Thermodynamics of aqueous association and ionization reactions at high temperatures and pressures

International Nuclear Information System (INIS)

Mesmer, R.E.; Marshall, W.L.; Palmer, D.A.; Simonson, J.M.; Holmes, H.F.

1990-01-01

Electrochemical and electrical conductance cells have been widely used at ORNL over the years to quantitatively determine equilibrium constants and their salt effects to 300 degree C (EMF) and 800 degree C (conductance) at the saturation pressure of water (EMF) and to 4000 bars (conductance). The most precise results to 300 degree C for a large number of weak acids and bases show very similar thermodynamic behavior, which will be discussed. Results for the ionization constants of water, NH 3 (aq), HCl(aq), and NaCl(aq), which extend well into the supercritical region, have been fitted in terms of a model with dependence on density and temperature. The entropy change is found to be the driving force for ion-association reactions and this tendency increases (as it must) with increasing temperature at a given pressure. Also, the variation of all thermodynamic properties is greatly reduced at high fixed densities. Considerable variation occurs at low densities. From this analysis, the dependence of the reaction thermodynamics on the P-V-T properties of the solvent is shown, and the implication of large changes in hydration for solutes in the vicinity of the critical temperature will be discussed. Finally, the change in the molar compressibility coefficient for all reactions in water is shown to be the same and dependent only on the compressibility of the solvent

High temperature reactions between molybdenum and metal halides

International Nuclear Information System (INIS)

Boeroeczki, A.; Dobos, G.; Josepovits, V.K.; Hars, Gy.

2006-01-01

Good colour rendering properties, high intensity and efficacy are of vital importance for high-end lighting applications. These requirements can be achieved by high intensity discharge lamps doped with different metal halide additives (metal halide lamps). To improve their reliability, it is very important to understand the different failure processes of the lamps. In this paper, the corrosion reactions between different metal halides and the molybdenum electrical feed-through electrode are discussed. The reactions were studied in the feed-through of real lamps and on model samples too. X-ray photoelectron spectroscopy (XPS) was used to establish the chemical states. In case of the model samples we have also used atomic absorption spectroscopy (AAS) to measure the reaction product amounts. Based on the measurement results we were able to determine the most corrosive metal halide components and to understand the mechanism of the reactions

Surface modification of highly oriented pyrolytic graphite by reaction with atomic nitrogen at high temperatures

International Nuclear Information System (INIS)

Zhang Luning; Pejakovic, Dusan A.; Geng Baisong; Marschall, Jochen

2011-01-01

Dry etching of {0 0 0 1} basal planes of highly oriented pyrolytic graphite (HOPG) using active nitridation by nitrogen atoms was investigated at low pressures and high temperatures. The etching process produces channels at grain boundaries and pits whose shapes depend on the reaction temperature. For temperatures below 600 deg. C, the majority of pits are nearly circular, with a small fraction of hexagonal pits with rounded edges. For temperatures above 600 deg. C, the pits are almost exclusively hexagonal with straight edges. The Raman spectra of samples etched at 1000 deg. C show the D mode near 1360 cm -1 , which is absent in pristine HOPG. For deep hexagonal pits that penetrate many graphene layers, neither the surface number density of pits nor the width of pit size distribution changes substantially with the nitridation time, suggesting that these pits are initiated at a fixed number of extended defects intersecting {0 0 0 1} planes. Shallow pits that penetrate 1-2 graphene layers have a wide size distribution, which suggests that these pits are initiated on pristine graphene surfaces from lattice vacancies continually formed by N atoms. A similar wide size distribution of shallow hexagonal pits is observed in an n-layer graphene sample after N-atom etching.

Thermogravimetric studies of high temperature reactions between potassium salts and chromium

International Nuclear Information System (INIS)

Lehmusto, J.; Lindberg, D.; Yrjas, P.; Skrifvars, B.-J.; Hupa, M.

