thermomicroscopy have been used. It was found that PSAN promotes the lowering of the decomposition temperature of DNAM. The beginning of this process occurs when both components are in the solid state irrespective of the composition. However, the composition appears as the main ...
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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.
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Effects of Thermal Aging on Microstructure and Impact Properties of 316LN Stainless Steel Weld
Directory of Open Access Journals (Sweden)
LUO Qiang
2017-12-01
Full Text Available To study the thermal aging of nuclear primary pipe material 316LN stainless steel weld, accelerated thermal aging experiment was performed at 400℃ for 15000h. Microstructure evolution of weld after aging was investigated by TEM and HREM. Impact properties of weld thermally aged at different time was measured by Charpy impact test. Meanwhile, taking Charpy impact energy as the standard of thermal aging embrittlement, the thermal kinetics formula was obtained by the fitting method. Finally, the Charpy impact properties of the weld during 60 years of service at the actual operation temperature were estimated by the thermal kinetics formula. The results indicate that the spinodal decomposition occurs in the ferrite of the weld after thermal aging at 400℃ for 1000h, results in α (Fe-rich and α'(Cr-rich phases, and meanwhile, the G-phase is precipitated in the ferrite; the spinodal decomposition and the G-phase precipitation lead to the decrease in the impact energy of weld as time prolongs; the prediction results show that the Charpy impact energy of weld decreases quickly in the early 25 years, and then undergoes a slow decrease during the subsequent operation process.
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Single step thermal decomposition approach to prepare supported γ-Fe2O3 nanoparticles
International Nuclear Information System (INIS)
Sharma, Geetu; Jeevanandam, P.
2012-01-01
γ-Fe 2 O 3 nanoparticles supported on MgO (macro-crystalline and nanocrystalline) were prepared by an easy single step thermal decomposition method. Thermal decomposition of iron acetylacetonate in diphenyl ether, in the presence of the supports followed by calcination, leads to iron oxide nanoparticles supported on MgO. The X-ray diffraction results indicate the stability of γ-Fe 2 O 3 phase on MgO (macro-crystalline and nanocrystalline) up to 1150 °C. The scanning electron microscopy images show that the supported iron oxide nanoparticles are agglomerated while the energy dispersive X-ray analysis indicates the presence of iron, magnesium and oxygen in the samples. Transmission electron microscopy images indicate the presence of smaller γ-Fe 2 O 3 nanoparticles on nanocrystalline MgO. The magnetic properties of the supported magnetic nanoparticles at various calcination temperatures (350-1150 °C) were studied using a superconducting quantum interference device which indicates superparamagnetic behavior.
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Energy Technology Data Exchange (ETDEWEB)
Kondrat’ev, Yu.V.; Butlak, A.V.; Kazakov, I.V.; Timoshkin, A.Y., E-mail: a.y.timoshkin@spbu.edu
2015-12-20
Highlights: • We measured sublimation enthalpy of ammonia borane at 357 K by drop-calorimetry. • We determined activation energy for ammonia borane decomposition by tensimetry. • At 357 K decomposition and sublimation are competitive and depend on the pressure. • We propose new values for the Δ{sub f}H° of solid ammonia borane and polyamidoborane. - Abstract: Thermal behavior of ammonia borane BH{sub 3}NH{sub 3} (AB) has been studied by calorimetry, tensimetry and mass spectrometry methods. It is shown, that depending on vapor pressure in the system two competitive processes are taking place at 357 K. At atmospheric pressure thermal decomposition with hydrogen evolution is the dominant process: BH{sub 3}NH{sub 3(s)} = 1/n (BH{sub 2}NH{sub 2}){sub n(s)} + H{sub 2(g)} (1). At low pressures (circa 4 mTorr) the major process is endothermic sublimation of AB: BH{sub 3}NH{sub 3(s)} = BH{sub 3}NH{sub 3(g)} (2). At intermediate pressures both processes occur simultaneously. Enthalpies for the processes (1) and (2) have been determined by drop-calorimetry method: Δ{sub (1)}H{sub 357}° = −24.8 ± 2.3 kJ mol{sup −1} and Δ{sub sub}H{sub 357}°(BH{sub 3}NH{sub 3}) = 76.3 ± 3.0 kJ mol{sup −1}. Solid products after sublimation and decomposition have been characterized by IR and NMR spectroscopy; gaseous forms were studied by mass spectrometry. Activation energy of 94 ± 11 kJ mol{sup −1} for the process (1) in range 327–351 K was determined by static tensimetry method. Based on the analysis of available thermodynamic characteristics, new values for the standard formation enthalpy of solid AB −133.4 ± 5.2 kJ mol{sup −1} and polyamidoborane −156.7 ± 5.8 kJ mol{sup −1} are recommended.
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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.
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Kinetic Model of Resin－Catalyzed Decomposition of Acetone Cyanohydrin in Organic Solvent
Institute of Scientific and Technical Information of China (English)
章亭洲; 杨立荣; 朱自强; 吴坚平
2003-01-01
Decomposition of acetone cyanohydrin is the first-step reaction for preparing (S)-α-cyano-3-phenoxybenzyl alcohol (CPBA) by the one-pot method in organic media. Considering the compatibility of biocatalysts with chemical catalysts and the successive operation in the bioreactor, anion exchange resin (D301) was used as catalyst for this reaction. External diffusion limitation was excluded by raising rotational speed to higher than 190r·min-1 in both solvents. Internal diffusion limitation was verified to be insignificant in this reaction system. The effect of acetone cyanohydrin concentration on the reaction was also investigated. An intrinsic kinetic model was proposed when the mass transfer limitation was excluded, and the average deviation of the model is 10.5%.
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Suresh Mathew; K. Krishnan; K. N. Ninan
1999-01-01
Phase-stabilised ammonium nitrate (PSAN) was prepared by incorporating copper (II) diamine nitrate in the ammonium nitrate (AN) crystal lattice, thereby avoiding the abrupt volume change within the useful temperature range. The effect of RDX on the thermal decomposition of PSAN has been investigated. Decomposition temperatures of PSAN and RDX are almost in the same temperature range. The synergetic effect of the interaction between PSAN and RDX resulted in a net exothermic reaction of PSAN. T...
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Liu, Leili; Li, Jie; Zhang, Lingyao; Tian, Siyu
2018-01-15
MgH 2 , Mg 2 NiH 4 , and Mg 2 CuH 3 were prepared, and their structure and hydrogen storage properties were determined through X-ray photoelectron spectroscopy and thermal analyzer. The effects of MgH 2 , Mg 2 NiH 4 , and Mg 2 CuH 3 on the thermal decomposition, burning rate, and explosive heat of ammonium perchlorate-based composite solid propellant were subsequently studied. Results indicated that MgH 2 , Mg 2 NiH 4 , and Mg 2 CuH 3 can decrease the thermal decomposition peak temperature and increase the total released heat of decomposition. These compounds can improve the effect of thermal decomposition of the propellant. The burning rates of the propellant increased using Mg-based hydrogen storage materials as promoter. The burning rates of the propellant also increased using MgH 2 instead of Al in the propellant, but its explosive heat was not enlarged. Nonetheless, the combustion heat of MgH 2 was higher than that of Al. A possible mechanism was thus proposed. Copyright © 2017. Published by Elsevier B.V.
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International Nuclear Information System (INIS)
Devyatykh, G.G.; Gavrishchuk, E.M.; Gibin, A.M.; Dadanov, A.Yu.; Dzyubenko, N.G.; Kaul', A.R.; Nichiporuk, R.V.; Snezhko, N.T.; Ul'yanov, A.A.
1990-01-01
Heterogeneous oxidative decomposition of adduct of yttrium acetylacetonate with o-phenanthroline, copper acetylacetonate and barium dipivaloylmethanate in a flow-type reactor was carried out. The basic kinetic characteristics of chemical precipitation processes of films of yttrium, copper and barium oxides, which are components of high-temperature superconductors, were obtained. The values of activation energy of precipitation process of yttrium, copper and barium oxides constituted 76±10, 108±15, 81±12 (t 600 deg C) respectively
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Evidence for a kinetic bias towards antisite formation in SiC nano-decomposition
International Nuclear Information System (INIS)
Roma, G.; Crocombette, J.-P.
2010-01-01
This paper is devoted to the investigation of the mechanisms of Frenkel pair recombination in cubic silicon carbide. We use first principles calculations in the framework of Density Functional Theory (DFT) and we explore a variety of possible recombination paths using constrained relaxations and the Nudged-Elastic-Band (NEB) method for various possible neutral Frenkel pairs, including those formed by defects on different sublattices (carbon and silicon). We detect several metastable configurations, some of which have not been described previously. We also consider that silicon vacancies can assume the form of carbon antisite-carbon vacancy complexes and, as such, their recombination with interstitials can occur along specific paths. In particular, in this case, we find that the recombination with silicon interstitials would probably produce antisite pairs. Finally, we use our calculated recombination barriers for a simplified kinetic model which shows that, under certain hypotheses, the annealing of irradiation defects can lead to the build up of a non negligible concentration of antisites, i.e., to a nanoscale decomposition of the material driven by a kinetic bias.
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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.
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Decomposition and reduction of AUC in hydrogen
International Nuclear Information System (INIS)
Ge Qingren; Kang Shifang; Zhou Meng
1987-01-01
AUC (Ammonium Uranyl Carbonate) conversion processes have been adopted extensively in nuclear fuel cycle. The kinetics investigation of these processes, however, has not yet been reported in detail at the published literatures. In the present work, the decomposition kinetics of AUC in hydrogen has been determined by non-isothermal method. DSC curves are solved with computer by Ge Qingren method. The results show that the kinetics obeys Avrami-Erofeev equation within 90% conversion. The apparent activation energy and preexponent are found to be 113.0 kJ/mol and 7.11 x 10 11 s -1 respectively. The reduction kinetics of AUC decomposition product in hydrogen at the range of 450 - 600 deg C has been determined by isothermal thermogravimetric method. The results show that good linear relationship can be obtained from the plot of conversion vs time, and that the apparent activation energy is found to be 113.9 kJ/mol. The effects of particle size and partial pressure of hydrogen are examined in reduction of AUC decomposition product. The reduction mechanism and the structure of particle are discussed according to the kinetics behaviour and SEM (scanning electron microscope) photograph
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Studies on the thermal decomposition of lanthanum(III) valerate and lanthanum(III) caproate in argon
Energy Technology Data Exchange (ETDEWEB)
Grivel, J.-C., E-mail: jean@dtu.dk [Department of Energy Conversion and Storage, Technical University of Denmark, Frederiksborgvej 399, DK - 4000 Roskilde (Denmark); Zhao, Y.; Suarez Guevara, M.J. [Department of Energy Conversion and Storage, Technical University of Denmark, Frederiksborgvej 399, DK - 4000 Roskilde (Denmark); Watenphul, A. [Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, 22603 Hamburg (Germany); Institute of Mineralogy and Petrography, University of Hamburg, Grindelallee 48, 20146 Hamburg (Germany)
2015-07-20
Highlights: • The thermal decomposition of Lathanum valerate and caproate has been studied in Ar. • The compounds melt prior to decomposition. • Gas release in the molten state results in irregular mass loss. • CO{sub 2} and symmetrical ketones are the main evolving gas species. - Abstract: The decomposition of La-valerate (La(C{sub 4}H{sub 9}CO{sub 2}){sub 3}·xH{sub 2}O (x ≈ 0.45)) and La-caproate (La(C{sub 5}H{sub 11}CO{sub 2}){sub 3}·xH{sub 2}O (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 sources as well as hot-stage microscopy, it was found that both compounds melt prior to decomposition and that the main decomposition stage from the molten, anhydrous state leads to the formation of La-dioxycarbonate (La{sub 2}O{sub 2}CO{sub 3}) via an unstable intermediate product and release of symmetrical ketones. Final decomposition to La{sub 2}O{sub 3} takes place with release of CO{sub 2}.
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Voit, E. I.; Didenko, N. A.; Gaivoronskaya, K. A.
2018-03-01
Thermal decomposition of (NH4)2ZrF6 resulting in ZrO2 formation within the temperature range of 20°-750°C has been investigated by means of thermal and X-ray diffraction analysis and IR and Raman spectroscopy. It has been established that thermolysis proceeds in six stages. The vibrational-spectroscopy data for the intermediate products of thermal decomposition have been obtained, systematized, and summarized.
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Bach, Quang-Vu; Chen, Wei-Hsin
2017-12-01
Pyrolysis is a promising route for biofuels production from microalgae at moderate temperatures (400-600°C) in an inert atmosphere. Depending on the operating conditions, pyrolysis can produce biochar and/or bio-oil. In practice, knowledge for thermal decomposition characteristics and kinetics of microalgae during pyrolysis is essential for pyrolyzer design and pyrolysis optimization. Recently, the pyrolysis kinetics of microalgae has become a crucial topic and received increasing interest from researchers. Thermogravimetric analysis (TGA) has been employed as a proven technique for studying microalgae pyrolysis in a kinetic control regime. In addition, a number of kinetic models have been applied to process the TGA data for kinetic evaluation and parameters estimation. This paper aims to provide a state-of-the art review on recent research activities in pyrolysis characteristics and kinetics of various microalgae. Common kinetic models predicting the thermal degradation of microalgae are examined and their pros and cons are illustrated. Copyright © 2017 Elsevier Ltd. All rights reserved.
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Thermal decomposition of FC(O)OCH3 and FC(O)OCH2CH3.
Berasategui, M; Argüello, G A; Burgos Paci, M A
2018-05-09
The thermal decomposition of methyl and ethyl formates has been extensively studied due to their importance in the oxidation of several fuels, pesticidal properties and their presence in interstellar space. We hitherto present the study of the thermal decomposition of methyl and ethyl fluoroformates, which could help in the elucidation of the reaction mechanisms. The reaction mechanisms were studied using FTIR spectroscopy in the temperature range of 453-733 K in the presence of different pressures of N2 as bath gas. For FC(O)OCH3 two different channels were observed; the unimolecular decomposition which is favored at higher temperatures and has a rate constant kFC(O)OCH3 = (5.3 ± 0.5) × 1015 exp[-(246 ± 10 kJ mol-1/RT)] (in units of s-1) and a bimolecular channel with a rate constant kFC(O)OCH3 = (1.6 ± 0.5) × 1011 exp[-(148 ± 10 kJ mol-1/RT)] (in units of s-1 (mol L)-1). However for ethyl formate, only direct elimination of CO2, HF and ethylene operates. The rate constants of the homogeneous first-order process fit the Arrhenius equation kFC(O)OCH2CH3 = (2.06 ± 0.09) × 1013 exp[-(169 ± 6 kJ mol-1/RT)] (in units of s-1). The difference between the mechanisms of the two fluoroformates relies on the stabilization of a six-centered transition state that only exists for ethyl formate. First principles calculations for the different channels were carried out to understand the dynamics of the decomposition.
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Denisov, E. A.; Kompaniets, T. N.; Voyt, A. P.
2018-05-01
The hydrogen permeation technique in the surface-limited regime (SLR) was first used to study the isothermal decomposition of zirconium hydride. It is shown that under isothermal conditions, the hydrogen terminal solid solubility in the α-phase for hydride precipitation (TSSp) and dissolution (TSSd) differ only by 6%, in contrast to the 20-30% indicated in the available literature. It is demonstrated that even the minimum heating/cooling rate (1 C/min) used in the traditional methods of studying TSSp and TSSd is too high to exclude the effect of kinetics on the results obtained.
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Weiss, Ingrid M; Muth, Christina; Drumm, Robert; Kirchner, Helmut O K
2018-01-01
The pathways of thermal instability of amino acids have been unknown. New mass spectrometric data allow unequivocal quantitative identification of the decomposition products. Calorimetry, thermogravimetry and mass spectrometry were used to follow the thermal decomposition of the eight amino acids G, C, D, N, E, Q, R and H between 185 °C and 280 °C. Endothermic heats of decomposition between 72 and 151 kJ/mol are needed to form 12 to 70% volatile products. This process is neither melting nor sublimation. With exception of cysteine they emit mainly H 2 O, some NH 3 and no CO 2 . Cysteine produces CO 2 and little else. The reactions are described by polynomials, AA→ a NH 3 + b H 2 O+ c CO 2 + d H 2 S+ e residue, with integer or half integer coefficients. The solid monomolecular residues are rich in peptide bonds. Eight of the 20 standard amino acids decompose at well-defined, characteristic temperatures, in contrast to commonly accepted knowledge. Products of decomposition are simple. The novel quantitative results emphasize the impact of water and cyclic condensates with peptide bonds and put constraints on hypotheses of the origin, state and stability of amino acids in the range between 200 °C and 300 °C.
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Mechanistic and kinetic insights into the thermally induced rearrangement of alpha-pinene.
Stolle, Achim; Ondruschka, Bernd; Findeisen, Matthias
2008-11-07
The thermal rearrangement of alpha-pinene (1) is interesting from mechanistic as well as kinetic point of view. Carrier gas pyrolyses with 1 and its acyclic isomers ocimene (2) and alloocimene (3) were performed to investigate the thermal network of these hydrocarbons. Kinetic analysis of the major reaction steps allows for a deeper insight in the reaction mechanism. Thus it was possible to explain the racemization of 1, the formation of racemic limonene (4), and the absence of the primary pyrolysis product 2 in the reaction mixture resulting from thermal rearrangement of 1. Results supported the conclusion that the reactions starting with 1 involve biradical transition states.
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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, respe......, 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....
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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.
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In situ study of glasses decomposition layer
International Nuclear Information System (INIS)
Zarembowitch-Deruelle, O.
1997-01-01
The aim of this work is to understand the involved mechanisms during the decomposition of glasses by water and the consequences on the morphology of the decomposition layer, in particular in the case of a nuclear glass: the R 7 T 7 . The chemical composition of this glass being very complicated, it is difficult to know the influence of the different elements on the decomposition kinetics and on the resulting morphology because several atoms have a same behaviour. Glasses with simplified composition (only 5 elements) have then been synthesized. The morphological and structural characteristics of these glasses have been given. They have then been decomposed by water. The leaching curves do not reflect the decomposition kinetics but the solubility of the different elements at every moment. The three steps of the leaching are: 1) de-alkalinization 2) lattice rearrangement 3) heavy elements solubilization. Two decomposition layer types have also been revealed according to the glass heavy elements rate. (O.M.)
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Danburite decomposition by sulfuric acid
International Nuclear Information System (INIS)
Mirsaidov, U.; Mamatov, E.D.; Ashurov, N.A.
2011-01-01
Present article is devoted to decomposition of danburite of Ak-Arkhar Deposit of Tajikistan by sulfuric acid. The process of decomposition of danburite concentrate by sulfuric acid was studied. The chemical nature of decomposition process of boron containing ore was determined. The influence of temperature on the rate of extraction of boron and iron oxides was defined. The dependence of decomposition of boron and iron oxides on process duration, dosage of H 2 SO 4 , acid concentration and size of danburite particles was determined. The kinetics of danburite decomposition by sulfuric acid was studied as well. The apparent activation energy of the process of danburite decomposition by sulfuric acid was calculated. The flowsheet of danburite processing by sulfuric acid was elaborated.
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Decomposition and particle release of a carbon nanotube/epoxy nanocomposite at elevated temperatures
International Nuclear Information System (INIS)
Schlagenhauf, Lukas; Kuo, Yu-Ying; Bahk, Yeon Kyoung; Nüesch, Frank; Wang, Jing
2015-01-01
Carbon nanotubes (CNTs) as fillers in nanocomposites have attracted significant attention, and one of the applications is to use the CNTs as flame retardants. For such nanocomposites, possible release of CNTs at elevated temperatures after decomposition of the polymer matrix poses potential health threats. We investigated the airborne particle release from a decomposing multi-walled carbon nanotube (MWCNT)/epoxy nanocomposite in order to measure a possible release of MWCNTs. An experimental set-up was established that allows decomposing the samples in a furnace by exposure to increasing temperatures at a constant heating rate and under ambient air or nitrogen atmosphere. The particle analysis was performed by aerosol measurement devices and by transmission electron microscopy (TEM) of collected particles. Further, by the application of a thermal denuder, it was also possible to measure non-volatile particles only. Characterization of the tested samples and the decomposition kinetics were determined by the usage of thermogravimetric analysis (TGA). The particle release of different samples was investigated, of a neat epoxy, nanocomposites with 0.1 and 1 wt% MWCNTs, and nanocomposites with functionalized MWCNTs. The results showed that the added MWCNTs had little effect on the decomposition kinetics of the investigated samples, but the weight of the remaining residues after decomposition was influenced significantly. The measurements with decomposition in different atmospheres showed a release of a higher number of particles at temperatures below 300 °C when air was used. Analysis of collected particles by TEM revealed that no detectable amount of MWCNTs was released, but micrometer-sized fibrous particles were collected
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Decomposition and particle release of a carbon nanotube/epoxy nanocomposite at elevated temperatures
Schlagenhauf, Lukas; Kuo, Yu-Ying; Bahk, Yeon Kyoung; Nüesch, Frank; Wang, Jing
2015-11-01
Carbon nanotubes (CNTs) as fillers in nanocomposites have attracted significant attention, and one of the applications is to use the CNTs as flame retardants. For such nanocomposites, possible release of CNTs at elevated temperatures after decomposition of the polymer matrix poses potential health threats. We investigated the airborne particle release from a decomposing multi-walled carbon nanotube (MWCNT)/epoxy nanocomposite in order to measure a possible release of MWCNTs. An experimental set-up was established that allows decomposing the samples in a furnace by exposure to increasing temperatures at a constant heating rate and under ambient air or nitrogen atmosphere. The particle analysis was performed by aerosol measurement devices and by transmission electron microscopy (TEM) of collected particles. Further, by the application of a thermal denuder, it was also possible to measure non-volatile particles only. Characterization of the tested samples and the decomposition kinetics were determined by the usage of thermogravimetric analysis (TGA). The particle release of different samples was investigated, of a neat epoxy, nanocomposites with 0.1 and 1 wt% MWCNTs, and nanocomposites with functionalized MWCNTs. The results showed that the added MWCNTs had little effect on the decomposition kinetics of the investigated samples, but the weight of the remaining residues after decomposition was influenced significantly. The measurements with decomposition in different atmospheres showed a release of a higher number of particles at temperatures below 300 °C when air was used. Analysis of collected particles by TEM revealed that no detectable amount of MWCNTs was released, but micrometer-sized fibrous particles were collected.
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Decomposition and particle release of a carbon nanotube/epoxy nanocomposite at elevated temperatures
Energy Technology Data Exchange (ETDEWEB)
Schlagenhauf, Lukas [Empa - Swiss Federal Laboratories for Materials Science and Technology, Laboratory for Functional Polymers (Switzerland); Kuo, Yu-Ying; Bahk, Yeon Kyoung [Empa - Swiss Federal Laboratories for Materials Science and Technology, Laboratory for Advanced Analytical Technologies (Switzerland); Nüesch, Frank [Empa - Swiss Federal Laboratories for Materials Science and Technology, Laboratory for Functional Polymers (Switzerland); Wang, Jing, E-mail: Jing.Wang@ifu.baug.ethz.ch [Empa - Swiss Federal Laboratories for Materials Science and Technology, Laboratory for Advanced Analytical Technologies (Switzerland)
2015-11-15
Carbon nanotubes (CNTs) as fillers in nanocomposites have attracted significant attention, and one of the applications is to use the CNTs as flame retardants. For such nanocomposites, possible release of CNTs at elevated temperatures after decomposition of the polymer matrix poses potential health threats. We investigated the airborne particle release from a decomposing multi-walled carbon nanotube (MWCNT)/epoxy nanocomposite in order to measure a possible release of MWCNTs. An experimental set-up was established that allows decomposing the samples in a furnace by exposure to increasing temperatures at a constant heating rate and under ambient air or nitrogen atmosphere. The particle analysis was performed by aerosol measurement devices and by transmission electron microscopy (TEM) of collected particles. Further, by the application of a thermal denuder, it was also possible to measure non-volatile particles only. Characterization of the tested samples and the decomposition kinetics were determined by the usage of thermogravimetric analysis (TGA). The particle release of different samples was investigated, of a neat epoxy, nanocomposites with 0.1 and 1 wt% MWCNTs, and nanocomposites with functionalized MWCNTs. The results showed that the added MWCNTs had little effect on the decomposition kinetics of the investigated samples, but the weight of the remaining residues after decomposition was influenced significantly. The measurements with decomposition in different atmospheres showed a release of a higher number of particles at temperatures below 300 °C when air was used. Analysis of collected particles by TEM revealed that no detectable amount of MWCNTs was released, but micrometer-sized fibrous particles were collected.
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Sakhno, Tamara V.; Pustovit, Sergey V.; Borisenko, Artem Y.; Senchishin, Vitaliy G.; Barashkov, Nikolay N.
2003-12-01
This paper is devoted to the investigation and computer modeling of radiation and thermal decomposition of luminescent polystyrene compositions. It has been shown, that the stability of the optical properties of luminescent polymer composition depends on its material structure. On the basis of quantum-chemical calculation has been obtained the possible products of PS gamma-radiolysis and the effect of formation of fragments with conjugated double bonds and products with quinone structure has been investigated.
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International Nuclear Information System (INIS)
Machala, Libor; Sharma, Virender K.; Kuzmann, Ernö; Homonnay, Zoltán; Filip, Jan; Kralchevska, Radina P.
2016-01-01
Simple high-valent iron-oxo species, ferrate(VI) (Fe VI O 4 2− , Fe(VI)) has applications in energy storage, organic synthesis, and water purification. Of the various salts of Fe(VI), barium ferrate(VI) (BaFeO 4 ) has also a great potential as a battery material. This paper presents the thermal decomposition of BaFeO 4 in static air and nitrogen atmosphere, monitored by combination of thermal analysis, Mössbauer spectroscopy, X-ray powder diffraction, and electron-microscopic techniques. The formation of Fe IV species in the form of BaFeO 3 was found to be the primary decomposition product of BaFeO 4 at temperature around 190 °C under both studied atmospheres. BaFeO 3 was unstable in air reacting with CO 2 to form barium carbonate and speromagnetic amorphous iron(III) oxide nanoparticles (<5 nm). Above 600 °C, a solid state reaction between BaCO 3 and Fe 2 O 3 occurred, leading to the formation of barium ferrite nanoparticles, BaFe 2 O 4 (20–100 nm). - Highlights: • We explained the mechanism of thermal decomposition of barium ferrate(VI). • We confirmed the formation of Fe(IV) intermediate phase during the decomposition. • The mechanism of the decomposition is influenced by a presence of carbon dioxide.
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Toxic pollutants emitted from thermal decomposition of phthalimide compounds
Energy Technology Data Exchange (ETDEWEB)
Chen Kai; Mackie, John C.; Wojtalewicz, Dominika; Kennedy, Eric M. [Process Safety and Environmental Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, New South Wales 2308 (Australia); Dlugogorski, Bogdan Z., E-mail: Bogdan.Dlugogorski@newcastle.edu.au [Process Safety and Environmental Protection Research Group, School of Engineering, University of Newcastle, Callaghan, New South Wales 2308 (Australia)
2011-03-15
Phthalimide (PI) and tetrahydrophthalimide (THPI) are two structurally similar compounds extensively used as intermediates for the synthesis of variety of industrial chemicals. This paper investigates the thermal decomposition of PI and THPI under oxygen rich to oxygen lean conditions, quantifying the production of toxicants and explaining their formation pathways. The experiments involved a plug flow reactor followed by silica cartridges, activated charcoal trap and a condenser, with the decomposition products identified and quantified by Fourier transform infrared spectroscopy (FTIR), gas chromatography-mass spectrometry (GC-MS) and micro gas chromatography ({mu}GC). The density functional theory (DFT) calculations served to obtain dissociation energies and reaction pathways, to elucidate the reaction mechanism. The oxidation of PI and THPI produced several toxic nitrogen-containing gases and volatile organic compounds, including hydrogen cyanide, isocyanic acid, nitrogen oxides, benzonitrile, maleimide and tentatively identified benzenemethanimine. The detection of dibenzo-p-dioxin (DD) and dibenzofuran (DF) suggests potential formation of the toxic persistent organic pollutants (POPs) in fires involving PI and THPI, in presence of a chlorine source. The oxidation of THPI produced 2-cyclohexen-1-one, a toxic unsaturated ketone. The results of the present study provide the data for quantitative risk assessments of emissions of toxicants in combustion processes involving PI and THPI.
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Toxic pollutants emitted from thermal decomposition of phthalimide compounds
International Nuclear Information System (INIS)
Chen Kai; Mackie, John C.; Wojtalewicz, Dominika; Kennedy, Eric M.; Dlugogorski, Bogdan Z.
2011-01-01
Phthalimide (PI) and tetrahydrophthalimide (THPI) are two structurally similar compounds extensively used as intermediates for the synthesis of variety of industrial chemicals. This paper investigates the thermal decomposition of PI and THPI under oxygen rich to oxygen lean conditions, quantifying the production of toxicants and explaining their formation pathways. The experiments involved a plug flow reactor followed by silica cartridges, activated charcoal trap and a condenser, with the decomposition products identified and quantified by Fourier transform infrared spectroscopy (FTIR), gas chromatography-mass spectrometry (GC-MS) and micro gas chromatography (μGC). The density functional theory (DFT) calculations served to obtain dissociation energies and reaction pathways, to elucidate the reaction mechanism. The oxidation of PI and THPI produced several toxic nitrogen-containing gases and volatile organic compounds, including hydrogen cyanide, isocyanic acid, nitrogen oxides, benzonitrile, maleimide and tentatively identified benzenemethanimine. The detection of dibenzo-p-dioxin (DD) and dibenzofuran (DF) suggests potential formation of the toxic persistent organic pollutants (POPs) in fires involving PI and THPI, in presence of a chlorine source. The oxidation of THPI produced 2-cyclohexen-1-one, a toxic unsaturated ketone. The results of the present study provide the data for quantitative risk assessments of emissions of toxicants in combustion processes involving PI and THPI.
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Bañón, E; Marcilla, A; García, A N; Martínez, P; León, M
2016-02-01
The thermal decomposition of chrome tanned leather before and after a soaking treatment with NaOH was studied using thermogravimetric analysis (TGA). The effect of the solution concentration (0.2M and 0.5M) and the soaking time (5min and 15min) was evaluated. TGA experiments at four heating rates (5, 10, 15 and 20°Cmin(-1)) were run in a nitrogen atmosphere for every treatment condition. A kinetic model was developed considering the effect of the three variables studied, i.e.: the NaOH solution concentration, the soaking time and the heating rate. The proposed model for chrome tanned leather pyrolysis involves a set of four reactions, i.e.: three independent nth order reactions, yielding the corresponding products and one of them undergoing a successive cero order reaction. The model was successfully applied simultaneously to all the experimental data obtained. The evaluation of the kinetic parameters obtained (activation energy, pre-exponential factor and reaction order) allowed a better understanding of the effect of the alkali treatment on these wastes. Copyright © 2015 Elsevier Ltd. All rights reserved.
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Thermal stability of rare earth oxychlorides
International Nuclear Information System (INIS)
Bunda, V.V.; Shtilikha, M.V.; Golovej, V.M.
1984-01-01
The thermal stability of oxichlorides of the lanthanum series is investigated to determine the possibility of preparing them in the form of crystals by the method of l chemical gas-transport reactions (CTR). The lanthanide oxichlorides were subjected to thermogravimetric studies in the 20-1500 deg C temperature range under normal conditions. The temperatures of initiation of incongruent decomposition reactions are found. It is found that the process of LnOCl decomposition is preceeded by the exothermal effect connected with the Ln 2 OCl 4 recrsytallization to LnOCl. The thermodynamic and kinetic parameters of decomposition reactions are determined, such as reaction heats ΔH, decomposition rate constants K, dissociation energies E, reaction orders n. The LnOCl specific heats (Csub(P))sub(T) are estimated. It is shown that the LnOCl compounds can be prepared in the form of monocrystals by the CTR method
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Pyrolysis characteristics and kinetics of β-cyclodextrin and its two derivatives
Directory of Open Access Journals (Sweden)
Zhu Guangyong
2015-12-01
Full Text Available β-cyclodextrin (β-CD and its derivatives have been widely used to prepare inclusion complexes. However, systematic research on their thermal stabilities, pyrolysis characteristics and kinetics has rarely been reported. In this paper, thermogravimetric analysis was employed to investigate β-cyclodextrin and its two derivatives, 2-Hydroxypropyl-β-cyclodextrin (HP-β-CD and monochlorotriazinyl-β-cyclodextrin (MCT-β-CD. The pyrolysis characteristics and kinetic parameters were obtained. The results show that three stages can be distinguished during the heating process of the above three samples. The temperature of initial decomposition of HP-β-CD (309.5°C is higher than that of β-CD (297.8°C, while the temperature of initial decomposition of MCT-β-CD (231.4°C is lower than that of β-CD. For the three cyclodextrins, the thermal stability in descending order is HP-β-CD, β-CD and MCT-HP-β-CD. The activation energy values are 350.6, 303.3 and 113.9 KJ/mol, and the pre-exponential factor values are 1.11×1031, 1.37×1026 and 1.39×1010 for β-CD, HP-β-CD and MCT-β-CD respectively.
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Kinetically controlled thermal response of beta2-microglobulin amyloid fibrils.
Sasahara, Kenji; Naiki, Hironobu; Goto, Yuji
2005-09-23
Calorimetric measurements were carried out using a differential scanning calorimeter in the temperature range from 10 to 120 degrees C for characterizing the thermal response of beta2-microglobulin amyloid fibrils. The thermograms of amyloid fibril solution showed a remarkably large decrease in heat capacity that was essentially released upon the thermal unfolding of the fibrils, in which the magnitude of negative heat capacity change was not explicable in terms of the current accessible surface area model of protein structural thermodynamics. The heat capacity-temperature curve of amyloid fibrils prior to the fibril unfolding exhibited an unusual dependence on the fibril concentration and the heating rate. Particularly, the heat needed to induce the thermal response was found to be linearly dependent on the heating rate, indicating that its thermal response is under a kinetic control and precluding the interpretation in terms of equilibrium thermodynamics. Furthermore, amyloid fibrils of amyloid beta peptides also exhibited a heating rate-dependent exothermic process before the fibril unfolding, indicating that the kinetically controlled thermal response may be a common phenomenon to amyloid fibrils. We suggest that the heating rate-dependent negative change in heat capacity is coupled to the association of amyloid fibrils with characteristic hydration pattern.
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Directory of Open Access Journals (Sweden)
C. M. Mateo
2000-03-01
Full Text Available The thermal decomposition reaction of acetophenone cyclic diperoxide (trans-3,6-dimethyl-3,6-diphenyl-1,2,4,5-tetroxane; APDP at the initial concentration of c.a. 0.01 mol kg-1 and temperature ranges of 135.5 to 185.0° C has been investigated in dioxane and acetonitrile solutions, and in an 2-propanol/benzene mixture.
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Energy Technology Data Exchange (ETDEWEB)
Borghei, Maryam; Karimzadeh, Ramin [Chemical Engineering Department, Tarbiat Modares University, Tehran (Iran); Rashidi, Alimorad; Izadi, Nosrat [Research Center of Nanotechnology, Research Institute of Petroleum Industry, Tehran (Iran)
2010-09-15
Kinetic modeling of methane decomposition to CO{sub x}-free hydrogen and carbon nanofiber has been carried out in the temperature range 550-650 C over Ni-Cu/MgO catalyst from CH{sub 4}-H{sub 2} mixtures at atmospheric pressure. Assuming the different mechanisms of the reaction, several kinetic models were derived based on Langmuir-Hinshelwood type. The optimum value of kinetic parameters has been obtained by Genetic Algorithm and statistical analysis has been used for the model discrimination. The suggested kinetic model relates to the mechanism when the dissociative adsorption of methane molecule is the rate-determining stage and the estimated activation energy is 50.4 kJ/mol in agreement with the literature. The catalyst deactivation was found to be dependent on the time, reaction temperature, and partial pressures of methane and hydrogen. Inspection of the behavior of the catalyst activity in relation to time, led to a model of second order for catalyst deactivation. (author)
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International Nuclear Information System (INIS)
Pekarek, S.; Khun, J.
2006-01-01
The non-thermal plasma technologies based on electrical discharges play an important role in ecological applications. The classical corona discharge is however relatively low power discharge. With the aim to extend its current-voltage range we studied hollow needle-to-plate DC corona discharge enhanced by the flow of a gas through the needle electrode. With this type of the discharge we performed an extensive study of ozone generation and volatile organic compounds decomposition. We found that supply of air through the needle substantially increases current-voltage range of the discharge in comparison with classical pin-to-plate corona discharge. Consequently the ozone generation as well as toluene decomposition efficiency was increased (Authors)
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International Nuclear Information System (INIS)
Li, Ping; Zhou, Zhen; Xu, Hongbin; Zhang, Yi
2012-01-01
Highlights: ► Synthesis of Cr(OH) 3 nanoparticles in Cr 3+ –F − aqueous solution. ► The F − ion tailors coagulated materials, Cr(OH) 3 nanoparticles are obtained. ► Adding nanosized Cr(OH) 3 , AP thermal decomposition temperature decreases to 200 °C. ► The nanosized Cr(OH) 3 catalyzes NH 3 oxidation, accelerating AP thermal decomposition. - Abstract: A procedure for the preparation of spherical Cr(OH) 3 nanoparticles was developed based on the aging of chromium nitrate aqueous solutions in the presence of sodium fluoride, urea, and polyvinylpyrrolidone. Using scanning electron microscopy, transmission electron microscopy, and energy dispersive spectroscopy, the morphological characteristics of Cr(OH) 3 were controlled by altering the molar ratio of fluoride ion to chromium ion, as well as the initial pH and chromium ion concentration. The prepared nanosized Cr(OH) 3 decreased the temperature required to decompose ammonium perchlorate from 450 °C to about 250 °C as the catalyst. The possible catalytic mechanism of the thermal decomposition of ammonium perchlorate was also discussed.
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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.
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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.
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Ventura, Isaac Aguilar; Rahaman, Ariful; Lubineau, Gilles
2013-01-01
conductivity, and degradation kinetics were studied. Introducing the MWCNTs increased the curing activation energy as revealed by differential scanning calorimetry. The final thermal conductivity of the 0.5 and 1.0 wt % MWCNT-enriched epoxy samples measured
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Thermoanalytical study of the decomposition of yttrium trifluoroacetate thin films
International Nuclear Information System (INIS)
Eloussifi, H.; Farjas, J.; Roura, P.; Ricart, S.; Puig, T.; Obradors, X.; Dammak, M.
2013-01-01
We present the use of the thermal analysis techniques to study yttrium trifluoroacetate thin films decomposition. In situ analysis was done by means of thermogravimetry, differential thermal analysis, and evolved gas analysis. Solid residues at different stages and the final product have been characterized by X-ray diffraction and scanning electron microscopy. The thermal decomposition of yttrium trifluoroacetate thin films results in the formation of yttria and presents the same succession of intermediates than powder's decomposition, however, yttria and all intermediates but YF 3 appear at significantly lower temperatures. We also observe a dependence on the water partial pressure that was not observed in the decomposition of yttrium trifluoroacetate powders. Finally, a dependence on the substrate chemical composition is discerned. - Highlights: • Thermal decomposition of yttrium trifluoroacetate films. • Very different behavior of films with respect to powders. • Decomposition is enhanced in films. • Application of thermal analysis to chemical solution deposition synthesis of films
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Novel route for layered double hydroxides preparation by enzymatic decomposition of urea
Vial, S.; Prevot, V.; Forano, C.
2006-05-01
This study presents a new route for the preparation of a series of layered double hydroxide materials with controlled textural properties. It concerns the biogenesis of hydrotalcite like phases by Jack bean urease through the enzymatic decomposition process of urea. Different conditions of LDH biogenesis are investigated (urease activity, urea concentration). A comparative study with the precipitation method based on the thermal decomposition of urea (90 °C) is conducted in order to asses the effect of the various urea hydrolysis conditions (kinetic, temperature) and the presence of enzyme in the reaction medium on the structural and textural properties of the as prepared LDH materials. Mechanisms of formation of the LDH phases for both synthesis processes are discussed on basis of their pH control. The PXRD and SEM analysis of samples prepared by the thermal process evidence higher crystallinity and greater particle sizes than LDH obtained in mild biogenic conditions. In the latter case, presence of urease or effect of some M(II) metals may inhibit the crystallization.
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Energy Technology Data Exchange (ETDEWEB)
Amindzhanov, A A; Gagieva, S Ch; Kotegov, K V [Tadzhikskij Gosudarstvennyj Univ., Dushanbe (Tajikistan)
1991-01-01
Processes of thermal decomposition of rhenium (5) complexes with 1,2,4-triazole were studied. Thermolysis products were identified on the basis of data of the element analysis, IR spectra, conductometry and other methods. It is ascertained that at the first stage of thermolysis of hydroxyl-containing monomer complexes removal of water molecules occurs, and at the second one - dimerization process with formation of Re-O-Re group. It is shown that the nature of halide ion practically does not affect the temperature of the start of intensive thermal decomposition of the complexes.
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Danburite decomposition by hydrochloric acid
International Nuclear Information System (INIS)
Mamatov, E.D.; Ashurov, N.A.; Mirsaidov, U.
2011-01-01
Present article is devoted to decomposition of danburite of Ak-Arkhar Deposit of Tajikistan by hydrochloric acid. The interaction of boron containing ores of Ak-Arkhar Deposit of Tajikistan with mineral acids, including hydrochloric acid was studied. The optimal conditions of extraction of valuable components from danburite composition were determined. The chemical composition of danburite of Ak-Arkhar Deposit was determined as well. The kinetics of decomposition of calcined danburite by hydrochloric acid was studied. The apparent activation energy of the process of danburite decomposition by hydrochloric acid was calculated.
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Filipchuk, D. V.; Litvinov, A. V.; Etrekova, M. O.; Nozdrya, D. A.
2017-12-01
Sensitivity of the MIS-sensor to products of thermal decomposition of insulation and jacket of the most common types of cables is investigated. It is shown that hydrogen is evolved under heating the insulation to temperatures not exceeding 250 °C. Registration of the evolved hydrogen by the MIS-sensor can be used for detection of fires at an early stage.
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Lisowski, W.F.; Keim, Enrico G.; Kaszkur, Zbigniew; Smithers, M.A.; Smithers, Mark A.
2008-01-01
The thermal evolution of deuterium from thin titanium films, prepared under UHV conditions and deuterated in situ at room temperature, has been studied by means of thermal desorption mass spectrometry (TDMS) and a combination of scanning electron microscopy (SEM), transmission electron microscopy
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Study of 'liquid gold' coatings: Thermal decomposition and formation of metallic thin films
International Nuclear Information System (INIS)
Deram, V.; Turrell, S.; Darque-Ceretti, E.; Aucouturier, M.
2006-01-01
Organo-metallic solutions called liquid gold are largely used to obtain thin gilded films which are employed for decorative, technological and functional uses. However, these films often prove to be fragile with respect to use, resulting in loss of brilliance or even eventual film removal. An understanding of the behaviour of the layers requires good knowledge of the materials themselves. The present work was undertaken to better understand the evolution of the structural properties of liquid gold as it undergoes heat-processing. Accordingly, we followed the thermal decomposition processes of liquid gold coatings and the formation of the gilded metal layer using a combination of experimental techniques. First, thermal analyses coupled with mass spectrometry and infrared spectroscopy gave information concerning the decomposition of the organic medium. It has been found that the process of film formation can be decomposed into three steps, the second of which is an abrupt transition between 300 and 350 deg. C. Details on this transition have been obtained using real-time X-ray Diffraction and Rutherford Backscattering Spectrometry. Above 350 deg. C, the microstructure of the coating is reorganized to obtain a final layer which contains particles, of the size of a few hundreds nanometers, as shown by Transmission Electron Microscopy
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Thermal decomposition of ammonium uranate; X-ray study
International Nuclear Information System (INIS)
El-Fekey, S.A.; Rofail, N.H.; Khilla, M.A.
1984-01-01
Ammonium uranate was precipitated from a nuclear-pure uranyl nitrate solution using gaseous ammonia. Thermal decomposition of the obtained uranate, at different calcining temperatures, resulted in the formation of amorphous (A-)UO 3 , β-UO 3 , UOsub(2.9), U 3 O 8 (H) and U 3 O 8 (O). The influence of ammonia content, occluded nitrate ions and rate of heating, on the formation of these phases, was studied using X-ray powder diffraction analysis. The results indicated that ammonium uranate UO 2 (OH)sub(2-x)(ONH 4 )x . YH 2 O is a continuous non-stoichiometric system is a continuous non-stoichiometric system with no intermediate stoichiometric compounds and its composition varies according to mode of preparation. The results indicated also that the rate of heating and formation of hydrates are important factors for both UOsub(2.9) and U 3 O 8 (O) formation. (orig.)
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Thermal decomposition of titanium deuteride thin films
International Nuclear Information System (INIS)
Malinowski, M.E.
1983-01-01
The thermal desorption spectra of deuterium from essentially clean titanium deuteride thin films were measured by ramp heating the films in vacuum; the film thicknesses ranged from 20 to 220 nm and the ramp rates varied from 0.5 to about 3 0 C s - 1 . Each desorption spectrum consisted of a low nearly constant rate at low temperatures followed by a highly peaked rate at higher temperatures. The cleanliness and thinness of the films permitted a description of desorption rates in terms of a simple phenomenological model based on detailed balancing in which the low temperature pressure-composition characteristics of the two-phase (α-(α+#betta#)-#betta#) region of the Ti-D system were used as input data. At temperatures below 340 0 C the model predictions were in excellent agreement with the experimentally measured desorption spectra. Interpretations of the spectra in terms of 'decomposition trajectories'' are possible using this model, and this approach is also used to explain deviations of the spectra from the model at temperatures of 340 0 C and above. (Auth.)
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Kinetic study of the catalytic pyrolysis of elephant grass using Ti-MCM-41
Energy Technology Data Exchange (ETDEWEB)
Fontes, Maria do Socorro Braga; Melo, Dulce Maria de Araujo; Rodrigues, Glicelia, E-mail: socorro.fontes@yahoo.com.br [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil); Barros, Joana Maria de Farias [Universidade Federal de Campina Grande (UFCG), Cuite, PB (Brazil). Dept. de Quimica; Braga, Renata Martins [Universidade Federal da Paraiba (UFPB/CEAR/DEER), Joao Pessoa, PB (Brazil). Centro de Energias Alternativas e Renovaveis. Dept. de Engenharia de Energia Renovaveis
2014-08-15
This work aimed to study the kinetics of thermal and catalytic pyrolysis using Ti-MCM-41 as catalyst in order to assess the catalytic pyrolysis efficiency compared to thermal pyrolysis of elephant grass. Ti-MCM-41 molecular sieve was synthesized by hydrothermal method from hydrogel with the following molar composition: 1.00 CTMABr: 4.00 SiO{sub 2}:X TiO{sub 2}: 1 + X Na{sub 2}O: 200.00 H{sub 2}O, which structure template used was cetyltrimethylammonium bromide (CTMABr). The materials synthesized were characterized by X-ray diffraction, IR spectroscopy, thermogravimetric analysis and specific area by the BET method, for subsequent application in the biomass pyrolysis process. The kinetic models proposed by Vyazovkin and Flynn-Wall were used to determine the apparent activation energy involved in the thermal and catalytic pyrolysis of elephant grass and the results showed that the catalyst used was effective in reducing the apparent activation energy involved in the thermal decomposition of elephant grass. (author)
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Energy Technology Data Exchange (ETDEWEB)
Linkmann, Moritz; Sahoo, Ganapati; Biferale, Luca [Department of Physics and INFN, University of Rome Tor Vergata, Via della Ricerca Scientifica 1, I-00133 Rome (Italy); McKay, Mairi; Berera, Arjun [School of Physics and Astronomy, University of Edinburgh, Peter Guthrie Tait Road, EH9 3FD, Edinburgh (United Kingdom)
2017-02-10
We present a numerical and analytical study of incompressible homogeneous conducting fluids using a helical Fourier representation. We analytically study both small- and large-scale dynamo properties, as well as the inverse cascade of magnetic helicity, in the most general minimal subset of interacting velocity and magnetic fields on a closed Fourier triad. We mainly focus on the dependency of magnetic field growth as a function of the distribution of kinetic and magnetic helicities among the three interacting wavenumbers. By combining direct numerical simulations of the full magnetohydrodynamics equations with the helical Fourier decomposition, we numerically confirm that in the kinematic dynamo regime the system develops a large-scale magnetic helicity with opposite sign compared to the small-scale kinetic helicity, a sort of triad-by-triad α -effect in Fourier space. Concerning the small-scale perturbations, we predict theoretically and confirm numerically that the largest instability is achived for the magnetic component with the same helicity of the flow, in agreement with the Stretch–Twist–Fold mechanism. Vice versa, in the presence of Lorentz feedback on the velocity, we find that the inverse cascade of magnetic helicity is mostly local if magnetic and kinetic helicities have opposite signs, while it is more nonlocal and more intense if they have the same sign, as predicted by the analytical approach. Our analytical and numerical results further demonstrate the potential of the helical Fourier decomposition to elucidate the entangled dynamics of magnetic and kinetic helicities both in fully developed turbulence and in laminar flows.
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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.
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Infrared X-ray and thermal analysis of terbium soaps
International Nuclear Information System (INIS)
Mehrotra, K.N.; Sharma, N.
1996-01-01
Terbium sops (laureate, myristate and palmitate) were synthesized by direct metathesis of corresponding potassium soap with an aqueous solution of terbium nitrate. The physico-chemical characteristics of soaps in solid state were investigated by IR spectra, X-ray diffraction patterns and TGA measurements. The IR results revealed that the fatty acids exist in dimeric state through hydrogen bonding while the soaps possess partial ionic character. The X-ray analysis showed that the soaps have double layer structure with molecular axes slightly inclined to the basal plane. The thermal analysis suggested that the decomposition of soaps occur in two steps. The energy of activation, order of reaction and various kinetic parameters (i.e. frequency factor, entropy of activation and free energy) for the thermal decomposition of soaps were evaluated. (author). 26 refs, 4 figs, 4 tabs
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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.
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Lu, Zhipeng; Zeng, Qun; Xue, Xianggui; Zhang, Zengming; Nie, Fude; Zhang, Chaoyang
2017-08-30
Performances and behaviors under high temperature-high pressure conditions are fundamentals for many materials. We study in the present work the pressure effect on the thermal decomposition of a new energetic ionic salt (EIS), TKX-50, by confining samples in a diamond anvil cell, using Raman spectroscopy measurements and ab initio simulations. As a result, we find a quadratic increase in decomposition temperature (T d ) of TKX-50 with increasing pressure (P) (T d = 6.28P 2 + 12.94P + 493.33, T d and P in K and GPa, respectively, and R 2 = 0.995) and the decomposition under various pressures initiated by an intermolecular H-transfer reaction (a bimolecular reaction). Surprisingly, this finding is contrary to a general observation about the pressure effect on the decomposition of common energetic materials (EMs) composed of neutral molecules: increasing pressure will impede the decomposition if it starts from a bimolecular reaction. Our results also demonstrate that increasing pressure impedes the H-transfer via the enhanced long-range electrostatic repulsion of H +δ H +δ of neighboring NH 3 OH + , with blue shifts of the intermolecular H-bonds. And the subsequent decomposition of the H-transferred intermediates is also suppressed, because the decomposition proceeds from a bimolecular reaction to a unimolecular one, which is generally prevented by compression. These two factors are the basic root for which the decomposition retarded with increasing pressure of TKX-50. Therefore, our finding breaks through the previously proposed concept that, for the condensed materials, increasing pressure will accelerate the thermal decomposition initiated by bimolecular reactions, and reveals a distinct mechanism of the pressure effect on thermal decomposition. That is to say, increasing pressure does not always promote the condensed material decay initiated through bimolecular reactions. Moreover, such a mechanism may be feasible to other EISs due to the similar intermolecular
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Directory of Open Access Journals (Sweden)
Song Yang
Full Text Available Nickel laterites cannot be effectively used in physical methods because of their poor crystallinity and fine grain size. Na2SO4 is the most efficient additive for grade enrichment and Ni recovery. However, how Na2SO4 affects the selective reduction of laterite ores has not been clearly investigated. This study investigated the decomposition of laterite with and without the addition of Na2SO4 in an argon atmosphere using thermogravimetry coupled with mass spectrometry (TG-MS. Approximately 25 mg of samples with 20 wt% Na2SO4 was pyrolyzed under a 100 ml/min Ar flow at a heating rate of 10°C/min from room temperature to 1300°C. The kinetic study was based on derivative thermogravimetric (DTG curves. The evolution of the pyrolysis gas composition was detected by mass spectrometry, and the decomposition products were analyzed by X-ray diffraction (XRD. The decomposition behavior of laterite with the addition of Na2SO4 was similar to that of pure laterite below 800°C during the first three stages. However, in the fourth stage, the dolomite decomposed at 897°C, which is approximately 200°C lower than the decomposition of pure laterite. In the last stage, the laterite decomposed and emitted SO2 in the presence of Na2SO4 with an activation energy of 91.37 kJ/mol. The decomposition of laterite with and without the addition of Na2SO4 can be described by one first-order reaction. Moreover, the use of Na2SO4 as the modification agent can reduce the activation energy of laterite decomposition; thus, the reaction rate can be accelerated, and the reaction temperature can be markedly reduced.
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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.
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Spatial Inhomogeneity of Kinetic and Magnetic Dissipations in Thermal Convection
Energy Technology Data Exchange (ETDEWEB)
Hotta, H. [Department of Physics, Graduate School of Science, Chiba university, 1-33 Yayoi-cho, Inage-ku, Chiba, 263-8522 (Japan)
2017-08-20
We investigate the inhomogeneity of kinetic and magnetic dissipations in thermal convection using high-resolution calculations. In statistically steady turbulence, the injected and dissipated energies are balanced. This means that a large amount of energy is continuously converted into internal energy via dissipation. As in thermal convection, downflows are colder than upflows and the inhomogeneity of the dissipation potentially changes the convection structure. Our investigation of the inhomogeneity of the dissipation shows the following. (1) More dissipation is seen around the bottom of the calculation domain, and this tendency is promoted with the magnetic field. (2) The dissipation in the downflow is much larger than that in the upflow. The dissipation in the downflow is more than 80% of the total at maximum. This tendency is also promoted with the magnetic field. (3) Although 2D probability density functions of the kinetic and magnetic dissipations versus the vertical velocity are similar, the kinetic and magnetic dissipations are not well correlated. Our result suggests that the spatial inhomogeneity of the dissipation is significant and should be considered when modeling a small-scale strong magnetic field generated with an efficient small-scale dynamo for low-resolution calculations.
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Verma, Madhu; Gupta, Rashmi; Singh, Harjinder; Bamzai, K. K.
2018-04-01
The growth of cadmium doped magnesium hydrogen phosphate was successfully carried out by using room temperature solution technique i.e., gel encapsulation technique. Grown crystals were confirmed by single crystal X-ray diffraction (XRD). The structure of the grown crystal belongs to orthorhombic crystal system and crystallizes in centrosymmetric space group. Kinetics of the decomposition of the grown crystals were studied by non-isothermal analysis. Thermo gravimetric / differential thermo analytical (TG/DTA) studies revealed that the grown crystal is stable upto 119 °C. The various steps involved in the thermal decomposition of the material have been analysed using Horowitz-Metzger, Coats-Redfern and Piloyan-Novikova equations for evaluating various kinetic parameters. The optical studies shows that the grown crystals possess wide transmittance in the visible region and significant optical band gap of 5.5ev with cut off wavelength of 260 nm.
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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.
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Guesmi, Hazar; Berthomieu, Dorothee; Bromley, Bryan; Coq, Bernard; Kiwi-Minsker, Lioubov
2010-03-28
The characterization of Fe/ZSM5 zeolite materials, the nature of Fe-sites active in N(2)O direct decomposition, as well as the rate limiting step are still a matter of debate. The mechanism of N(2)O decomposition on the binuclear oxo-hydroxo bridged extraframework iron core site [Fe(II)(mu-O)(mu-OH)Fe(II)](+) inside the ZSM-5 zeolite has been studied by combining theoretical and experimental approaches. The overall calculated path of N(2)O decomposition involves the oxidation of binuclear Fe(II) core sites by N(2)O (atomic alpha-oxygen formation) and the recombination of two surface alpha-oxygen atoms leading to the formation of molecular oxygen. Rate parameters computed using standard statistical mechanics and transition state theory reveal that elementary catalytic steps involved into N(2)O decomposition are strongly dependent on the temperature. This theoretical result was compared to the experimentally observed steady state kinetics of the N(2)O decomposition and temperature-programmed desorption (TPD) experiments. A switch of the reaction order with respect to N(2)O pressure from zero to one occurs at around 800 K suggesting a change of the rate determining step from the alpha-oxygen recombination to alpha-oxygen formation. The TPD results on the molecular oxygen desorption confirmed the mechanism proposed.
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International Nuclear Information System (INIS)
Rofail, N.H.; ELfekey, S.A.
1992-01-01
Ammonium uranates (AU) were precipitated from a nuclear-pure uranyl nitrate solution using different precipitating agents. IR spectra of the obtained uranates and oxides formed during their thermal decomposition have been studied. The results indicated that the precipitating agent, mode of stirring, washing and calcining temperature are important factors for a specific oxide formation.4 FIG., 3 TAB
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Kinetic Study of Cotton Stalk and Rice Husk Samples under an Inert and Oxy Combustion Atmospheres
Directory of Open Access Journals (Sweden)
Ghulamullah Mailto
2018-04-01
Full Text Available Biomass materials such as CS (Cotton Stalks and RH (Rice Husk are a renewable source of energy. As biomass resources have potential to offer a uninterpted supply of biofuels through thermal decomposition processes. Nevertheless, an appropriate understanding of reaction kinetics and thermal properties of biomasses play a vital role in designing of the commercial plants using biomass as a raw material for energy generation. The kinetic characteristics of the CS and RH samples under pure nitrogen 99.9% and pure oxygen 99.9% was performed. The temperature was raised from ambient to 900oC maintaining the heating rate of 10oC/min. CS and RH decomposition was noticed in three dissimilar regions. The kinetic characteristics such as (pre-exponential factor, the order of reaction and activation energy were calculated for both selected materials. The activation energies calculated under nitrogen environment for CS and RH was 68.77 and 72.31 kJ/mole, whereas the regression coefficient (R2 was 0.9877 and 0.9731 respectively. The activation energies under oxygen environment were higher, it was 106 and 118 kJ/mole. The regression coefficient (R2 under oxygen environment was 0.9987 and 0.99883 for above sample sequence.
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Thermal inactivation kinetics of β-galactosidase during bread baking.
Zhang, Lu; Chen, Xiao Dong; Boom, Remko M; Schutyser, Maarten A I
2017-06-15
In this study, β-galactosidase was utilized as a model enzyme to investigate the mechanism of enzyme inactivation during bread baking. Thermal inactivation of β-galactosidase was investigated in a wheat flour/water system at varying temperature-moisture content combinations, and in bread during baking at 175 or 205°C. In the wheat flour/water system, the thermostability of β-galactosidase increased with decreased moisture content, and a kinetic model was accurately fitted to the corresponding inactivation data (R 2 =0.99). Interestingly, the residual enzyme activity in the bread crust (about 30%) was hundredfold higher than that in the crumb (about 0.3%) after baking, despite the higher temperature in the crust throughout baking. This result suggested that the reduced moisture content in the crust increased the thermostability of the enzyme. Subsequently, the kinetic model reasonably predicted the enzyme inactivation in the crumb using the same parameters derived from the wheat flour/water system. However, the model predicted a lower residual enzyme activity in the crust compared with the experimental result, which indicated that the structure of the crust may influence the enzyme inactivation mechanism during baking. The results reported can provide a quantitative understanding of the thermal inactivation kinetics of enzyme during baking, which is essential to better retain enzymatic activity in bakery products supplemented with heat-sensitive enzymes. Copyright © 2017 Elsevier Ltd. All rights reserved.
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Hou, Lixia; Du, Yanli; Johnson, Judy A; Wang, Shaojin
2015-10-01
Thermal death kinetics of Conogethes punctiferalis (Guenée) (Lepidoptera: Pyralidae) at different life stages, heating rate, and temperature is essential for developing postharvest treatments to control pests in chestnuts. Using a heating block system (HBS), the most heat-tolerant life stage of C. punctiferalis and the effects of heating rate (0.1, 0.5, 1, 5, and 10°C/min) on insect mortality were determined. The thermal death kinetic data of fifth-instar C. punctiferalis were obtained at temperatures between 44 and 50°C at a heating rate of 5°C/min. The results showed that the relative heat tolerance of C. punctiferalis was found to be fifth instars>pupae> third instars> eggs. To avoid the enhanced thermal tolerance of C. punctiferalis at low heating rates (0.1 or 0.5°C/min), a high heating rate of 5°C/min was selected to simulate the fast radio frequency heating in chestnuts and further determine the thermal death kinetic data. Thermal death curves of C. punctiferalis followed a 0th-order kinetic reaction model. The minimum exposure time to achieve 100% mortality was 55, 12, 6, and 3 min at 44, 46, 48, and 50°C, respectively. The activation energy for controlling C. punctiferalis was 482.15 kJ/mol with the z value of 4.09°C obtained from the thermal death-time curve. The information provided by thermal death kinetics for C. punctiferalis is useful in developing effective postharvest thermal treatment protocols for disinfesting chestnuts. © The Authors 2015. Published by Oxford University Press on behalf of Entomological Society of America. All rights reserved. For Permissions, please email: journals.permissions@oup.com.
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Thermal decomposition of UO3-2H20
International Nuclear Information System (INIS)
Flament, T.A.
1998-01-01
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
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Shan, Tzu-Ray; van Duin, Adri C T; Thompson, Aidan P
2014-02-27
We have developed a new ReaxFF reactive force field parametrization for ammonium nitrate. Starting with an existing nitramine/TATB ReaxFF parametrization, we optimized it to reproduce electronic structure calculations for dissociation barriers, heats of formation, and crystal structure properties of ammonium nitrate phases. We have used it to predict the isothermal pressure-volume curve and the unreacted principal Hugoniot states. The predicted isothermal pressure-volume curve for phase IV solid ammonium nitrate agreed with electronic structure calculations and experimental data within 10% error for the considered range of compression. The predicted unreacted principal Hugoniot states were approximately 17% stiffer than experimental measurements. We then simulated thermal decomposition during heating to 2500 K. Thermal decomposition pathways agreed with experimental findings.
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The kinetics of hydrogen removal from liquid sodium
International Nuclear Information System (INIS)
Gwyther, J.R.; Whittingham, A.C.
1981-01-01
The rates of hydrogen removal from liquid sodium-sodium hydride mixtures have been measured as a function of sodium stirring rate at temperatures up to 420 0 C. Two techniques have been employed - removal under continuous evacuation in which hydrogen flow rates were measured using a capillary flow technique and by argon purging in which hydrogen concentrations in the argon carrier gas were measured by gas chromatography. The results have been used to assess the feasibility of thermal decomposition of sodium hydride for the regeneration of hydride-laden LMFBR cold traps. Studies on the kinetics of desorption of hydrogen from solution in liquid sodium at temperatures up to 400 0 C are also presented and possible kinetic mechanisms discussed. (orig.)
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An ab initio molecular dynamics study of thermal decomposition of 3,6-di(azido)-1,2,4,5-tetrazine.
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.
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Thermal, infrared and X-ray studies on praseodymium and neodymium myristates
International Nuclear Information System (INIS)
Upadhyaya, S.K.; Sharma, P.S.
1993-01-01
The thermal decomposition of praseodymium and neodymium myristates has been studied both as a function of temperature and of time. The thermogravimetric analysis has shown that order of decomposition reaction is kinetically of zero order and the energy of activation for the decomposition process lies in the range of 10-15 kcal mol -1 . The IR results showed that lanthanide myristates have an ionic character. The X-ray analysis indicated that the zigzag chains of the fatty acid radical constituent of the soap molecules extend straight forward on both sides of each basal plane and the molecular axes of the soap molecules are somewhat inclined to the basal plane. (author). 5 refs., 2 tabs
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Kinetic Analysis of the Thermal Processing of Silica and Organosilica
Kappert, Emiel; Bouwmeester, Henricus J.M.; Benes, Nieck Edwin; Nijmeijer, Arian
2014-01-01
The incorporation of an organic group into sol–gel-derived silica causes significant changes in the structure and properties of these materials. Therefore, the thermal treatment of organosilica materials may require a different approach. In the present paper, kinetic parameters (activation energy,
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Global Kinetic Constants for Thermal Oxidative Degradation of a Cellulosic Paper
Kashiwagi, Takashi; Nambu, Hidesaburo
1992-01-01
Values of global kinetic constants for pyrolysis, thermal oxidative degradation, and char oxidation of a cellulosic paper were determined by a derivative thermal gravimetric study. The study was conducted at heating rates of 0.5, 1, 1.5, 3, and 5 C/min in ambient atmospheres of nitrogen, 0.28, 1.08, 5.2 percent oxygen concentrations, and air. Sample weight loss rate, concentrations of CO, CO2, and H2O in the degradation products, and oxygen consumption were continuously measured during the experiment. Values of activation energy, preexponential factor, orders of reaction, and yields of CO, CO2, H2O, total hydrocarbons, and char for each degradation reaction were derived from the results. Heat of reaction for each reaction was determined by differential scanning calorimetry. A comparison of the calculated CO, CO2, H2O, total hydrocarbons, sample weight loss rate, and oxygen consumption was made with the measured results using the derived kinetic constants, and the accuracy of the values of kinetic constants was discussed.
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Numerical simulations of subcritical reactor kinetics in thermal hydraulic transient phases
Energy Technology Data Exchange (ETDEWEB)
Yoo, J; Park, W S [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of)
1999-12-31
A subcritical reactor driven by a linear proton accelerator has been considered as a nuclear waste incinerator at Korea Atomic Energy Research Institute (KAERI). Since the multiplication factor of a subcritical reactor is less than unity, to compensate exponentially decreasing fission neutrons, external neutrons form spallation reactions are essentially required for operating the reactor in its steady state. Furthermore, the profile of accelerator beam currents is very important in controlling a subcritical reactor, because the reactor power varies in accordance to the profile of external neutrons. We have developed a code system to find numerical solutions of reactor kinetics equations, which are the simplest dynamic model for controlling reactors. In a due course of our previous numerical study of point kinetics equations for critical reactors, however, we learned that the same code system can be used in studying dynamic behavior of the subcritical reactor. Our major motivation of this paper is to investigate responses of subcritical reactors for small changes in thermal hydraulic parameters. Building a thermal hydraulic model for the subcritical reactor dynamics, we performed numerical simulations for dynamic responses of the reactor based on point kinetics equations with a source term. Linearizing a set of coupled differential equations for reactor responses, we focus our research interest on dynamic responses of the reactor to variations of the thermal hydraulic parameters in transient phases. 5 refs., 8 figs. (Author)
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Numerical simulations of subcritical reactor kinetics in thermal hydraulic transient phases
Energy Technology Data Exchange (ETDEWEB)
Yoo, J.; Park, W. S. [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of)
1998-12-31
A subcritical reactor driven by a linear proton accelerator has been considered as a nuclear waste incinerator at Korea Atomic Energy Research Institute (KAERI). Since the multiplication factor of a subcritical reactor is less than unity, to compensate exponentially decreasing fission neutrons, external neutrons form spallation reactions are essentially required for operating the reactor in its steady state. Furthermore, the profile of accelerator beam currents is very important in controlling a subcritical reactor, because the reactor power varies in accordance to the profile of external neutrons. We have developed a code system to find numerical solutions of reactor kinetics equations, which are the simplest dynamic model for controlling reactors. In a due course of our previous numerical study of point kinetics equations for critical reactors, however, we learned that the same code system can be used in studying dynamic behavior of the subcritical reactor. Our major motivation of this paper is to investigate responses of subcritical reactors for small changes in thermal hydraulic parameters. Building a thermal hydraulic model for the subcritical reactor dynamics, we performed numerical simulations for dynamic responses of the reactor based on point kinetics equations with a source term. Linearizing a set of coupled differential equations for reactor responses, we focus our research interest on dynamic responses of the reactor to variations of the thermal hydraulic parameters in transient phases. 5 refs., 8 figs. (Author)
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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.
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Thermal Decomposition Properties of Materials from Different Parts of Corn Stalk
Directory of Open Access Journals (Sweden)
Siwei Huang
2015-02-01
Full Text Available To help better utilize corn stalk (CS, pyrolysis behavior of materials from different parts of the CS including corn stalk without pith, corn root, and corn leaf were analyzed using thermogravimetric analysis (TGA at heating rates of 5, 10, 20, and 25 °C/min. The apparent activation energies determined by the Friedman method for corn stalk without pith, corn root, and corn leaf were in the range of 26.4 to 103.6 kJ/mol, 37.6 to 69.5 kJ/mol, and 35.0 to 103.9 kJ/mol, respectively, depending on the conversion. The main thermal decomposition occurred within a temperature range of 200 to 350 °C (±10 °C. Most of the volatile materials decomposed at less than a 0.8 conversion rate. At greater than a 0.8 conversion rate, the remaining material was mainly char, and the decomposition of char proceeded at higher conversion rates. Different pyrolysis characteristics in the CS indicated that different treatments should be chosen according to different parts for achieving the optimum conversion rate in practical applications.
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Li, Gang; Liu, Xiaoli; Bai, Weiyang
2018-03-01
In this paper, porous MgCo2O4 with rod-like morphology was successfully synthesized through the thermal treatment of metal oxalates precursor originated by the reaction of metal sulfates and oxalic acid, without the addition of other additives. The porous rod-like MgCo2O4, with a diameter of several hundred nanometers and a length of several micrometers, was formed through the agglomeration of numerous crystalline grains sized in 10–25 nm. Its catalytic effect on ammonium perchlorate (AP) thermal decomposition was evaluated using differential scanning calorimetry (DSC) techniques. It was found that the pyrolysis temperature of AP reduced by 129 °C and the heat release increased more than 3.19-fold with a 2 wt% addition of MgCo2O4. Meanwhile, the addition of MgCo2O4 resulted in an AP decomposition activation energy reduction from 216 kJ mol‑1 to 155 kJ mol‑1, calculated using the Kissinger correlation. This study provides new insights into the design and development of high performance catalysts for AP thermal decomposition.
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International Nuclear Information System (INIS)
Chi, Jen-Hao; Wu, Sheng-Hung; Shu, Chi-Min
2009-01-01
In the past, process incidents attributed to organic peroxides (OPs) that involved near misses, over-pressures, runaway reactions, and thermal explosions occurred because of poor training, human error, incorrect kinetic assumptions, insufficient change management, and inadequate chemical knowledge in the manufacturing process. Calorimetric applications were employed broadly to test organic peroxides on a small-scale because of their thermal hazards, such as exothermic behavior and self-accelerating decomposition in the laboratory. In essence, methyl ethyl ketone peroxide (MEKPO) is highly reactive and exothermically unstable. In recent years, it has undergone many thermal explosions and runaway reaction incidents in the manufacturing process. Differential scanning calorimetry (DSC), vent sizing package 2 (VSP2), and thermal activity monitor (TAM) were employed to analyze thermokinetic parameters and safety index. The intent of the analyses was to facilitate the use of various auto-alarm equipments to detect over-pressure, over-temperature, and hazardous materials leaks for a wide spectrum of operations. Results indicated that MEKPO decomposition is detected at low temperatures (30-40 deg. C), and the rate of decomposition was shown to exponentially increase with temperature and pressure. Determining time to maximum rate (TMR), self-accelerating decomposition temperature (SADT), maximum temperature (T max ), exothermic onset temperature (T 0 ), and heat of decomposition (ΔH d ) was essential for identifying early-stage runaway reactions effectively for industries.
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Treatment of off-gas from lagoon sludge thermal decomposition
International Nuclear Information System (INIS)
Hwang, D. S.; Oh, J. H.; Choi, Y. D.; Hwang, S. T.; Park, J. H.; Ga, M. J.
2005-01-01
Korea Atomic Energy Research Institute (KAERI) has launched a decommissioning program of the uranium conversion plant in 2001. The treatment of the sludge waste, which was generated during the operation of the plant and stored in the lagoon, is one of the most important tasks in the decommissioning program of the plant. The major compounds of the lagoon sludge are ammonium nitrate, sodium nitrate, calcium nitrate, calcium carbonate, and uranium compounds. The minor compounds are iron, magnesium, aluminum, silicon and phosphorus. A treatment process of the sludge was developed as figure 1 based on the results of the sludge characteristics and the developed treatment technologies. A treatment of off-gas evolved from the nitrate salts thermal decomposition is one of the important process. Off-gas treatment by using a selective catalytic reduction (SCR) method was investigated in this study
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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.
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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.
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Institute of Scientific and Technical Information of China (English)
Jiangbo WANG; Zhong XIN
2009-01-01
The thermal degradation behaviors of poly-carbonate/polymethylphenylsilsesquioxane (FRPC) composites were investigated by thermogravimetric analysis (TGA) under isothermal conditions in nitrogen atmosphere. The isothermal kinetics equation was used to describe the thermal degradation process. The results showed that activation energy (E), in the case of isothermal degradation, was a quick increasing function of conversion (a) for polycarbonate (PC) but was a strong and decreasing function of conversion for FRPC. Under the isothermal condition, the addition of polymethylphenylsilsesquioxane (PMPSQ) retardanted the thermal degradation and enhanced the thermal stability of PC during the early and middle stages of thermal degradation. It also indicated a possible existence of a difference in nucleation, nuclei growth, and gas diffusion mechanism in the thermal degradation process between PC and FRPC. Meanwhile, the addition of PMPSQ influenced the lifetime of PC, but the composite still met the demand in manufacturing and application.
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Ionic liquid thermal stabilities: decomposition mechanisms and analysis tools.
Maton, Cedric; De Vos, Nils; Stevens, Christian V
2013-07-07
The increasing amount of papers published on ionic liquids generates an extensive quantity of data. The thermal stability data of divergent ionic liquids are collected in this paper with attention to the experimental set-up. The influence and importance of the latter parameters are broadly addressed. Both ramped temperature and isothermal thermogravimetric analysis are discussed, along with state-of-the-art methods, such as TGA-MS and pyrolysis-GC. The strengths and weaknesses of the different methodologies known to date demonstrate that analysis methods should be in line with the application. The combination of data from advanced analysis methods allows us to obtain in-depth information on the degradation processes. Aided with computational methods, the kinetics and thermodynamics of thermal degradation are revealed piece by piece. The better understanding of the behaviour of ionic liquids at high temperature allows selective and application driven design, as well as mathematical prediction for engineering purposes.
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Raghupathy, Arun; Ghia, Karman; Ghia, Urmila
2008-11-01
Compact Thermal Models (CTM) to represent IC packages has been traditionally developed using the DELPHI-based (DEvelopment of Libraries of PHysical models for an Integrated design) methodology. The drawbacks of this method are presented, and an alternative method is proposed. A reduced-order model that provides the complete thermal information accurately with less computational resources can be effectively used in system level simulations. Proper Orthogonal Decomposition (POD), a statistical method, can be used to reduce the order of the degree of freedom or variables of the computations for such a problem. POD along with the Galerkin projection allows us to create reduced-order models that reproduce the characteristics of the system with a considerable reduction in computational resources while maintaining a high level of accuracy. The goal of this work is to show that this method can be applied to obtain a boundary condition independent reduced-order thermal model for complex components. The methodology is applied to the 1D transient heat equation.
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Modelling of thermal degradation kinetics of ascorbic acid in ...
African Journals Online (AJOL)
Ascorbic acid (vitamin C) loss in thermally treated pawpaw and potato was modelled mathematically. Isothermal experiments in the temperature range of 50 -80 oC for the drying of pawpaw and 60 -100 oC for the blanch-drying of potato were utilized to determine the kinetics of ascorbic acid loss in both fruit and vegetable.
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Energy Technology Data Exchange (ETDEWEB)
Zou, Min, E-mail: zoumin3362765@163.com; Wang, Xin, E-mail: wangx@mail.njust.edu.cn; Jiang, Xiaohong, E-mail: jxh0668@sina.com; Lu, Lude, E-mail: lulude17@yahoo.com
2014-05-01
Catalyzed thermal decomposition process of ammonium perchlorate (AP) over neodymium oxide (Nd{sub 2}O{sub 3}) was investigated. Catalytic performances of nanometer-sized Nd{sub 2}O{sub 3} and micrometer-sized Nd{sub 2}O{sub 3} were evaluated by differential scanning calorimetry (DSC). In contrast to universal concepts, catalysts in different sizes have nearly similar catalytic activities. Based on structural and morphological variation of the catalysts during the reaction, combined with mass spectrum analyses and studies of unmixed style, a new understanding of this catalytic process was proposed. We believed that the newly formed chloride neodymium oxide (NdOCl) was the real catalytic species in the overall thermal decomposition of AP over Nd{sub 2}O{sub 3}. Meanwhile, it was the “self-distributed” procedure which occurred within the reaction that also worked for the improvement of overall catalytic activities. This work is of great value in understanding the roles of micrometer-sized catalysts used in heterogeneous reactions, especially the solid–solid reactions which could generate a large quantity of gaseous species. - Graphical abstract: In-situ and self-distributed reaction process in thermal decomposition of AP catalyzed by Nd{sub 2}O{sub 3}. - Highlights: • Micro- and nano-Nd{sub 2}O{sub 3} for catalytic thermal decomposition of AP. • No essential differences on their catalytic performances. • Structural and morphological variation of catalysts digs out catalytic mechanism. • This catalytic process is “in-situ and self-distributed” one.
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Decomposition of dioxin analogues and ablation study for carbon nanotube
International Nuclear Information System (INIS)
Yamauchi, Toshihiko
2002-01-01
Two application studies associated with the free electron laser are presented separately, which are the titles of 'Decomposition of Dioxin Analogues' and 'Ablation Study for Carbon Nanotube'. The decomposition of dioxin analogues by infrared (IR) laser irradiation includes the thermal destruction and multiple-photon dissociation. It is important for us to choose the highly absorbable laser wavelength for the decomposition. The thermal decomposition takes place by the irradiation of the low IR laser power. Considering the model of thermal decomposition, it is proposed that adjacent water molecules assist the decomposition of dioxin analogues in addition to the thermal decomposition by the direct laser absorption. The laser ablation study is performed for the aim of a carbon nanotube synthesis. The vapor by the ablation is weakly ionized in the power of several-hundred megawatts. The plasma internal energy is kept over an 8.5 times longer than the vacuum. The cluster was produced from the weakly ionized gas in the enclosed gas, which is composed of the rough particles in the low power laser more than the high power which is composed of the fine particles. (J.P.N.)
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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
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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
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Thermal and X-ray diffraction analysis studies during the decomposition of ammonium uranyl nitrate
Kim, B. H.; Lee, Y. B.; Prelas, M. A.; Ghosh, T. K.
2012-01-01
Two types of ammonium uranyl nitrate (NH4)2UO2(NO3)4?2H2O and NH4UO2(NO3)3, were thermally decomposed and reduced in a TG-DTA unit in nitrogen, air, and hydrogen atmospheres. Various intermediate phases produced by the thermal decomposition and reduction process were investigated by an X-ray diffraction analysis and a TG/DTA analysis. Both (NH4)2UO2(NO3)4?2H2O and NH4UO2(NO3)3 decomposed to amorphous UO3 regardless of the atmosphere used. The amorphous UO3 from (NH4)2UO2(NO3)4?2H2O was crysta...
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International Nuclear Information System (INIS)
Gaur, Rama; Jeevanandam, P.
2015-01-01
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
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Mathematical modelling of the decomposition of explosives
International Nuclear Information System (INIS)
Smirnov, Lev P
2010-01-01
Studies on mathematical modelling of the molecular and supramolecular structures of explosives and the elementary steps and overall processes of their decomposition are analyzed. Investigations on the modelling of combustion and detonation taking into account the decomposition of explosives are also considered. It is shown that solution of problems related to the decomposition kinetics of explosives requires the use of a complex strategy based on the methods and concepts of chemical physics, solid state physics and theoretical chemistry instead of empirical approach.
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Liu, Xuan; Zhang, Yang; Li, Zifu; Feng, Rui; Zhang, Yaozhong
2014-10-01
In this study, thermal and physicochemical characterization results of corncob (CC) and its derived biochars were analyzed and differentiated from sawdust (SD) and cornstalk (CS). The pyrolysis temperature shows the largest effect on the yield of biochar produced compare with residing time, heating rate, and feedstock particle size. The CC-derived biochars produced at temperatures ranging from 300 to 600°C were analyzed. The CC was thermochemically altered to a stable biochar when the pyrolysis temperature was set to over 500°C. To deduce the reaction mechanism of the CC during the major thermal decomposition stage, 16 mechanisms in solid-state reactions were applied. The reaction order and nucleation mechanisms described the thermal decomposition of the CC. By using the best-fitted mechanisms, the kinetic parameters were calculated. The weight active energy of the CC was 122.42kJ/mol, which was the lowest value compared to those of CS and SD. Copyright © 2014 Elsevier Ltd. All rights reserved.
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Bernard, Samuel; Fiaty, Koffi; Cornu, David; Miele, Philippe; Laurent, Pierre
2006-05-11
A complete kinetic modeling of the polymer-derived ceramics (PDCs) route is achieved for the first time through the investigation of the solid-state decomposition of a typical melt-spinnable poly[B-(methylamino)borazine] into boron nitride fibers at various heating rates. Through the use of the Lorentz fitting approach, it is shown that the two-step weight loss associated with the polymer-to-ceramic conversion is governed by a complex interplay of five diffusion-type transport mechanisms that are independent of the applied heating schedule. The application of the Friedman method to dynamic thermogravimetry data yields Ea and ln A values that are seen to increase with the extent of the ceramic conversion from region one (Ea = 38.73 kJ mol(-1)) to region five (Ea = 146.64 kJ mol(-1)). This fact indicates that both the mechanisms within those regions are parallel routes to the formation of the final solid-state material and their complexity increases with the conversion progress. The cross-linking process (first weight loss) of the polymer is governed by three dependent poorly energetic mechanisms. The first weight loss is activated by ammonolysis reactions that provide a modified polymer capable of undergoing condensation reactions in regions two and three to yield a highly cross-linked polymer. A large evolution of methylamine is identified during this process. Mineralization (region four) and ceramization (region five) steps are represented by two highly energetic multistep mechanisms. The mineralization step is associated with a large evolution of methylamine and occurs during the transition between the cross-linking and ceramization processes through the cleavage of the inter-ring B-N bonds. Ceramization represents the end of the polymer-to-ceramic conversion in which the planar consolidation of BN hexagons occurs through complex structural rearrangements of the borazine units (cleavage of the intraring B-N bonds) accompanied with an ammonia evolution. Finally
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International Nuclear Information System (INIS)
Aboulkas, A.; El harfi, K.; El Bouadili, A.
2010-01-01
Study of the decomposition kinetics is an important tool for the development of polymer recycling in industrial scale. In this work, the activation energy and the reaction model of the pyrolysis of high density polyethylene (HDPE), low density polyethylene (LDPE) and polypropylene (PP) have been estimated from non-isothermal kinetic results. Firstly, the activation energy values obtained by Friedman, Kissinger-Akahira-Sunose and Flynn-Wall-Ozawa isoconversional methods, are 238-247 kJ/mol for HDPE, 215-221 kJ/mol for LDPE and 179-188 kJ/mol for PP. Secondly, the appropriate conversion model of the process was determined by Coats-Redfern and Criado methods. The pyrolysis reaction models of HDPE and LDPE are accounted for by 'Contracting Sphere' model, whereas that of PP by 'Contracting Cylinder' model.
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Modelling and determination of the kinetic parameters of the pyrolysis of Dichrostachys cinerea
International Nuclear Information System (INIS)
Abreu Naranjo, Reinier; Romero Romero, Osvaldo
2011-01-01
In the present study were analyzed biomass samples of Dichrostachys cinerea, commonly known in Cuba as marabou, by thermogravimetric method at various heating rates of devolatilization in nitrogen atmosphere at 5, 10 and 20 C min-1. On the kinetic analysis was used a mechanism of three independent reactions of order 1, generally attributed to three chief components of this kind of lignocellulose materials, hemicelluloses, cellulose and lignin. The values of activation energy, pre-exponential factor and contribution factor were similar to those reported in previous research for this type of biomass. The proposed model predicts with acceptable correlation the experimental and calculated curves of the decomposition of D. cinerea, with a deviation factor less than 5% for the temperature range studied. On the other hand, the kinetic parameters of the thermal decomposition coupled at equations of transport phenomena are essential to optimize the design and use of biomass thermochemical conversion processes, hence the importance of the research. (author)
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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
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Watson-Wright, Christa; Singh, Dilpreet; Demokritou, Philip
2017-01-01
Nano-enabled thermoplastics are part of the growing market of nano-enabled products (NEPs) that have vast utility in several industries and consumer goods. The use and disposal of NEPs at their end of life has raised concerns about the potential release of constituent engineered nanomaterials (ENMs) during thermal decomposition and their impact on environmental health and safety. To investigate this issue, industrially relevant nano-enabled thermoplastics including polyurethane, polycarbonate, and polypropylene containing carbon nanotubes (0.1 and 3% w/v, respectively), polyethylene containing nanoscale iron oxide (5% w/v), and ethylene vinyl acetate containing nanoscale titania (2 and 5% w/v) along with their pure thermoplastic matrices were thermally decomposed using the recently developed lab based Integrated Exposure Generation System (INEXS). The life cycle released particulate matter (called LCPM) was monitored using real time instrumentation, size fractionated, sampled, extracted and prepared for toxicological analysis using primary small airway epithelial cells to assess potential toxicological effects. Various cellular assays were used to assess reactive oxygen species and total glutathione as measurements of oxidative stress along with mitochondrial function, cellular viability, and DNA damage. By comparing toxicological profiles of LCPM released from polymer only (control) with nano-enabled LCPM, potential nanofiller effects due to the use of ENMs were determined. We observed associations between NEP properties such as the percent nanofiller loading, host matrix, and nanofiller chemical composition and the physico-chemical properties of released LCPM, which were linked to biological outcomes. More specifically, an increase in percent nanofiller loading promoted a toxicological response independent of increasing LCPM dose. Importantly, differences in host matrix and nanofiller composition were shown to enhance biological activity and toxicity of LCPM
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Trávníček, Zdeněk; Zbořil, Radek; Matiková-Maľarová, Miroslava; Drahoš, Bohuslav; Cernák, Juraj
2013-01-01
The Prussian blue analogues represent well-known and extensively studied group of coordination species which has many remarkable applications due to their ion-exchange, electron transfer or magnetic properties. Among them, Co-Fe Prussian blue analogues have been extensively studied due to the photoinduced magnetization. Surprisingly, their suitability as precursors for solid-state synthesis of magnetic nanoparticles is almost unexplored. In this paper, the mechanism of thermal decomposition of [Co(en)3][Fe(CN)6] ∙∙ 2H2O (1a) is elucidated, including the topotactic dehydration, valence and spins exchange mechanisms suggestion and the formation of a mixture of CoFe2O4-Co3O4 (3:1) as final products of thermal degradation. The course of thermal decomposition of 1a in air atmosphere up to 600°C was monitored by TG/DSC techniques, (57)Fe Mössbauer and IR spectroscopy. As first, the topotactic dehydration of 1a to the hemihydrate [Co(en)3][Fe(CN)6] ∙∙ 1/2H2O (1b) occurred with preserving the single-crystal character as was confirmed by the X-ray diffraction analysis. The consequent thermal decomposition proceeded in further four stages including intermediates varying in valence and spin states of both transition metal ions in their structures, i.e. [Fe(II)(en)2(μ-NC)Co(III)(CN)4], Fe(III)(NH2CH2CH3)2(μ-NC)2Co(II)(CN)3] and Fe(III)[Co(II)(CN)5], which were suggested mainly from (57)Fe Mössbauer, IR spectral and elemental analyses data. Thermal decomposition was completed at 400°C when superparamagnetic phases of CoFe2O4 and Co3O4 in the molar ratio of 3:1 were formed. During further temperature increase (450 and 600°C), the ongoing crystallization process gave a new ferromagnetic phase attributed to the CoFe2O4-Co3O4 nanocomposite particles. Their formation was confirmed by XRD and TEM analyses. In-field (5 K / 5 T) Mössbauer spectrum revealed canting of Fe(III) spin in almost fully inverse spinel structure of CoFe2O4. It has been found that the thermal
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Directory of Open Access Journals (Sweden)
A. Kmita
2018-03-01
Full Text Available The article presents the results of research on thermal decomposition of Ester-Cured Alkaline Phenolic No-Bake (ALPHASET binders used in molding technology. In the ALPHASET system phenol-formaldehyde resin of resole type is cured with a liquid mixture of esters. Under the influence of the molten metal the thermal decomposition of the binder follows, resulting in the evolution of gases, often harmful, e.g. from benzene, toluene, ethylbenzene and xylenes (BTEX or Polycyclic Aromatic Hydrocarbon (PAH groups. The identification of gases evolved during the pyrolysis of the binders was carried out and their decomposition temperatures were determined using the Thermogravimetry–Gas Chromatography–Mass Spectrometry (TG–GC–MS technique. The tests were subjected to two types of binders from different manufacturers. Among the products of pyrolysis there have been identified mainly benzene and its derivatives, and phenol and its derivatives. Compounds identified in pyrolytic gas are largely considered to be harmful to humans and the environment (some of the compounds are carcinogenic and mutagenic. The presented results of the TG–GC–MS measurements show that the applied analytic methods are feasible to perform a qualitative and also quantitative characterization of the binder samples.
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International Nuclear Information System (INIS)
Orr, R.M.; Sims, H.E.; Taylor, R.J.
2015-01-01
Plutonium (IV) and (III) ions in nitric acid solution readily form insoluble precipitates with oxalic acid. The plutonium oxalates are then easily thermally decomposed to form plutonium dioxide powder. This simple process forms the basis of current industrial conversion or ‘finishing’ processes that are used in commercial scale reprocessing plants. It is also widely used in analytical or laboratory scale operations and for waste residues treatment. However, the mechanisms of the thermal decompositions in both air and inert atmospheres have been the subject of various studies over several decades. The nature of intermediate phases is of fundamental interest whilst understanding the evolution of gases at different temperatures is relevant to process control. The thermal decomposition is also used to control a number of powder properties of the PuO_2 product that are important to either long term storage or mixed oxide fuel manufacturing. These properties are the surface area, residual carbon impurities and adsorbed volatile species whereas the morphology and particle size distribution are functions of the precipitation process. Available data and experience regarding the thermal and radiation-induced decompositions of plutonium oxalate to oxide are reviewed. The mechanisms of the thermal decompositions are considered with a particular focus on the likely redox chemistry involved. Also, whilst it is well known that the surface area is dependent on calcination temperature, there is a wide variation in the published data and so new correlations have been derived. Better understanding of plutonium (III) and (IV) oxalate decompositions will assist the development of more proliferation resistant actinide co-conversion processes that are needed for advanced reprocessing in future closed nuclear fuel cycles. - Highlights: • Critical review of plutonium oxalate decomposition reactions. • New analysis of relationship between SSA and calcination temperature. • New SEM
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Energy Technology Data Exchange (ETDEWEB)
Machala, Libor, E-mail: libor.machala@upol.cz [Regional Centre of Advanced Technologies and Materials, Department of Experimental Physics, Faculty of Science, Palacký University, Olomouc (Czech Republic); Sharma, Virender K. [Department of Environmental and Occupational Health, School of Public Health, Texas A& M University, 1266 TAMU, College Station, TX 77843 (United States); Kuzmann, Ernö; Homonnay, Zoltán [Institute of Chemistry, Eötvös Loránd University, Budapest (Hungary); Filip, Jan; Kralchevska, Radina P. [Regional Centre of Advanced Technologies and Materials, Department of Experimental Physics, Faculty of Science, Palacký University, Olomouc (Czech Republic)
2016-05-25
Simple high-valent iron-oxo species, ferrate(VI) (Fe{sup VI}O{sub 4}{sup 2−}, Fe(VI)) has applications in energy storage, organic synthesis, and water purification. Of the various salts of Fe(VI), barium ferrate(VI) (BaFeO{sub 4}) has also a great potential as a battery material. This paper presents the thermal decomposition of BaFeO{sub 4} in static air and nitrogen atmosphere, monitored by combination of thermal analysis, Mössbauer spectroscopy, X-ray powder diffraction, and electron-microscopic techniques. The formation of Fe{sup IV} species in the form of BaFeO{sub 3} was found to be the primary decomposition product of BaFeO{sub 4} at temperature around 190 °C under both studied atmospheres. BaFeO{sub 3} was unstable in air reacting with CO{sub 2} to form barium carbonate and speromagnetic amorphous iron(III) oxide nanoparticles (<5 nm). Above 600 °C, a solid state reaction between BaCO{sub 3} and Fe{sub 2}O{sub 3} occurred, leading to the formation of barium ferrite nanoparticles, BaFe{sub 2}O{sub 4} (20–100 nm). - Highlights: • We explained the mechanism of thermal decomposition of barium ferrate(VI). • We confirmed the formation of Fe(IV) intermediate phase during the decomposition. • The mechanism of the decomposition is influenced by a presence of carbon dioxide.
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Directory of Open Access Journals (Sweden)
Elihu Paternina
2009-01-01
Full Text Available The kinetic study of decomposition of hydrogen peroxide catalyzed by activated carbon was carried out. The effect of concentrations of reactants and temperature were experimentally studied. Kinetic data were evaluated using differential method of initial rates of reaction. When a typical kinetic law for reactions in homogeneous phase is used, first order of reaction is obtained for hydrogen peroxide and activated carbon, and activation energy of 27 kJ mol-1 for the reaction was estimated. Experimentally was observed that surface of activated carbon is chemically modified during decomposition of hydrogen peroxide, based on this result a scheme of reaction was proposed and evaluated. Experimental data fits very well to a Langmuir- Hinshelwood kinetic model and activation energy of 40 kJ mol-1 was estimated for reaction in heterogeneous phase.
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Energy Technology Data Exchange (ETDEWEB)
Chrissafis, Konstantinos; Pavlidou, Eleni [Solid State Physics Section, Physics Department, Aristotle University of Thessaloniki, GR-541 24 Thessaloniki, Macedonia (Greece); Vouvoudi, Evangelia [Laboratory of Polymer Chemistry and Technology, Department of Chemistry, Aristotle University of Thessaloniki, GR-541 24 Thessaloniki, Macedonia (Greece); Bikiaris, Dimitrios, E-mail: dbic@chem.auth.gr [Laboratory of Polymer Chemistry and Technology, Department of Chemistry, Aristotle University of Thessaloniki, GR-541 24 Thessaloniki, Macedonia (Greece)
2014-05-01
Graphical abstract: - Highlights: • Syndiotactic polystyrene nanocomposites containing MWCNTs and nanodiamonds were prepared for first time. • Addition of nanofillers causes a substantial improvement of sPS thermal stability. • From EGA and Py-GC/MS, it was found that sPS decomposes through a radical process. • The decomposition mechanism of sPS was not affected by the addition of nanoparticles. - Abstract: In the present work, syndiotactic polystyrene (sPS) based nanocomposites containing 3 wt% of multi-walled carbon nanotubes (MWCNTs) and nanodiamonds (NDs) were prepared using the melt-mixing technique. Transmission electron microscopy (TEM) micrographs verified a good dispersion of the nanoparticles in the polymeric matrix, which resulted in a slight improvement of the mechanical properties of the nanocomposites. The addition of MWCNTs promotes the formation of β-type crystals while in sPS and sPS/NDs α-type crystals are mainly formed. From the thermogravimetric analysis experiments a substantial enhancement of sPS thermal stability was found, caused by the addition of nanofillers, especially from NDs. The temperature corresponding to a mass loss of 0.5% was found 295 °C for sPS, 352.4 °C for sPS-MWCNTs and 370.7 °C for sPS-NDs nanocomposites. The analytical method of Py-GC/MS was also used for further characterization of the samples. The main chain fragments collected from sPS pyrolysis were styrene monomers, dimers and trimers, while the three pyrolization temperatures applied (390, 420 and 500 °C) indicated some variations in intensity of decomposition fragments. The decomposition temperature as well as the nanoparticle addition (NDs or MWCNTs) affected the intensity of the recorded fragments but did not induce a change on the decomposition mechanism of sPS.
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Thermal degradation of CR-39 polymer in an inert atmosphere
International Nuclear Information System (INIS)
Kalsi, P.C.; Pandey, A.K.; Iyer, R.H.; Singh Mudher, K.D.
1995-01-01
The thermal degradation of CR-39 (allyl diglycol carbonate), a polymer widely used in nuclear science and technology, in an inert atmosphere has been studied using thermogravimetric analysis (TGA) and differential thermal analysis (DTA) techniques. The results are compared with the thermal degradation data of the polymer in an air atmosphere. The present studies showed that the thermal degradation of the polymer proceeds in two steps in an argon atmosphere as compared to three steps in air atmosphere. The mass losses in air are higher than that in argon due to the oxidative decomposition of the residue. The kinetics of the different stages of degradation were also evaluated from the TG curves. (author). 7 refs., 1 tab
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International Nuclear Information System (INIS)
Kandula, Syam; Jeevanandam, P.
2014-01-01
Highlights: • SiO 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 x @CdS nanoparticles show different optical properties compared to pure CdS. - Abstract: SiO x @CdS core–shell nanoparticles have been synthesized by a simple thermal decomposition approach. The synthesis involves two steps. In the first step, SiO x spheres were synthesized using StÖber’s process. Then, cadmium sulfide nanoparticles were deposited on the SiO 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 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 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 x @CdS core–shell nanoparticles compared to pure cadmium sulfide nanoparticles
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Coupling Chemical Kinetics and Flashes in Reactive, Thermal and Compositional Reservoir Simulation
DEFF Research Database (Denmark)
Kristensen, Morten Rode; Gerritsen, Margot G.; Thomsen, Per Grove
2007-01-01
of convergence and error test failures by more than 50% compared to direct integration without the new algorithm. To facilitate the algorithmic development we construct a virtual kinetic cell model. We use implicit one-step ESDIRK (Explicit Singly Diagonal Implicit Runge-Kutta) methods for integration...... of the kinetics. The kinetic cell model serves both as a tool for the development and testing of tailored solvers as well as a testbed for studying the interactions between chemical kinetics and phase behavior. A comparison between a Kvalue correlation based approach and a more rigorous equation of state based......Phase changes are known to cause convergence problems for integration of stiff kinetics in thermal and compositional reservoir simulations. We propose an algorithm for detection and location of phase changes based on discrete event system theory. The algorithm provides a robust way for handling...
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Synthesis and degradation kinetics of a novel polyester containing bithiazole rings
Energy Technology Data Exchange (ETDEWEB)
He, W., E-mail: hwdut2003@yahoo.com [Research Center of Plastic Engineering, Shenyang University of Chemical Technology, Shenyang 110142 (China); State Key Laboratory of Robotics (China); Department of Chemistry, University of the Free State (Qwaqwa Campus), Private Bag X13, Phuthaditjhaba 9866 (South Africa); Jiang, Y.Y. [Research Center of Plastic Engineering, Shenyang University of Chemical Technology, Shenyang 110142 (China); State Key Laboratory of Robotics (China); Luyt, A.S. [Department of Chemistry, University of the Free State (Qwaqwa Campus), Private Bag X13, Phuthaditjhaba 9866 (South Africa); Ocaya, R.O. [Department of Physics, University of the Free State (Qwaqwa Campus), Private Bag X13, Phuthaditjhaba 9866 (South Africa); Ge, T.J. [Research Center of Plastic Engineering, Shenyang University of Chemical Technology, Shenyang 110142 (China); State Key Laboratory of Robotics (China)
2011-10-20
Highlights: {yields} A novel Schiff base type polyester was synthesized and characterized by FTIR spectroscopy, elemental analysis, and X-ray diffraction spectroscopy. {yields} Thermal degradation of the polyester in nitrogen has been studied at several heating rates by thermogravimetric analysis. {yields} The activation energies were calculated by different methods. And the possible conversation function was estimated. {yields} The life time estimates for the polyester can be determined and the results demonstrate that the polymer possesses good thermal resistance. - Abstract: A novel Schiff base type polyester containing 2,2'-diamino-4,4'-bithiazole (DABT) was prepared by low-temperature interface polycondensation of 1,4-benzenedicarbonyl dichloride with 4,4'-(4,4'-bithiazole-2,2'-diylbis(imine-2,1-diyl) diphenol (BDDP), which is derived from a 2,2'-diamino-4,4'-bithiazole (DABT) Schiff base reacted with a 4-hydroxybenzaldehyde monomer. The newly generated polyester was characterized by FTIR spectroscopy, elemental analysis, and X-ray diffraction spectroscopy. The thermal decomposition was investigated in nitrogen atmosphere using thermogravimetric analysis. The activation energies of the decomposition step of the polyester were calculated through the isoconversional methods of Kissinger-Akahira-Sunose (K-A-S) and the iterative equation. In order to estimate the reaction model that best describes the experimental data, the use of an empirical kinetic equation based on that proposed by Sestak-Berggren was investigated here. On the basis of the kinetic data, the life time estimates for the polyester generated from the weight loss of 5%, 10%, and 15% were also constructed.
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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
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Xue, Kun; Wang, Lei; An, Jin; Xu, Jianbin
2011-05-13
The thermal decomposition of ultrathin HfO(2) films (∼0.6-1.2 nm) on Si by ultrahigh vacuum annealing (25-800 °C) is investigated in situ in real time by scanning tunneling microscopy. Two distinct thickness-dependent decomposition behaviors are observed. When the HfO(2) thickness is ∼ 0.6 nm, no discernible morphological changes are found below ∼ 700 °C. Then an abrupt reaction occurs at 750 °C with crystalline hafnium silicide nanostructures formed instantaneously. However, when the thickness is about 1.2 nm, the decomposition proceeds gradually with the creation and growth of two-dimensional voids at 800 °C. The observed thickness-dependent behavior is closely related to the SiO desorption, which is believed to be the rate-limiting step of the decomposition process.
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Thermal degradation of ternary blend films containing PVA/chitosan/vanillin
Kasai, Deepak; Chougale, Ravindra; Masti, Saraswati; Narasgoudar, Shivayogi
2018-05-01
The ternary chitosan/poly (vinyl alcohol)/vanillin blend films were prepared by solution casting method. The influence of equal weight percent of poly (vinyl alcohol) and vanillin on thermal stability of the chitosan blend films were investigated by using thermogravimetric analysis (TGA). The kinetic parameters such as enthalpy (ΔH*), entropy (ΔS*), and Gibbs free energy (ΔG*) in the first and second decomposition steps based on the thermogravimetric data were calculated. The thermal stabilities of the blend films were confirmed by thermodynamic parameters obtained in the activation energies, which indicated that increase in the equal weight percent of PVA/vanillin decreased the thermal stability of the chitosan film.
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Volkov, R. S.; Zhdanova, A. O.; Kuznetsov, G. V.; Strizhak, P. A.
2018-05-01
Experimental investigations on the characteristic time of suppression of the thermal decomposition reaction of typical forest combustible materials (aspen twigs, birch leaves, spruce needles, pine chips, and a mixture of these materials) and the volume of water required for this purpose have been performed for model fire hotbeds of different areas: SFCM = 0.0003-0.007 m2 and SFCM = 0.045-0.245 m2. In the experiments, aerosol water flows with droplets of size 0.01-0.25 mm were used for the spraying of model fire hotbeds, and the density of spraying was 0.02 L/(m2·s). It was established that the characteristics of suppression of a fire by an aerosol water flow are mainly determined by the sizes of the droplets in this flow. Prognostic estimates of changes in the dispersivity of a droplet cloud, formed from large (as large as 0.5 L) "drops" (water agglomerates) thrown down from a height, have been made. It is shown that these changes can influence the conditions and characteristics of suppression of a forest fire. Dependences, allowing one to forecast the characteristics of suppression of the thermal decomposition of forest combustible materials with the use of large water agglomerates thrown down from an aircraft and aerosol clouds formed from these agglomerates in the process of their movement to the earth, are presented.
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Volkov, R. S.; Zhdanova, A. O.; Kuznetsov, G. V.; Strizhak, P. A.
2018-03-01
Experimental investigations on the characteristic time of suppression of the thermal decomposition reaction of typical forest combustible materials (aspen twigs, birch leaves, spruce needles, pine chips, and a mixture of these materials) and the volume of water required for this purpose have been performed for model fire hotbeds of different areas: SFCM = 0.0003-0.007 m2 and SFCM = 0.045-0.245 m2. In the experiments, aerosol water flows with droplets of size 0.01-0.25 mm were used for the spraying of model fire hotbeds, and the density of spraying was 0.02 L/(m2·s). It was established that the characteristics of suppression of a fire by an aerosol water flow are mainly determined by the sizes of the droplets in this flow. Prognostic estimates of changes in the dispersivity of a droplet cloud, formed from large (as large as 0.5 L) "drops" (water agglomerates) thrown down from a height, have been made. It is shown that these changes can influence the conditions and characteristics of suppression of a forest fire. Dependences, allowing one to forecast the characteristics of suppression of the thermal decomposition of forest combustible materials with the use of large water agglomerates thrown down from an aircraft and aerosol clouds formed from these agglomerates in the process of their movement to the earth, are presented.
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International Nuclear Information System (INIS)
Mercadante, A.
1991-01-01
Solid state compounds of lanthanides (III) and yttrium derived from ethyl ene diamine tetraacetic acid were prepared from respective basic carbonates, that were neutralized with EDTA stoichiometry quantities. Complexometry with EDTA, thermogravimetry (TG), differential thermal analysis (DTA) and X-ray diffraction have been used in the study of these compounds. The results of complexometry with EDTA as well as TG and DTA curves bed to the stoichiometry of these compounds the following general formula is obeyed: H[Ln(EDTA]. n H 2 O. X-ray powder patterns of these compounds permitted to establish two isomorphous series. The DTA ant TG curves allowed us to study the dehydration process, the thermal stability and thermal decomposition of these compounds. (C.G.C.)
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Duemichen, E; Braun, U; Senz, R; Fabian, G; Sturm, H
2014-08-08
For analysis of the gaseous thermal decomposition products of polymers, the common techniques are thermogravimetry, combined with Fourier transformed infrared spectroscopy (TGA-FTIR) and mass spectrometry (TGA-MS). These methods offer a simple approach to the decomposition mechanism, especially for small decomposition molecules. Complex spectra of gaseous mixtures are very often hard to identify because of overlapping signals. In this paper a new method is described to adsorb the decomposition products during controlled conditions in TGA on solid-phase extraction (SPE) material: twisters. Subsequently the twisters were analysed with thermal desorption gas chromatography mass spectrometry (TDS-GC-MS), which allows the decomposition products to be separated and identified using an MS library. The thermoplastics polyamide 66 (PA 66) and polybutylene terephthalate (PBT) were used as example polymers. The influence of the sample mass and of the purge gas flow during the decomposition process was investigated in TGA. The advantages and limitations of the method were presented in comparison to the common analysis techniques, TGA-FTIR and TGA-MS. Copyright © 2014 Elsevier B.V. All rights reserved.
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Thermal contact through a two-temperature kinetic Ising chain
Bauer, M.; Cornu, F.
2018-05-01
We consider a model for thermal contact through a diathermal interface between two macroscopic bodies at different temperatures: an Ising spin chain with nearest neighbor interactions is endowed with a Glauber dynamics with different temperatures and kinetic parameters on alternating sites. The inhomogeneity of the kinetic parameter is a novelty with respect to the model of Racz and Zia (1994 Phys. Rev. E 49 139), and we exhibit its influence upon the stationary non equilibrium values of the two-spin correlations at any distance. By mapping to the dynamics of spin domain walls and using free fermion techniques, we determine the scaled generating function for the cumulants of the exchanged heat amounts per unit of time in the long time limit.
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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.
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Study of 'liquid gold' coatings: Thermal decomposition and formation of metallic thin films
Energy Technology Data Exchange (ETDEWEB)
Deram, V. [Laboratoire de Spectrochimie Infrarouge et Raman, Universite des Sciences et Technologies de Lille, UMR CNRS 8516, Bat C5 - 59655 Villeneuve d' Ascq (France) and Ecole Nationale Superieure des Mines de Paris, Centre de Mise en Forme des Materiaux, UMR CNRS 7635, BP 207, 06904 Sophia-Antipolis (France)]. E-mail: virginie.deram@ensmp.fr; Turrell, S. [Laboratoire de Spectrochimie Infrarouge et Raman, Universite des Sciences et Technologies de Lille, UMR CNRS 8516, Bat C5 - 59655 Villeneuve d' Ascq (France); Darque-Ceretti, E. [Ecole Nationale Superieure des Mines de Paris, Centre de Mise en Forme des Materiaux, UMR CNRS 7635, BP 207, 06904 Sophia-Antipolis (France); Aucouturier, M. [Centre de Recherche et de Restauration des Musees de France, UMR CNRS 171, Palais du Louvre, Porte des Lions, 14 quai F. Mitterrand, 75001 Paris Cedex (France)
2006-09-25
Organo-metallic solutions called liquid gold are largely used to obtain thin gilded films which are employed for decorative, technological and functional uses. However, these films often prove to be fragile with respect to use, resulting in loss of brilliance or even eventual film removal. An understanding of the behaviour of the layers requires good knowledge of the materials themselves. The present work was undertaken to better understand the evolution of the structural properties of liquid gold as it undergoes heat-processing. Accordingly, we followed the thermal decomposition processes of liquid gold coatings and the formation of the gilded metal layer using a combination of experimental techniques. First, thermal analyses coupled with mass spectrometry and infrared spectroscopy gave information concerning the decomposition of the organic medium. It has been found that the process of film formation can be decomposed into three steps, the second of which is an abrupt transition between 300 and 350 deg. C. Details on this transition have been obtained using real-time X-ray Diffraction and Rutherford Backscattering Spectrometry. Above 350 deg. C, the microstructure of the coating is reorganized to obtain a final layer which contains particles, of the size of a few hundreds nanometers, as shown by Transmission Electron Microscopy.
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Directory of Open Access Journals (Sweden)
Su-Ju Kim
1997-12-01
Full Text Available To understand the mass-independent isotopic fractionation effects, thermal decomposition of ozone was performed. Initial oxygen gas was converted to ozone completely. Then, the ozone was decomposed to oxygen at various temperatures(30~150C. Isotopic compositions of product oxygen and residual ozone were measured using a stable isotope mass spectrometer. The experimental results were compared with the studies which were peformed at the similar conditions. From the raw experimental data, the functions of the instantaneous fractionation factors were calculated by the least square fit. The results clearly showed the temperature dependence. They also showed the pressure dependence and the surface effect. This study may play an important role in the study of ozone decomposition mechanism. It can be applied to explain the mass-independent isotopic pattern found in stratospheric ozone and in meteorites.
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Kinetic analysis of the termal decomposition of colombian vacuum residua by termogravimetry
Directory of Open Access Journals (Sweden)
Fabian Andrey Diaz Mateus
2015-09-01
Full Text Available Five different Colombian vacuum residues were thermally decomposed in a thermogravimetric analyzer. Three heating rates were employed to heat the sample up to 650°C. The kinetic analysis was performed by the Coats-Redfern method to describe the non-isothermal pyrolysis of the residua, a reaction model where the reaction order gradually increases from first to second order is proposed and an excellent agreement of the experimental with the calculated data is presented. The results also indicate that the pyrolysis of a vacuum residue cannot be modeled by a single reaction mechanism.
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Reactor thermal behaviors under kinetics parameters variations in fast reactivity insertion
Energy Technology Data Exchange (ETDEWEB)
Abou-El-Maaty, Talal [Reactors Department, Atomic Energy Authority, Cairo 13759 (Egypt)], E-mail: talal22969@yahoo.com; Abdelhady, Amr [Reactors Department, Atomic Energy Authority, Cairo 13759 (Egypt)
2009-03-15
The influences of variations in some of the kinetics parameters affecting the reactivity insertion are considered in this study, it has been accomplished in order to acquire knowledge about the role that kinetic parameters play in prompt critical transients from the safety point of view. The kinetics parameters variations are limited to the effective delayed neutron fraction ({beta}{sub eff}) and the prompt neutron generation time ({lambda}). The reactor thermal behaviors under the variations in effective delayed neutron fraction and prompt neutron generation time included, the reactor power, maximum fuel temperature, maximum clad temperature, maximum coolant temperature and the mass flux variations at the hot channel. The analysis is done for a typical swimming pool, plate type research reactor with low enriched uranium. The scram system is disabled during the accidents simulations. Calculations were done using PARET code. As a result of simulations, it is concluded that, the reactor (ETRR2) thermal behavior is considerably more sensitive to the variation in the effective delayed neutron fraction than to the variation in prompt neutron generation time and the fast reactivity insertion in both cases causes a flow expansion and contraction at the hot channel exit. The amplitude of the oscillated flow is a qualitatively increases with the decrease in both {beta}{sub eff} and {lambda}.
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International Nuclear Information System (INIS)
Li Yongsheng; Zhu Hao; Zhang Lei; Cheng Xiaoling
2012-01-01
Highlights: ► Effects of variation mobility and applied strain on phase decomposition of Fe–Cr alloy were studied. ► Rate of phase decomposition rises as aging temperature and concentration increase. ► Phase transformation mechanism affects the volume fraction of equilibrium phase. ► Elongate morphology is intensified at higher aging temperature under applied strain. - Abstract: The phase decomposition and morphology evolution in thermal aging Fe–Cr alloys were investigated using the phase field method. In the simulation, the effects of atomic mobility, applied strain, alloy concentration and aging temperature were studied. The simulation results show that the rate of phase decomposition is influenced by the aging temperature and the alloy concentration, the equilibrium volume fractions (V f e ) of Cr-rich phase increases as aging temperature rises for the alloys of lower concentration, and the V f e decreases for the alloys with higher concentration. Under the applied strain, the orientation of Cr-rich phase is intensified as the aging temperature rises, and the stripe morphology is formed for the middle concentration alloys. The simulation results are helpful for understanding the phase decomposition in Fe–Cr alloys and the designing of duplex stainless steels working at high temperature.
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The thermal stability of sodium beta'-Alumina solid electrolyte ceramic in AMTEC cells
International Nuclear Information System (INIS)
Williams, Roger M.; Ryan, Margaret A.; Homer, Margie L.; Lara, Liana; Manatt, Ken; Shields, Virgil; Cortez, Roger H.; Kulleck, James
1999-01-01
A critical component of alkali metal thermal-to electric converter (AMTEC) devices for long duration space missions is the beta'-alumina solid electrolyte ceramic (BASE), for which there exists no substitute. The temperature and environmental conditions under which BASE remains stable control operational parameters of AMTEC devices. We have used mass loss experiments in vacuum to 1573K to characterize the kinetics of BASE decomposition, and conductivity and exchange current measurements in sodium vapor filled exposure cells to 1223K to investigate changes in the BASE which affect its ionic conductivity. There is no clear evidence of direct thermal decomposition of BASE below 1273K, although limited soda loss may occur. Reactive metals such as Mn or Cr can react with BASE at temperatures at least as low as 1223K
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Revisiting the effects of organic solvents on the thermal reduction of graphite oxide
International Nuclear Information System (INIS)
Barroso-Bujans, Fabienne; Fierro, José Luis G.; Alegría, Angel; Colmenero, Juan
2011-01-01
Highlights: ► Retention of organic solvent on graphite oxide interlayer space. ► Decreasing exfoliation temperature. ► Close link between structure and thermal behavior of solvent treated graphite oxide. ► Restacking inhibition of thermally reduced graphite oxide sheets. ► Changes in kinetic mechanisms of thermal reduction. - Abstract: Treatment of graphite oxide (GO) with organic solvents via sorption from either liquid or gas phase, and subsequent desorption, induces profound changes in the layered GO structure: loss of stacking order, retention of trace amounts of solvents and decreasing decomposition temperature. This study presents new evidences of the effect of organic solvents on the thermal reduction of GO by means of thermogravimetric analysis, X-ray diffraction and X-ray photoelectron spectroscopy. The results reveal a relative higher decrease of the oxygen amounts in solvent-treated GO as compared to untreated GO and the restacking inhibition of the thermally reduced GO sheets upon slow heating. The kinetic experiments evidence changes occurring in the reduction mechanisms of the solvent-treated GO, which support the close link between GO structure and thermal properties.
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Directory of Open Access Journals (Sweden)
Daniele Cavalli
2016-09-01
Full Text Available Two features distinguishing soil organic matter simulation models are the type of kinetics used to calculate pool decomposition rates, and the algorithm used to handle the effects of nitrogen (N shortage on carbon (C decomposition. Compared to widely used first-order kinetics, Monod kinetics more realistically represent organic matter decomposition, because they relate decomposition to both substrate and decomposer size. Most models impose a fixed C to N ratio for microbial biomass. When N required by microbial biomass to decompose a given amount of substrate-C is larger than soil available N, carbon decomposition rates are limited proportionally to N deficit (N inhibition hypothesis. Alternatively, C-overflow was proposed as a way of getting rid of excess C, by allocating it to a storage pool of polysaccharides. We built six models to compare the combinations of three decomposition kinetics (first-order, Monod, and reverse Monod, and two ways to simulate the effect of N shortage on C decomposition (N inhibition and C-overflow. We conducted sensitivity analysis to identify model parameters that mostly affected CO2 emissions and soil mineral N during a simulated 189-day laboratory incubation assuming constant water content and temperature. We evaluated model outputs sensitivity at different stages of organic matter decomposition in a soil amended with three inputs of increasing C to N ratio: liquid manure, solid manure, and low-N crop residue. Only few model parameters and their interactions were responsible for consistent variations of CO2 and soil mineral N. These parameters were mostly related to microbial biomass and to the partitioning of applied C among input pools, as well as their decomposition constants. In addition, in models with Monod kinetics, CO2 was also sensitive to a variation of the half-saturation constants. C-overflow enhanced pool decomposition compared to N inhibition hypothesis when N shortage occurred. Accumulated C in the
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Energy Technology Data Exchange (ETDEWEB)
Orr, R.M.; Sims, H.E.; Taylor, R.J., E-mail: robin.j.taylor@nnl.co.uk
2015-10-15
Plutonium (IV) and (III) ions in nitric acid solution readily form insoluble precipitates with oxalic acid. The plutonium oxalates are then easily thermally decomposed to form plutonium dioxide powder. This simple process forms the basis of current industrial conversion or ‘finishing’ processes that are used in commercial scale reprocessing plants. It is also widely used in analytical or laboratory scale operations and for waste residues treatment. However, the mechanisms of the thermal decompositions in both air and inert atmospheres have been the subject of various studies over several decades. The nature of intermediate phases is of fundamental interest whilst understanding the evolution of gases at different temperatures is relevant to process control. The thermal decomposition is also used to control a number of powder properties of the PuO{sub 2} product that are important to either long term storage or mixed oxide fuel manufacturing. These properties are the surface area, residual carbon impurities and adsorbed volatile species whereas the morphology and particle size distribution are functions of the precipitation process. Available data and experience regarding the thermal and radiation-induced decompositions of plutonium oxalate to oxide are reviewed. The mechanisms of the thermal decompositions are considered with a particular focus on the likely redox chemistry involved. Also, whilst it is well known that the surface area is dependent on calcination temperature, there is a wide variation in the published data and so new correlations have been derived. Better understanding of plutonium (III) and (IV) oxalate decompositions will assist the development of more proliferation resistant actinide co-conversion processes that are needed for advanced reprocessing in future closed nuclear fuel cycles. - Highlights: • Critical review of plutonium oxalate decomposition reactions. • New analysis of relationship between SSA and calcination temperature.
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A generalized interface module for the coupling of spatial kinetics and thermal-hydraulics codes
Energy Technology Data Exchange (ETDEWEB)
Barber, D.A.; Miller, R.M.; Joo, H.G.; Downar, T.J. [Purdue Univ., West Lafayette, IN (United States). Dept. of Nuclear Engineering; Wang, W. [SCIENTECH, Inc., Rockville, MD (United States); Mousseau, V.A.; Ebert, D.D. [Nuclear Regulatory Commission, Washington, DC (United States). Office of Nuclear Regulatory Research
1999-03-01
A generalized interface module has been developed for the coupling of any thermal-hydraulics code to any spatial kinetics code. The coupling scheme was designed and implemented with emphasis placed on maximizing flexibility while minimizing modifications to the respective codes. In this design, the thermal-hydraulics, general interface, and spatial kinetics codes function independently and utilize the Parallel Virtual Machine software to manage cross-process communication. Using this interface, the USNRC version of the 3D neutron kinetics code, PARCX, has been coupled to the USNRC system analysis codes RELAP5 and TRAC-M. RELAP5/PARCS assessment results are presented for two NEACRP rod ejection benchmark problems and an NEA/OECD main steam line break benchmark problem. The assessment of TRAC-M/PARCS has only recently been initiated, nonetheless, the capabilities of the coupled code are presented for a typical PWR system/core model.
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A generalized interface module for the coupling of spatial kinetics and thermal-hydraulics codes
International Nuclear Information System (INIS)
Barber, D.A.; Miller, R.M.; Joo, H.G.; Downar, T.J.; Mousseau, V.A.; Ebert, D.D.
1999-01-01
A generalized interface module has been developed for the coupling of any thermal-hydraulics code to any spatial kinetics code. The coupling scheme was designed and implemented with emphasis placed on maximizing flexibility while minimizing modifications to the respective codes. In this design, the thermal-hydraulics, general interface, and spatial kinetics codes function independently and utilize the Parallel Virtual Machine software to manage cross-process communication. Using this interface, the USNRC version of the 3D neutron kinetics code, PARCX, has been coupled to the USNRC system analysis codes RELAP5 and TRAC-M. RELAP5/PARCS assessment results are presented for two NEACRP rod ejection benchmark problems and an NEA/OECD main steam line break benchmark problem. The assessment of TRAC-M/PARCS has only recently been initiated, nonetheless, the capabilities of the coupled code are presented for a typical PWR system/core model
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International Nuclear Information System (INIS)
Jimenez, J.; Herrero, J. J.; Cuervo, D.; Aragones, J. M.
2010-10-01
Nowadays coupled 3-dimensional neutron kinetics and thermal-hydraulic core calculations are performed by applying a radial average channel approach using a meshing of one quarter of assembly in the best case. This approach does not take into account the subchannels effects due to the averaging of the physical fields and the loose of heterogeneity in the thermal-hydraulic model. Therefore the models do not have enough resolution to predict those subchannels effects which are important for the fuel design safety margins, because it is in the local scale, where we can search the hottest pellet or the maximum heat flux. The Polytechnic University of Madrid advanced multi-scale neutron-kinetics and thermal-hydraulics methodologies being implemented in COBAYA3 include domain decomposition by alternate core dissections for the local 3-dimensional fine-mesh scale problems (pin cells/subchannels) and an analytical nodal diffusion solver for the coarse mesh scale coupled with the thermal-hydraulic using a model of one channel per assembly or per quarter of assembly. In this work, we address the domain decomposition by the alternate core dissections methodology applied to solve coupled 3-dimensional neutronic-thermal-hydraulic problems at the fine-mesh scale. The neutronic-thermal-hydraulic coupling at the cell-subchannel scale allows the treatment of the effects of the detailed thermal-hydraulic feedbacks on cross-sections, thus resulting in better estimates of the local safety margins at the pin level. (Author)
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Asanova, Tatyana I.; Asanov, Igor P.; Kim, Min-Gyu; Gerasimov, Evgeny Yu.; Zadesenets, Andrey V.; Plyusnin, Pavel E.; Korenev, Sergey V.
2013-10-01
The formation mechanism of Pd-Ir nanoparticles during thermal decomposition of double complex salt [Pd(NH3)4][IrCl6] 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 °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.
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International Nuclear Information System (INIS)
Asanova, Tatyana I.; Asanov, Igor P.; Kim, Min-Gyu; Gerasimov, Evgeny Yu.; Zadesenets, Andrey V.; Plyusnin, Pavel E.; Korenev, Sergey V.
2013-01-01
The formation mechanism of Pd–Ir nanoparticles during thermal decomposition of double complex salt [Pd(NH 3 ) 4 ][IrCl 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 °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
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Atmospheric chemistry of HFC-134a. Kinetic and mechanistic study of the CF3CFHO2 + NO2 reaction
DEFF Research Database (Denmark)
Møgelberg, T.E.; Nielsen, O.J.; Sehested, J.
1994-01-01
A pulse radiolysis system was used to study the kinetics of the reaction of CF3CFHO2 with NO2. By monitoring the rate of the decay of NO2 using its absorption at 400 nm the reaction rate constant was determined to be k = (5.0 +/- 0.5) x 10(-12) cm3 molecule-1 s-1. A long path length Fourier......-transform infrared technique was used to investigate the thermal decomposition of the product CF3CFHO2NO2. At 296 K in the presence of 700 Torr of air, decomposition of CF3CFHO2NO2 was rapid (greater than 90% decomposition within 3 min). The results are discussed in the context of atmospheric chemistry of CF3CFH2...
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Synthesis of In2O3nanoparticles by thermal decomposition of a citrate gel precursor
International Nuclear Information System (INIS)
Rey, J. F. Q.; Plivelic, T. S.; Rocha, R. A.; Tadokoro, S. K.; Torriani, I.; Muccillo, E. N. S.
2005-01-01
This paper describes the synthesis of indium oxide by a modified sol-gel method, and the study of thermal decomposition of the metal complex in air. The characterization of the intermediate as well as the final compounds was carried out by thermogravimetry, differential thermal analysis, Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy, and small angle X-ray scattering. The results show that the indium complex decomposes to In 2 O 3 with the formation of an intermediate compound. Nanoparticles of cubic In 2 O 3 with crystallite sizes in the nanosize range were formed after calcination at temperatures up to 900 deg. C. Calcined materials are characterized by a polydisperse distribution of spherical particles with sharp and smooth surfaces
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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.
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Liu, Qiusheng; Yabe, Akira; Kajiyama, Shiro; Fukuda, Katsuya
The study on thermal energy transport system by synthesis and decomposition reactions of methanol was reviewed. To promote energy conservation and global environment protection, a two-step liquid-phase methanol synthesis process, which starts with carbonylation of methanol to methyl formate, then followed by the hydrogenolysis of the formate, was studied to recover wasted or unused discharged heat from industrial sources for the thermal energy demands of residential and commercial areas by chemical reactions. The research and development of the system were focused on the following three points. (1) Development of low-temperature decomposition and synthetic catalysts, (2) Development of liquid phase reactor (heat exchanger accompanying chemical reaction), (3) Simulation of the energy transport efficiency of entire system which contains heat recovery and supply sections. As the result of the development of catalyst, promising catalysts which agree with the development purposes for the methyl formate decomposition reaction and the synthetic reaction are being developed though some studies remain for the methanol decomposition and synthetic reactions. In the fundamental development of liquid phase reactor, the solubilities of CO and H2 gases in methanol and methyl formate were measured by the method of total pressure decrease due to absorption under pressures up to 1500kPa and temperatures up to 140°C. The diffusivity of CO gas in methanol was determined by measuring the diameter and solution time of single CO bubbles in methanol. The chemical reaction rate of methanol synthesis by hydrogenolysis of methyl formate was measured using a plate-type of Raney copper catalyst in a reactor with rectangular channel and in an autoclave reactor. The reaction characteristics were investigated by carrying out the experiments at various temperatures, flow rates and at various catalyst development conditions. We focused on the effect of Raney copper catalyst thickness on the liquid
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International Nuclear Information System (INIS)
Frost, Ray L.; Erickson, Kristy L.; Weier, Matt L.; McKinnon, Adam R.; Williams, Peter A.; Leverett, Peter
2005-01-01
The thermal decomposition of a suite of synthetic agardites of formula ACu 6 (AsO 4 ) 2 (OH) 6 ·3H 2 O where A is given by a rare earth element has been studied using thermogravimetric analysis techniques. Dehydration of the agardites occurs at low temperatures and over an extended temperature range from ambient to around 60 deg. C. This loss of water is attributed to the loss of zeolitic water. The mass loss of water indicates 3 mol of zeolitic water in the structure. Dehydroxylation occurs in steps over a wide range of temperatures from 235 to 456 deg. C. The mass loss during dehydroxylation shows the number of moles of hydroxyl units is six. There is a linear relationship between the first dehydroxylation temperature and the electronegativity of the agardites (REE)
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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.
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Numerical Investigation into CO Emission, O Depletion, and Thermal Decomposition in a Reacting Slab
Directory of Open Access Journals (Sweden)
O. D. Makinde
2011-01-01
Full Text Available The emission of carbon dioxide (CO2 is closely associated with oxygen (O2 depletion, and thermal decomposition in a reacting stockpile of combustible materials like fossil fuels (e.g., coal, oil, and natural gas. Moreover, it is understood that proper assessment of the emission levels provides a crucial reference point for other assessment tools like climate change indicators and mitigation strategies. In this paper, a nonlinear mathematical model for estimating the CO2 emission, O2 depletion, and thermal stability of a reacting slab is presented and tackled numerically using a semi-implicit finite-difference scheme. It is assumed that the slab surface is subjected to a symmetrical convective heat and mass exchange with the ambient. Both numerical and graphical results are presented and discussed quantitatively with respect to various parameters embedded in the problem.
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Xu, Xin-Qi; Shi, Yan; Wu, Xiao-Bing; Zhan, Xi-Lan; Zhou, Han-Tao; Chen, Qing-Xi
2015-11-01
Thermal inactivation kinetics of Hypocrea orientalis β-glucosidase and effect of glucose on thermostability of the enzyme have been determined in this paper. Kinetic studies showed that the thermal inactivation was irreversible and first-order reaction. The microscopic rate constants for inactivation of free enzyme and substrate-enzyme complex were both determined, which suggested that substrates can protect β-glucosidase against thermal deactivation effectively. On the other hand, glucose was found to protect β-glucosidase from heat inactivation to remain almost whole activity below 70°C at 20mM concentration, whereas the apparent inactivation rate of BG decreased to be 0.3×10(-3)s(-1) in the presence of 5mM glucose, smaller than that of sugar-free enzyme (1.91×10(-3)s(-1)). The intrinsic fluorescence spectra results showed that glucose also had stabilizing effect on the conformation of BG against thermal denaturation. Docking simulation depicted the interaction mode between glucose and active residues of the enzyme to produce stabilizing effect. Copyright © 2015 Elsevier B.V. All rights reserved.
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Volpe, V; Brunetti, B; Gigli, G; Lapi, A; Vecchio Ciprioti, S; Ciccioli, A
2017-11-16
The evaporation/decomposition behavior of the imidazolium ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMImPF 6 ) was investigated in the overall temperature range 425-551 K by means of the molecular-effusion-based techniques Knudsen effusion mass loss (KEML) and Knudsen effusion mass spectrometry (KEMS), using effusion orifices of different size (from 0.2 to 3 mm in diameter). Specific effusion fluxes measured by KEML were found to depend markedly on the orifice size, suggesting the occurrence of a kinetically delayed evaporation/decomposition process. KEMS experiments revealed that other species are present in the vapor phase besides the intact ion pair BMImPF 6 (g) produced by the simple evaporation BMImPF 6 (l) = BMImPF 6 (g), with relative abundances depending on the orifice size-the larger the orifice, the larger the contribution of the BMImPF 6 (g) species. By combining KEML and KEMS results, the conclusion is drawn that in the investigated temperature range, when small effusion orifices are used, a significant part of the mass loss/volatility of BMImPF 6 is due to molecular products formed by decomposition/dissociation processes rather than to evaporated intact ion pairs. Additional experiments performed by nonisothermal thermogravimetry-differential thermal analysis (TG-DTA) further support the evidence of simultaneous evaporation/decomposition, although the conventional decomposition temperature derived from TG curves is much higher than the temperatures covered in effusion experiments. Partial pressures of the BMImPF 6 (g) species were derived from KEMS spectra and analyzed by second- and third-law methods giving a value of Δ evap H 298K ° = 145.3 ± 2.9 kJ·mol -1 for the standard evaporation enthalpy of BMImPF 6 . A comparison is done with the behavior of the 1-butyl-3-methylimidazolium bis(trifluoromethyl)sulfonylimide (BMImNTf 2 ) ionic liquid.
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Thermal degradation kinetics and estimation of lifetime of radiation grafted polypropylene films
International Nuclear Information System (INIS)
Mandal, Dev K.; Bhunia, Haripada; Bajpai, Pramod K.; Bhalla, Vinod Kumar
2017-01-01
In this research work, thermal stability and degradation behavior of acrylic acid grafted polypropylene (PP-g-PAAc) films were investigated by using thermogravimetric (TGA) analysis at four different heating rates 5, 10, 15 and 20 °C/min over a temperature range of 40–550 °C in nitrogen atmosphere. The kinetic parameters namely activation energy (E a ), reaction order (n) and frequency factor (Z) were calculated by three multiple heating rate methods. The thermal stability of PP-g-PAAc films is found to decrease with increase in degree of grafting. The TGA data and thermal kinetic parameters were also used to predict the lifetime of grafted PP films. The estimated lifetime of neat PP as well as grafted PP decreased with increase in temperature by all the three methods. Studies also indicated that E a and lifetime of PP-g-PAAc films decreased with increase in degree of grafting, which may also be helpful in biodegradation of grafted PP films. - Highlights: • Thermal stability of grafted polypropylene films have been observed lower than for neat polypropylene film. • Multiple heating rate methods have been used for determination of activation energy. • Activation energies of grafted polypropylene films were lower than polypropylene film. • The lifetimes of grafted polypropylene films were shorter than for neat polypropylene film.
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Orr, R. M.; Sims, H. E.; Taylor, R. J.
2015-10-01
Plutonium (IV) and (III) ions in nitric acid solution readily form insoluble precipitates with oxalic acid. The plutonium oxalates are then easily thermally decomposed to form plutonium dioxide powder. This simple process forms the basis of current industrial conversion or 'finishing' processes that are used in commercial scale reprocessing plants. It is also widely used in analytical or laboratory scale operations and for waste residues treatment. However, the mechanisms of the thermal decompositions in both air and inert atmospheres have been the subject of various studies over several decades. The nature of intermediate phases is of fundamental interest whilst understanding the evolution of gases at different temperatures is relevant to process control. The thermal decomposition is also used to control a number of powder properties of the PuO2 product that are important to either long term storage or mixed oxide fuel manufacturing. These properties are the surface area, residual carbon impurities and adsorbed volatile species whereas the morphology and particle size distribution are functions of the precipitation process. Available data and experience regarding the thermal and radiation-induced decompositions of plutonium oxalate to oxide are reviewed. The mechanisms of the thermal decompositions are considered with a particular focus on the likely redox chemistry involved. Also, whilst it is well known that the surface area is dependent on calcination temperature, there is a wide variation in the published data and so new correlations have been derived. Better understanding of plutonium (III) and (IV) oxalate decompositions will assist the development of more proliferation resistant actinide co-conversion processes that are needed for advanced reprocessing in future closed nuclear fuel cycles.
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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...
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International Nuclear Information System (INIS)
El-Sayed, Saad A.; Mostafa, M.E.
2014-01-01
Highlights: • The sugarcane bagasse powder has better energy value compared to the cotton stalks. • Bagasse moisture is entrained in its cell walls and its evaporation needs more energy. • The cotton stalks is more reactive and readily combustible than the bagasse powders. • A lower E and A 0 has been found for bagasse compared with cotton stalks powders. • Calculated E of bagasse and cotton stalks by direct and integral methods are different. - Abstract: The kinetics of the thermal decomposition of the two biomass materials (sugarcane bagasse and cotton stalks powders) were evaluated using a differential thermo-gravimetric analyzer under a non-isothermal condition. Two distinct reaction zones were observed for the two biomasses. The direct Arrhenius plot method and the integral method were applied for determination of kinetic parameters: activation energy, pre-exponential factor, and order of reaction. The weight loss curve showed that pyrolysis of sugarcane bagasse and cotton stalks took place mainly in the range of 200–500 °C. The activation energy of the sugarcane bagasse powder obtained by the direct Arrhenius plot method ranged between 43 and 53.5 kJ/mol. On the other side, the integral method shows larger values of activation energy (77–87.7 kJ/mol). The activation energy of the cotton stalks powder obtained by the direct Arrhenius plot method was ranged between 98.5 and 100.2 kJ/mol, but the integral method shows larger values of activation energy (72.5–127.8 kJ/mol)
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Kinetic mechanism of the decomposition of dimethyltin dichloride
Mol, van A.M.B.; Croon, de M.H.J.M.; Spee, C.I.M.A.; Schouten, J.C.
1999-01-01
Results are reported of a study of the intrinsic kinetics of gas phase reactions. For this purpose a reactor system is designed in such a way that concentration and temperature variations throughout the reactor can be neglected enabling investigation of intrinsic reaction kinetics. The gas phase
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Advanced kinetics for calorimetric techniques and thermal stability screening of sulfide minerals
International Nuclear Information System (INIS)
Iliyas, Abduljelil; Hawboldt, Kelly; Khan, Faisal
2010-01-01
Thermal methods of analysis such as differential scanning calorimetry (DSC) provide a powerful methodology for the study of solid reactions. This paper proposes an improved thermal analysis methodology for thermal stability investigation of complex solid-state reactions. The proposed methodology is based on differential iso-conversional approach and involves peak separation, individual peak analysis and combination of isothermal/non-isothermal DSC measurements for kinetic analysis and prediction. The proposed thermal analysis, which coupled with Mineral Libration Analyzer (MLA) technique was employed to investigate thermal behavior of sulfide mineral oxidation. The importance of various experimental variables such as particle size, heating rate and atmosphere were investigated and discussed. The information gained from such an advanced thermal analysis method is useful for scale-up processes with potential of significant savings in plant operations, as well as in mitigating adverse environmental and safety issues arising from handling and storage of sulfide minerals.
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Kinetic study of corn straw pyrolysis: comparison of two different three-pseudocomponent models.
Li, Zhengqi; Zhao, Wei; Meng, Baihong; Liu, Chunlong; Zhu, Qunyi; Zhao, Guangbo
2008-11-01
With heating rates of 20, 50 and 100 K min(-1), the thermal decomposition of corn straw samples (corn stalks skins, corn stalks cores, corn bracts and corn leaves) were studied using thermogravimetric analysis. The maximum pyrolysis rates increased with the heating rate increasing and the temperature at the peak pyrolysis rate also increased. Assuming the addition of three independent parallel reactions, corresponding to three pseudocomponents linked to the hemicellulose, cellulose and lignin, two different three-pseudocomponent models were used to simulate the corn straw pyrolysis. Model parameters of pyrolysis were given. It was found that the three-pseudocomponent model with n-order kinetics was more accurate than the model with first-order kinetics at most cases. It showed that the model with n-order kinetics was more accurate to describe the pyrolysis of the hemicellulose.
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The Decomposition of Surrogate Fuel Molecules During Combustion
National Research Council Canada - National Science Library
Tsang, Wing; Manion, Jeffrey A
2006-01-01
This project is aimed at developing a chemical kinetic database consisting of the rate constants of fundamental single step reactions that describe the pyrolytic decomposition of surrogate fuels molecules...
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Preparation, Structure Characterization and Thermal Decomposition ...
African Journals Online (AJOL)
NJD
Decomposition Process of the Dysprosium(III) m-Methylbenzoate 1 ... A dinuclear complex [Dy(m-MBA)3phen]2·H2O was prepared by the reaction of DyCl3·6H2O, m-methylbenzoic acid and .... ing rate of 10 °C min–1 are illustrated in Fig. 4.
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Thermal analysis of wood of the main tree species of Central Siberia
Directory of Open Access Journals (Sweden)
S. R. Loskutov
2015-12-01
Full Text Available Thermal decomposition of wood from coniferous and deciduous species of Siberia has been studied using thermogravimetry (TG and differential scanning calorimetry (DSC. The tree species were larch Larix sibirica Ledeb., Scots pine Pinus sylvestris L., spruce Picea obovata Ledeb., fir Abies sibirica Ledeb., Siberian pine Pinus sibirica Du Tour., birch Betula pendula Roth., and aspen Populus tremula L. Thermal analysis of wood samples was carried out under oxidative (air and inert (argon atmospheres from 25 to 700 °С at heating rates 10, 20, 40 °С • min–1 (TG/DTG and from 25 to 590 °С at heating rates 10, 40 °С • min–1 (DSC. The stages of thermal decomposition, the temperature intervals, the mass loss, the mass loss rate, the temperature of DTG/DSC peaks, and heating effects were determined for each tree species. The kinetic thermal degradation parameters of wood were obtained by the Broido and Ozawa–Flynn–Wall models. The wood of coniferous and deciduous species of Siberia was characterized on the base of analysis of activation energy values at various stages of thermal decomposition and the relations of activation energy on conversion level of wood substance of different tree species, and also the comparison of mass loss at the same stages of thermal destruction, heating effects, residual mass and other parameters of TG/DTG, DSC. In our opinion, the results of this work present interest for researchers and specialists in the field of forest pyrology, wood science, dendrochemistry.
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Yazici, A N
2003-01-01
In this paper, the thermal bleaching curves (TBCs) of specific optical absorption bands of LiF : Mg,Ti were measured as a function of temperature. The TBCs obtained were analysed to extract the kinetic parameters (the thermal activation energy (E) and the frequency factor (s)) of some TL glow peaks of LiF : Mg,Ti on the basis of the developed first-order kinetic model over a specified temperature region.
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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.
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International Nuclear Information System (INIS)
Herrera, Adriana P.; Polo-Corrales, Liliana; Chavez, Ermides; Cabarcas-Bolivar, Jari; Uwakweh, Oswald N.C.; Rinaldi, Carlos
2013-01-01
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 χ′and out-of-phase χ″ components of the complex susceptibility at the frequency of the Brownian magnetic relaxation peak, as expected for nanoparticles
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Thermal coupling of a high temperature PEM fuel cell with a complex hydride tank
DEFF Research Database (Denmark)
Pfeifer, P.; Wall, C.; Jensen, Jens Oluf
2009-01-01
the possibilities of a thermal coupling of a high temperature PEM fuel cell operating at 160-200 degrees C. The starting temperatures and temperature hold-times before starting fuel cell operation, the heat transfer characteristics of the hydride storage tanks, system temperature, fuel cell electrical power......Sodium alanate doped with cerium catalyst has been proven to have fast kinetics for hydrogen ab- and de-sorption as well as a high gravimetric storage density around 5 wt%. The kinetics of hydrogen sorption can be improved by preparing the alanate as nanocrystalline material. However, the second...... decomposition step, i.e. the decomposition of the hexahydride to sodium hydride and aluminium which refers to 1.8 wt% hydrogen is supposed to happen above 110 degrees C. The discharge of the material is thus limited by the level of heat supplied to the hydride storage tank. Therefore, we evaluated...
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57Fe Moessbauer spectroscopic study of the thermal decomposition of Fe(IO3)3
International Nuclear Information System (INIS)
Music, S.; Simmons, G.W.; Leidheiser, H. Jr
1981-01-01
Thermal decomposition of iron(III) iodate at temperatures up to 600 deg C has been followed by 57 Fe Moessbauer spectroscopy. The 57 Fe Moessbauer spectrum of iron(III) iodate is characterized by a single absorption peak. A magnetic splitting component of small intensity appears after 42 h heating at 370 deg C. Iron(III) iodate is completely decomposed after 1 h heating at 470 deg C. Moessbauer parameters of the component yielding the magnetic hyperfine split spectrum correspond to α-Fe 2 O 3 with crystal defects. Quantitative experimental data are summarized and discussed. (author)
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International Nuclear Information System (INIS)
Yan, P; Qin, D; An, Y K; Li, G Z; Xing, J; Liu, J J
2008-01-01
Herein we describe a thermal treatment route to synthesize gallium nitride (GaN) nanorods. In this method, GaN nanorods were synthesized by thermal treatment of GaN films at a temperature of 800 deg. C. The morphology and structure of GaN nanorods were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results show that GaN nanorods have a hexagonal wurtzite structure with diameters ranging from 30 to 50 nm. Additionally, GaN nanoplates are also founded in the products. The growth process of GaN nanostructures was investigated and a thermal decomposition mechanism was proposed. Our method provides a cost-effective route to fabricate GaN nanorods, which will benefit the fabrication of one-dimensional nanomaterials and device applications
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GENERAL EQUATIONS OF CARBONIZATION OF EUCALYPTUS SPP KINETIC MECHANISMS
Directory of Open Access Journals (Sweden)
Túlio Jardim Raad
2006-06-01
Full Text Available In the present work, a set of general equations related to kinetic mechanism of wood compound carbonization: hemicelluloses, cellulose and lignin was obtained by Avrami-Eroffev and Arrhenius equations and Thermogravimetry of Eucalyptus cloeziana, Eucalyptus camaldulensis, Corymbia citriodora, Eucalyptus urophylla and Eucalyptus grandis samples, TG-Isothermal and TG-Dynamic. The different thermal stabilities and decomposition temperature bands of those species compounds were applied as strategy to obtain the kinetic parameters: activation energy, exponential factor and reaction order. The kinetic model developed was validated by thermogravimetric curves from carbonization of others biomass such as coconut. The kinetic parameters found were - Hemicelluloses: E=98,6 kJmol, A=3,5x106s-1 n=1,0; - Cellulose: E=182,2 kJmol, A=1,2x1013s-1 n=1,5; - Lignin: E=46,6 kJmol, A=2,01s-1 n=0,41. The set of equations can be implemented in a mathematical model of wood carbonization simulation (with heat and mass transfer equations with the aim of optimizing the control and charcoal process used to produce pig iron.
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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).
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Czech Academy of Sciences Publication Activity Database
Asadi, Z.; Nasrollahi, R.; Dušek, Michal; Fejfarová, Karla; Ranjkeshshorkaei, M.; Firuzabadi, F.D.
2016-01-01
Roč. 13, č. 5 (2016), 913-924 ISSN 1735-207X R&D Projects: GA ČR(CZ) GA14-03276S Institutional support: RVO:68378271 Keywords : Schiff base complex * kinetic study * anticancer activity Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.407, year: 2016
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Kinetic evolution of the glasma and thermalization in heavy-ion collisions
International Nuclear Information System (INIS)
Huang, Xuguang; Liao, Jinfeng
2014-01-01
In relativistic heavy-ion collisions, a highly occupied gluonic matter is created shortly after initial impact, which is in a nonthermal state and often referred to as the Glasma. Successful phenomenology suggests that the glasma evolves rather quickly toward the thermal quark–gluon plasma (QGP) and a hydrodynamic behavior emerges at a very early time ~ô(1) fm/c. Exactly how such 'apparent thermalization' occurs and connects the initial conditions to the hydrodynamic onset, remains a significant challenge for theory as well as phenomenology. We briefly review various ideas and recent progress in understanding the approach of the glasma to the thermalized QGP, with an emphasis on the kinetic theory description for the evolution of such far-from-equilibrium and highly overpopulated, thus weakly-coupled yet strongly interacting glasma. (author)
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Kinetic study of the thermal hydrolysis of Agave salmiana for mezcal production.
Garcia-Soto, M J; Jimenez-Islas, H; Navarrete-Bolanos, J L; Rico-Martinez, R; Miranda-Lopez, R; Botello-Alvarez, J E
2011-07-13
The kinetics of the thermal hydrolysis of the fructans of Agave salmiana were determined during the cooking step of mezcal production in a pilot autoclave. Thermal hydrolysis was achieved at different temperatures and cooking times, ranging from 96 to 116 °C and from 20 to 80 h. A simple kinetic model of the depolymerization of fructans to monomers and other reducing sugars and of the degradation of reducing sugars to furans [principally 5-(hydroxymethyl)furfural, HMF] was developed. From this model, the rate constants of the reactions were calculated, as well as the pre-exponential factors and activation energies of the Arrhenius equation. The model was found to fit the experimental data well. The tradeoff between a maximum fructan hydrolysis and a critical furan concentration in allowing for the best ethanol yield during fermentation was investigated. The results indicated that the thermal hydrolysis of agave was optimal, from the point of view of ethanol yield in the ensuing fermentation, in the temperature range of 106-116 °C and the cooking range time of 6-14 h. The optimal conditions corresponded to a fructan hydrolysis of 80%, producing syrups with furan and reducing sugar concentrations of 1 ± 0.1 and 110 ± 10 g/L, respectively.
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Preparation, characterization and catalytic effects of copper oxalate nanocrystals
International Nuclear Information System (INIS)
Singh, Gurdip; Kapoor, Inder Pal Singh; Dubey, Reena; Srivastava, Pratibha
2012-01-01
Graphical abstract: Prepared copper oxalate nanocrystals were characterized by FE-SEM and bright field TEM micrographs. Its catalytic activity was evaluated on the thermal decomposition of ammonium perchlorate using TG and TG-DSC techniques. Highlights: ► Preparation of nanocrystals (∼9.0 nm) of copper oxalate using Cu(NO 3 ) 2 ·2H 2 O, oxalic acid and acetone under thermal conditions. ► Method is simple and novel. ► Characterization using XRD, SEM, TEM, HRTEM and ED pattern. ► Catalytic activity of copper oxalate nanocrystals on AP thermal decomposition using thermal techniques (TG, TG-DSC and ignition delay). ► Kinetics of thermal decomposition of AP + CONs using isoconversional and model fitting kinetic approaches. - Abstract: Recent work has described the preparation and characterization of copper oxalate nanocrystals (CONs). It was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM) and electron diffraction pattern (ED). The catalytic activity of CONs on the thermal decomposition of ammonium perchlorate (AP) and composite solid propellants (CSPs) has been done by thermogravimetry (TG), differential scanning calorimetry (DSC) and ignition delay measurements. Burning rate of CSPs was also found to be enhanced in presence of copper oxalate nanocrystals. Kinetics of thermal decomposition of AP with and without CONs has also been investigated. The model free (isoconversional) and model-fitting kinetic approaches have been applied to data for isothermal TG decomposition.
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Energy Technology Data Exchange (ETDEWEB)
Tan, Linghua, E-mail: tanlinghua@njit.edu.cn [School of Materials Science and Engineering, Nanjing Institute of Technology, Jiangsu (China); Jiangsu Key Laboratory of Advanced Structural Materials and Application Technology, Jiangsu (China); Xu, Jianhua [School of Materials Science and Engineering, Nanjing Institute of Technology, Jiangsu (China); Zhang, Xiaojuan [School of Material Engineering, Jinling Institute of Technology, Nanjing 211169 (China); Hang, Zusheng [School of Materials Science and Engineering, Nanjing Institute of Technology, Jiangsu (China); Jiangsu Key Laboratory of Advanced Structural Materials and Application Technology, Jiangsu (China); Jia, Yongqiang; Wang, Shanbin [School of Materials Science and Engineering, Nanjing Institute of Technology, Jiangsu (China)
2015-11-30
Graphical abstract: The CeO{sub 2} nanoparticles were uniformly loaded on the surface of g-C{sub 3}N{sub 4} via a simple mixing-calcination method, and the heterostructure construction of resulting from g-C{sub 3}N{sub 4}/CeO{sub 2} nanocomposites effectively suppressed the charge recombination. Interestingly, g-C{sub 3}N{sub 4}/CeO{sub 2} nanocomposites showed an enhanced catalytic activity for thermal decomposition of ammonium perchlorate. - Highlights: • Novel g-C{sub 3}N{sub 4}/CeO{sub 2} nanocomposites were synthesized through a simple mixing-calcination method. • The g-C{sub 3}N{sub 4}/CeO{sub 2} nanocomposites were applied in catalyzing the thermal decomposition of ammonium perchlorate. • The synergetic effect of g-C{sub 3}N{sub 4} and CeO{sub 2} was the origin of the high catalytic activity. • The catalytic mechanism of g-C{sub 3}N{sub 4}/CeO{sub 2} nanocomposites to the thermal decomposition of AP was investigated. - Abstract: Novel g-C{sub 3}N{sub 4}/CeO{sub 2} nanocomposites were synthesized through a simple mixing-calcination method. The structure, morphology and composition of g-C{sub 3}N{sub 4}/CeO{sub 2} nanocomposites were characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), as well as X-ray photoelectron spectroscopy (XPS). The results indicated that CeO{sub 2} nanoparticles with a diameter of 50–100 nm were uniformly loaded on the surface of g-C{sub 3}N{sub 4.} Furthermore, the catalytic effect of our prepared novel g-C{sub 3}N{sub 4}/CeO{sub 2} nanocomposites on the thermal decomposition of ammonium perchlorate (AP) was investigated by utilizing thermogravimetric and differential thermal analyses (TG-DTA). Compared with pure g-C{sub 3}N{sub 4} and CeO{sub 2}, the g-C{sub 3}N{sub 4}/CeO{sub 2} nanocomposites were proved to catalyze the thermal decomposition
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NDMA formation by chloramination of ranitidine: Kinetics and mechanism
Le Roux, Julien; Gallard, Hervé
; Croue, Jean-Philippe; Papot, Sé bastien; Deborde, Marie 2012-01-01
The kinetics of decomposition of the pharmaceutical ranitidine (a major precursor of NDMA) during chloramination was investigated and some decomposition byproducts were identified by using high performance liquid chromatography coupled with mass
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International Nuclear Information System (INIS)
Pareige, C.; Emo, J.; Pareige, P.; Saillet, S.; Domain, C.
2015-01-01
Duplex stainless steels (DSS), used in primary circuit of Pressurised Water Reactor (PWR), are prone to thermal ageing at service temperature, typically between 286 and 323 C. degrees. This ageing is due to the ferrite decomposition via two kinds of phase transformations: spinodal decomposition into Fe rich α zones and Cr rich α' zones and precipitation of G-phase enriched in Ni, Si, Mn and Mo. It has been shown by atom probe tomography (APT) that the G-phase particles form at the interface between α and α' regions thereby demonstrating that α-α' decomposition and G-phase precipitation are highly dependent. The synergy between the two decomposition processes should be related to both the thermodynamics of the system and the diffusion mechanisms active during ageing. This can be studied by atomistic kinetic Monte Carlo (AKMC) with a model that can reproduce the phase transformations which take place in ferrite of duplex stainless steels. This paper presents the first simulations of the kinetics of spinodal decomposition and G-phase precipitation occurring in ferrite of duplex stainless steels. The kinetics was simulated using a simple but effective atomic kinetic Monte Carlo model in a ternary alloy. The simulations reproduced the α/α' spinodal structure with precipitates at the α/α' interface. The comparison of simulated results with experiments shows that the simulations quantitatively reproduce the kinetics of phase transformation and the synergy observed experimentally between the spinodal decomposition and G-phase precipitation: the time evolution of the wavelength of the spinodal decomposition and the radius of G-phase precipitates were quantitatively reproduced. The simulations endorse the assumption that G-phase precipitation mainly results from the rejection of G-formers from α and α' domains. By following the vacancy pathway during simulation, we show that coarsening of the G-phase precipitates must proceed via
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Directory of Open Access Journals (Sweden)
Şeyda Taşar
2015-12-01
Full Text Available The pyrolysis process, which is applied for the aim of producing energy and raw materials which are implemented for the chemical industry from biomass sources, is a thermal conversion process. Determination of the pyrolysis kinetic parameters are important In order to suitable equipment and process design. In this target, in the study the pyrolysis of peanut shells was conducted in a muffle furnace at static atmosphere with temperatures ranging from 300-700 °C. The effects of various parameters on the rate of thermal decomposition rate and the solid yield were determined. The parameters of interest were temperature 300-700 °C, particle size 4-50 mesh, pelletizing, and pelletizing pressure 1.103-5.103 kgf/cm2. Regression coefficients for the total decomposition step were obtained using the thermographs were obtained as a result of the pyrolysis of the peanut shells, and 20 different theoretical model equations that represented the degradation by the Coast-Redfern method. According to regression coefficients of the theoretical model equations, we determined the kinetic model that best represented the degradation. Using this model to represent the degradation, the activation energy (Ea and Arhenius frequency factor ln(A for the total reaction were calculated to be 38.245 kJ/mol and 8.124, respectively.
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Modeling texture kinetics during thermal processing of potato products.
Moyano, P C; Troncoso, E; Pedreschi, F
2007-03-01
A kinetic model based on 2 irreversible serial chemical reactions has been proposed to fit experimental data of texture changes during thermal processing of potato products. The model links dimensionless maximum force F*(MAX) with processing time. Experimental texture changes were obtained during frying of French fries and potato chips at different temperatures, while literature data for blanching/cooking of potato cubes have been considered. A satisfactory agreement between experimental and predicted values was observed, with root mean square values (RMSs) in the range of 4.7% to 16.4% for French fries and 16.7% to 29.3% for potato chips. In the case of blanching/cooking, the proposed model gave RMSs in the range of 1.2% to 17.6%, much better than the 6.2% to 44.0% obtained with the traditional 1st-order kinetics. The model is able to predict likewise the transition from softening to hardening of the tissue during frying.
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Thermal stability and mechanism of decomposition of emulsion explosives in the presence of pyrite.
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.
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Thermal Analysis of the Fastrac Chamber/Nozzle
Davis, Darrell
2001-01-01
This paper will describe the thermal analysis techniques used to predict temperatures in the film-cooled ablative rocket nozzle used on the Fastrac 60K rocket engine. A model was developed that predicts char and pyrolysis depths, liner thermal gradients, and temperatures of the bondline between the overwrap and liner. Correlation of the model was accomplished by thermal analog tests performed at Southern Research, and specially instrumented hot fire tests at the Marshall Space Flight Center. Infrared thermography was instrumental in defining nozzle hot wall surface temperatures. In-depth and outboard thermocouple data was used to correlate the kinetic decomposition routine used to predict char and pyrolysis depths. These depths were anchored with measured char and pyrolysis depths from cross-sectioned hot-fire nozzles. For the X-34 flight analysis, the model includes the ablative Thermal Protection System (TPS) material that protects the overwrap from the recirculating plume. Results from model correlation, hot-fire testing, and flight predictions will be discussed.
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Muoto, Chigozie Kenechukwu
This research aims to identify the key feedstock characteristics and processing conditions to produce Y2O3-MgO composite coatings with high density and hardness using solution precursor plasma spray (SPPS) and suspension plasma spray (SPS) processes, and also, to explore the phenomena involved in the production of homogenized nano-composite powders of this material system by thermal decomposition of solution precursor mixtures. The material system would find potential application in the fabrication of components for optical applications such as transparent windows. It was shown that a lack of major endothermic events during precursor decomposition and the resultant formation of highly dense particles upon pyrolysis are critical precursor characteristics for the deposition of dense and hard Y2O3-MgO coatings by SPPS. Using these principles, a new Y2O3-MgO precursor solution was developed, which yielded a coating with Vickers hardness of 560 Hv. This was a considerable improvement over the hardness of the coatings obtained using conventional solution precursors, which was as low as 110 Hv. In the thermal decomposition synthesis process, binary solution precursor mixtures of: yttrium nitrate (Y[n]) or yttrium acetate (Y[a]), with magnesium nitrate (Mg[n]) or magnesium acetate (Mg[a]) were used in order to study the effects of precursor chemistry on the structural characteristics of the resultant Y2O3-MgO powders. The phase domains were coarse and distributed rather inhomogeneously in the materials obtained from the Y[n]Mg[n] and Y[a]Mg[a] mixtures; finer and more homogeneously-distributed phase domains were obtained for ceramics produced from the Y[a]Mg[n] and Y[n]Mg[a] mixtures. It was established that these phenomena were related to the thermal characteristics for the decomposition of the precursors and their effect on phase separation during oxide crystallization. Addition of ammonium acetate to the Y[n[Mg[n] mixture changed the endothermic process to exothermic
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Thermal Decomposition Mechanisms of Lignin Model Compounds: From Phenol to Vanillin
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
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International Nuclear Information System (INIS)
Achilias, Dimitris S.; Panayotidou, Elpiniki; Zuburtikudis, Ioannis
2011-01-01
Poly(3-hydroxybutyrate) (PHB)/organically modified clay nanocomposites were prepared by the melt mixing method and were characterized using wide-angle X-ray diffraction. Their thermal degradation kinetics was investigated using thermogravimetric analysis at various heating rates. Further kinetic analysis was performed using isoconversional methods and the invariant kinetic parameters method was used to estimate the so-called 'true' kinetic parameters, i.e. the pre-exponential factor, A and the activation energy, E, as well as the reaction model. It was found that intercalated structures are formed and the thermal stability of the material is improved by the addition of the nano-filler. From the isoconversional analysis, it was found that the activation energy does not vary significantly with the degree of degradation denoting degradation in one step with similar values for pure PHB and for all nanocomposites. Using the invariant kinetic parameters method, it was found that the model that best describes the experimental data was that of Sestak-Berggren's with f(a) = α n (1 - α) m , where the value of n is always larger than m and is increasing with the amount of the nano-filler. The value of the 'true' activation energy was found to be about 100 kJ mol -1 for all nanocomposites and the pre-exponential factor for PHB was estimated equal to 5.35 x 10 9 min -1 . Finally, the values of the kinetic rate constant k were found to decrease with the amount of the nano-filler up to 3 wt%, while for amounts larger than 3 wt% k increased reaching a value greater than that of pure PHB for the 10 wt% nanocomposites.
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New method for evaluating the kinetic constant of thermal protection materials
International Nuclear Information System (INIS)
Bae, Ji Yeul; Yi, Jong Ju; Park, Sul Ki; Cho, Hyung Hee; Bae, Ju Chan; Ham, Hee Cheol
2013-01-01
Thermal protection material (TPM) is used to protect rocket structures from extreme conditions created by the hot exhaust of the rocket. Designing TPM is an important step in the rocket design process. Considering that an increase in the system weight decreases the overall performance of a rocket, the amount of TPM is carefully determined during the design process. Therefore, the precise properties of TPM guarantee an accurate thermal analysis and the successful design of the rocket. Among the many properties of TPM, the kinetic constant and activation energy, which govern the thermochemical reaction of the TPM, are the most important. Thus, an experiment to measure the kinetic constant and activation energy is conducted as part of this research. A theoretical approach to deduce the properties from measured data is discussed, and a method to apply the theory to experimental data, termed the R 2 method, is developed. Compared to a previous method which was difficult to apply, the R 2 method reduces unclear selections of the reaction time and does not require intervention by an interpreter. The properties deduced by the R 2 method show good agreement with the other method despite the limited number of experimental results.
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Directory of Open Access Journals (Sweden)
Rajesh N. Singru
2009-01-01
Full Text Available The terpolymer resins (8-HQ5-SAOF have been synthesized by the condensation of 8-hydroxyquinoline 5-sulphonic acid (8-HQ5-SA and oxamide (O with formaldehyde (F in the presence of acid catalyst and using varied molar proportion of the reacting monomers. The synthesized terpolymer resins have been characterized by different physico-chemical techniques. Thermogravimetric analysis of all terpolymer resins in present study have been carried out by non-isothermal thermogravimetric analysis technique in which sample is subjected to condition of continuous increase in temperature at linear rate. Thermal study of the resins was carried out to determine their mode of decomposition and relative thermal stabilities. Thermal decomposition curves were studied carefully with minute details. The Freeman-Carroll and Sharp-Wentworth methods have been used in the present investigation to calculate thermal activation energy and different kinetic parameter of the terpolymer resins. Thermal activation energy (Ea calculated with above two mentioned methods are in close agreement. The advantage of Freeman-Carroll method is to calculate both the order of reaction (n and energy of activation in one single stage by keeping heating rate constant. By using data of thermogravimetric analysis, various thermodynamic parameters like frequency factor (Z, entropy change (Δ S, free energy change (Δ F and apparent entropy (S* have been determined using Freeman-Carroll method.
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Effect of dislocations on spinodal decomposition in Fe-Cr alloys
International Nuclear Information System (INIS)
Li Yongsheng; Li Shuxiao; Zhang Tongyi
2009-01-01
Phase-field simulations of spinodal decomposition in Fe-Cr alloys with dislocations were performed by using the Cahn-Hilliard diffusion equation. The stress field of dislocations was calculated in real space via Stroh's formalism, while the composition inhomogeneity-induced stress field and the diffusion equation were numerically calculated in Fourier space. The simulation results indicate that dislocation stress field facilitates, energetically and kinetically, spinodal decomposition, making the phase separation faster and the separated phase particles bigger at and near the dislocation core regions. A tilt grain boundary is thus a favorable place for spinodal decomposition, resulting in a special microstructure morphology, especially at the early stage of decomposition.
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Thermal Reduction of NOx with Recycled Plastics.
Oluwoye, Ibukun; Dlugogorski, Bogdan Z; Gore, Jeff; Vyazovkin, Sergey; Boyron, Olivier; Altarawneh, Mohammednoor
2017-07-05
This study develops technology for mitigation of NO x formed in thermal processes using recycled plastics such as polyethylene (PE). Experiments involve sample characterization, and thermogravimetric decomposition of PE under controlled atmospheres, with NO x concentration relevant to industrial applications. TGA-Fourier transform infrared (FTIR) spectroscopy and NO x chemiluminescence serve to obtain the removal efficiency of NO x by fragments of pyrolyzing PE. Typical NO x removal efficiency amounts to 80%. We apply the isoconversional method to derive the kinetic parameters, and observe an increasing dependency of activation energy on the reaction progress. The activation energies of the process span 135 kJ/mol to 226 kJ/mol, and 188 kJ/mol to 268 kJ/mol, for neat and recycled PE, respectively, and the so-called compensation effect accounts for the natural logarithmic pre-exponential ln (A/min -1 ) factors of ca. 19-35 and 28-41, in the same order, depending on the PE conversion in the experimental interval of between 5 and 95%. The observed delay in thermal events of recycled PE reflects different types of PE in the plastic, as measurements of intrinsic viscosity indicate that, the recycled PE comprises longer linear chains. The present evaluation of isoconversional activation energies affords accurate kinetic modeling of both isothermal and nonisothermal decomposition of PE in NO x -doped atmosphere. Subsequent investigations will focus on the effect of mass transfer and the presence of oxygen, as reburning of NO x in large-scale combustors take place at higher temperatures than those included in the current study.
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Thermal decomposition studies on tri-iso-amyl phosphate in n-dodecane-nitric acid system
International Nuclear Information System (INIS)
Chandran, K.; Sreenivasalu, B.; Suresh, A.; Sivaraman, N.; Anthonysamy, S.
2014-01-01
Tri-iso-amyl Phosphate (TiAP) is a promising alternative solvent to TBP, with near similar extraction behaviour and physical properties but lower aqueous phase solubility and does not form third phase during the extraction of Pu(IV). In addition to the solubilised extractant, inadvertent entrainment of the extractant into the aqueous stream is a concern during the evaporation operation as the extractant comes into contact with higher nitric acid concentrations and metal nitrates. Hence the thermal decomposition behaviour of TiAP-HNO 3 systems has been studied using an adiabatic calorimeter in closed air ambience, under heat-wait-search mode (H-W-S)
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A handbook of decomposition methods in analytical chemistry
International Nuclear Information System (INIS)
Bok, R.
1984-01-01
Decomposition methods of metals, alloys, fluxes, slags, calcine, inorganic salts, oxides, nitrides, carbides, borides, sulfides, ores, minerals, rocks, concentrates, glasses, ceramics, organic substances, polymers, phyto- and biological materials from the viewpoint of sample preparation for analysis have been described. The methods are systemitized according to decomposition principle: thermal with the use of electricity, irradiation, dissolution with participation of chemical reactions and without it. Special equipment for different decomposition methods is described. Bibliography contains 3420 references
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Divekar, Sandesh K.; Achary, S. Nagabhusan; Ajgaonkar, Vishnu R.
2018-06-01
A series of double selenates, as (CH3)4NLn(SeO4)2rad 4H2O (Ln = Rare earth ion like La, Pr, Nd, Sm, Gd, Tb, Dy) was crystallized from mixed solution and characterized in detail for their structure, vibrational and optical properties as well as thermal stabilities. The crystal structure of the praseodymium compound was obtained by single crystal X-ray diffraction (XRD) and revealed a monoclinic (C2/c) lattice with chains formed by PrO8 and SeO4 units. The chains with compositions [Pr(SeO4)4(H2O)4]- are stacked in three dimensions and the (CH3)4N+ ions located in between them provide charge neutrality to the structure. The characterization of other compounds were carried out from powder XRD data and revealed that they all are isostructural to Pr-compound. All the functional groups were identified by Raman and IR spectroscopic studies. Solid state 77Se NMR revealed noticeable changes in selenium environment in these compounds. The optical absorption studies on the compounds show strong band edge absorptions in UV region. Thermal stabilities of the compounds, as investigated by simultaneous TG-DTA techniques indicate their sequential decompositions due to loss of H2O, (CH3)4N+ group, SeO2 and finally leaving their corresponding rare earth oxides.
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Synthesis of magnetite nanoparticles obtained by the thermal decomposition method
International Nuclear Information System (INIS)
Fonseca, Renilma de Sousa Pinheiro; Sinfronio, Francisco Savio Mendes; Menezes, Alan Silva de; Sharma, Surender Kumar; Silva, Fernando Carvalho; Moscoso-Londono, Oscar; Muraca, Diego; Knobel, Marcelo
2016-01-01
Full text: Magnetite nanoparticles have found numerous applications in biomedicine such as magnetic separation, drug delivery, magnetic resonance imaging (MRI) and hyperthermia agents [1]. These features are related to their superparamagnetic behavior, low toxicity and high functionalization [2]. Thus, this work aims to obtain oleylamine-coated magnetite nanoparticles by means of thermal decomposition method at different temperatures and reaction time. All samples were characterized by FTIR, XRD and SQUID magnetometer. The infrared spectra showed two vibrational modes at 2920 and 2850 cm -1 , assigned to the asymmetrical and symmetrical stretching of C-H groups of the oleic acid and oleylamine, respectively. The XRD pattern of the samples confirmed the formation of magnetite phase (ICSD 36314) at all temperatures. The average size of the crystallites was determined by Debye-Scherrer equation with values in the range of 1.1-1.5 nm. Field-cooled and zero field-cooled analysis demonstrate that the blocking temperature (T B ) is below room temperature in all cases, indicating that all magnetite nanoparticles are superparamagnetic at room temperature and ferrimagnetic at low temperature. (author)
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Synthesis of magnetite nanoparticles obtained by the thermal decomposition method
Energy Technology Data Exchange (ETDEWEB)
Fonseca, Renilma de Sousa Pinheiro; Sinfronio, Francisco Savio Mendes; Menezes, Alan Silva de; Sharma, Surender Kumar; Silva, Fernando Carvalho, E-mail: renilma.ufma@gmail.com [Universidade Federal do Maranhao (UFMA), Sao Luis, MA (Brazil); Moscoso-Londono, Oscar; Muraca, Diego; Knobel, Marcelo [Universidade Estadual de Campinas (UNICAMP), SP (Brazil)
2016-07-01
Full text: Magnetite nanoparticles have found numerous applications in biomedicine such as magnetic separation, drug delivery, magnetic resonance imaging (MRI) and hyperthermia agents [1]. These features are related to their superparamagnetic behavior, low toxicity and high functionalization [2]. Thus, this work aims to obtain oleylamine-coated magnetite nanoparticles by means of thermal decomposition method at different temperatures and reaction time. All samples were characterized by FTIR, XRD and SQUID magnetometer. The infrared spectra showed two vibrational modes at 2920 and 2850 cm{sup -1}, assigned to the asymmetrical and symmetrical stretching of C-H groups of the oleic acid and oleylamine, respectively. The XRD pattern of the samples confirmed the formation of magnetite phase (ICSD 36314) at all temperatures. The average size of the crystallites was determined by Debye-Scherrer equation with values in the range of 1.1-1.5 nm. Field-cooled and zero field-cooled analysis demonstrate that the blocking temperature (T{sub B}) is below room temperature in all cases, indicating that all magnetite nanoparticles are superparamagnetic at room temperature and ferrimagnetic at low temperature. (author)
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International Nuclear Information System (INIS)
BEHRENS JR., RICHARD; MINIER, LEANNA M.G.
1999-01-01
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
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Chemical kinetics and oil shale process design
Energy Technology Data Exchange (ETDEWEB)
Burnham, A.K.
1993-07-01
Oil shale processes are reviewed with the goal of showing how chemical kinetics influences the design and operation of different processes for different types of oil shale. Reaction kinetics are presented for organic pyrolysis, carbon combustion, carbonate decomposition, and sulfur and nitrogen reactions.
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Zhang, Luzheng; Zybin, Sergey V; van Duin, Adri C T; Dasgupta, Siddharth; Goddard, William A; Kober, Edward M
2009-10-08
We report molecular dynamics (MD) simulations using the first-principles-based ReaxFF reactive force field to study the thermal decomposition of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) at various densities and temperatures. TATB is known to produce a large amount (15-30%) of high-molecular-weight carbon clusters, whereas detonation of nitramines such as HMX and RDX (1,3,5-trinitroperhydro-1,3,5-triazine) generate predominantly low-molecular-weight products. In agreement with experimental observation, these simulations predict that TATB decomposition quickly (by 30 ps) initiates the formation of large carbonaceous clusters (more than 4000 amu, or approximately 15-30% of the total system mass), and HMX decomposition leads almost exclusively to small-molecule products. We find that HMX decomposes readily on this time scale at lower temperatures, for which the decomposition rate of TATB is about an order of magnitude slower. Analyzing the ReaxFF MD results leads to the detailed atomistic structure of this carbon-rich phase of TATB and allows characterization of the kinetics and chemistry related to this phase and their dependence on system density and temperature. The carbon-rich phase formed from TATB contains mainly polyaromatic rings with large oxygen content, leading to graphitic regions. We use these results to describe the initial reaction steps of thermal decomposition of HMX and TATB in terms of the rates for forming primary and secondary products, allowing comparison to experimentally derived models. These studies show that MD using the ReaxFF reactive force field provides detailed atomistic information that explains such macroscopic observations as the dramatic difference in carbon cluster formation between TATB and HMX. This shows that ReaxFF MD captures the fundamental differences in the mechanisms of such systems and illustrates how the ReaxFF may be applied to model complex chemical phenomena
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Non-Parametric Kinetic (NPK Analysis of Thermal Oxidation of Carbon Aerogels
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Azadeh Seifi
2017-05-01
Full Text Available In recent years, much attention has been paid to aerogel materials (especially carbon aerogels due to their potential uses in energy-related applications, such as thermal energy storage and thermal protection systems. These open cell carbon-based porous materials (carbon aerogels can strongly react with oxygen at relatively low temperatures (~ 400°C. Therefore, it is necessary to evaluate the thermal performance of carbon aerogels in view of their energy-related applications at high temperatures and under thermal oxidation conditions. The objective of this paper is to study theoretically and experimentally the oxidation reaction kinetics of carbon aerogel using the non-parametric kinetic (NPK as a powerful method. For this purpose, a non-isothermal thermogravimetric analysis, at three different heating rates, was performed on three samples each with its specific pore structure, density and specific surface area. The most significant feature of this method, in comparison with the model-free isoconversional methods, is its ability to separate the functionality of the reaction rate with the degree of conversion and temperature by the direct use of thermogravimetric data. Using this method, it was observed that the Nomen-Sempere model could provide the best fit to the data, while the temperature dependence of the rate constant was best explained by a Vogel-Fulcher relationship, where the reference temperature was the onset temperature of oxidation. Moreover, it was found from the results of this work that the assumption of the Arrhenius relation for the temperature dependence of the rate constant led to over-estimation of the apparent activation energy (up to 160 kJ/mol that was considerably different from the values (up to 3.5 kJ/mol predicted by the Vogel-Fulcher relationship in isoconversional methods
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Understanding CO2 decomposition by thermal plasma with supersonic expansion quench
Tao, YANG; Jun, SHEN; Tangchun, RAN; Jiao, LI; Pan, CHEN; Yongxiang, YIN
2018-04-01
CO2 pyrolysis by thermal plasma was investigated, and a high conversion rate of 33% and energy efficiency of 17% were obtained. The high performance benefited from a novel quenching method, which synergizes the converging nozzle and cooling tube. To understand the synergy effect, a computational fluid dynamics simulation was carried out. A quick quenching rate of 107 K s‑1 could be expected when the pyrolysis gas temperature decreased from more than 3000 to 1000 K. According to the simulation results, the quenching mechanism was discussed as follows: first, the compressible fluid was adiabatically expanded in the converging nozzle and accelerated to sonic speed, and parts of the heat energy converted to convective kinetic energy; second, the sonic fluid jet into the cooling tube formed a strong eddy, which greatly enhanced the heat transfer between the inverse-flowing fluid and cooling tube. These two mechanisms ensure a quick quenching to prevent the reverse reaction of CO2 pyrolysis gas when it flows out from the thermal plasma reactor.
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Directory of Open Access Journals (Sweden)
Fei Wang
2014-12-01
Full Text Available Land surface temperature (LST images retrieved from the thermal infrared (TIR band data of Moderate Resolution Imaging Spectroradiometer (MODIS have much lower spatial resolution than the MODIS visible and near-infrared (VNIR band data. The coarse pixel scale of MODIS LST images (1000 m under nadir have limited their capability in applying to many studies required high spatial resolution in comparison of the MODIS VNIR band data with pixel scale of 250–500 m. In this paper we intend to develop an efficient approach for pixel decomposition to increase the spatial resolution of MODIS LST image using the VNIR band data as assistance. The unique feature of this approach is to maintain the thermal radiance of parent pixels in the MODIS LST image unchanged after they are decomposed into the sub-pixels in the resulted image. There are two important steps in the decomposition: initial temperature estimation and final temperature determination. Therefore the approach can be termed double-step pixel decomposition (DSPD. Both steps involve a series of procedures to achieve the final result of decomposed LST image, including classification of the surface patterns, establishment of LST change with normalized difference of vegetation index (NDVI and building index (NDBI, reversion of LST into thermal radiance through Planck equation, and computation of weights for the sub-pixels of the resulted image. Since the Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER with much higher spatial resolution than MODIS data was on-board the same platform (Terra as MODIS for Earth observation, an experiment had been done in the study to validate the accuracy and efficiency of our approach for pixel decomposition. The ASTER LST image was used as the reference to compare with the decomposed LST image. The result showed that the spatial distribution of the decomposed LST image was very similar to that of the ASTER LST image with a root mean square error
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Wang, Fei; Qin, Zhihao; Li, Wenjuan; Song, Caiying; Karnieli, Arnon; Zhao, Shuhe
2014-12-25
Land surface temperature (LST) images retrieved from the thermal infrared (TIR) band data of Moderate Resolution Imaging Spectroradiometer (MODIS) have much lower spatial resolution than the MODIS visible and near-infrared (VNIR) band data. The coarse pixel scale of MODIS LST images (1000 m under nadir) have limited their capability in applying to many studies required high spatial resolution in comparison of the MODIS VNIR band data with pixel scale of 250-500 m. In this paper we intend to develop an efficient approach for pixel decomposition to increase the spatial resolution of MODIS LST image using the VNIR band data as assistance. The unique feature of this approach is to maintain the thermal radiance of parent pixels in the MODIS LST image unchanged after they are decomposed into the sub-pixels in the resulted image. There are two important steps in the decomposition: initial temperature estimation and final temperature determination. Therefore the approach can be termed double-step pixel decomposition (DSPD). Both steps involve a series of procedures to achieve the final result of decomposed LST image, including classification of the surface patterns, establishment of LST change with normalized difference of vegetation index (NDVI) and building index (NDBI), reversion of LST into thermal radiance through Planck equation, and computation of weights for the sub-pixels of the resulted image. Since the Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) with much higher spatial resolution than MODIS data was on-board the same platform (Terra) as MODIS for Earth observation, an experiment had been done in the study to validate the accuracy and efficiency of our approach for pixel decomposition. The ASTER LST image was used as the reference to compare with the decomposed LST image. The result showed that the spatial distribution of the decomposed LST image was very similar to that of the ASTER LST image with a root mean square error (RMSE) of 2