2012-01-01

Highlights: ► K 2 CO 3 reacted with Cr 2 O 3 forming K 2 CrO 4 . ► Presence of chlorine did not alone explain the initiation of accelerated oxidation. ► More light was shed to the role of chromates in accelerated oxidation. ► Accelerated oxidation of chromia protected steels occurs in two consecutive stages. ► Both potassium and chloride are required, so that both stages of reaction occur. - Abstract: This study compares the high temperature reactions of potassium chloride (KCl) and potassium carbonate (K 2 CO 3 ), two salts found in fly ashes formed in biomass combustion, with both pure metallic chromium (Cr) and chromium oxide (Cr 2 O 3 ). The reactions were investigated with thermogravimetric measurements and the results discussed based on thermodynamic calculations. In simple terms: potassium chloride reacted with chromium forming potassium chromate (K 2 CrO 4 ) and chromium oxide. Potassium chloride did not react with chromium oxide. Potassium carbonate reacted with chromium oxide, but not with chromium. The presence of potassium is sufficient to initiate accelerated oxidation, but chloride is needed to sustain it.

High stereoselectivity on low temperature Diels-Alder reactions

Directory of Open Access Journals (Sweden)

Invernize Paulo

2005-12-01

Full Text Available Abstract We have found that some of the usually poor dienophiles (2-cycloenones can undergo Diels-Alder reaction at -78°C with unusually high stereoselectivity in the presence of niobium pentachloride as a Lewis acid catalyst. A remarkable difference in reaction rates for unsubstituted and α- or β-methyl substituted 2-cycloenones was also observed.

The use of on-line ion chromatography for high temperature and high pressure reaction studies

International Nuclear Information System (INIS)

Lynch, G.J.

1993-10-01

This paper describes the use of on-line ion chromatography as a tool for chemistry reaction studies in small volume systems. The technique was used to study chemistry behavior in a high temperature and high pressure autoclave system. A dual analyzer, multi-channel on-line ion chromatograph (IC) was configured to automate the sampling and analysis. Analytical channels were set up for analysis of inorganic anions, monovalent cations, conductivity, and pH. Conductivity and pH were measured using the IC as a flow injection analyzer. Use of the IC system provides significant advantages over conventional sampling and analysis techniques: Reduction in sample volume, a closed sampling system that protects air or light sensitive analytes from breakdown, around-the-clock test performance combined with automatic calibration and quality control checking, and detection and tracking of reaction products or unexpected contaminants. Methods used to correct measured concentrations for the effects of sampling and for calculation of control chemical loss half-lives are presented. A limited evaluation of the flow injection analysis methods for conductivity and pH is provided

Application of SSNTDs for measurements of fusion reaction products in high-temperature plasma experiments

Energy Technology Data Exchange (ETDEWEB)

Malinowska, A., E-mail: a.malinowska@ipj.gov.p [Andrzej Soltan Institute for Nuclear Studies (IPJ), 05-400 Otwock-Swierk (Poland); Szydlowski, A.; Malinowski, K. [Andrzej Soltan Institute for Nuclear Studies (IPJ), 05-400 Otwock-Swierk (Poland); Sadowski, M.J. [Andrzej Soltan Institute for Nuclear Studies (IPJ), 05-400 Otwock-Swierk (Poland); Institute of Plasma Physics and Laser Microfusion (IPPLM), 00-908 Warsaw (Poland); Zebrowski, J. [Andrzej Soltan Institute for Nuclear Studies (IPJ), 05-400 Otwock-Swierk (Poland); Scholz, M.; Paduch, M.; Zielinska, E. [Institute of Plasma Physics and Laser Microfusion (IPPLM), 00-908 Warsaw (Poland); Jaskola, M.; Korman, A. [Andrzej Soltan Institute for Nuclear Studies (IPJ), 05-400 Otwock-Swierk (Poland)

2009-10-15

The paper describes the application of SSNTDs of the PM-355 type to diagnostics of reaction products emitted from high-temperature deuterium plasmas produced in Plasma Focus (PF) facilities. Acceleration processes occurring in plasma lead often to the generation of high-energy ion beams. Such beams induce nuclear reactions and contribute to the emission of fast neutrons, fusion protons and alpha particles from PF discharges with a deuterium gas. Ion measurements are of primary importance for understanding the mechanisms of the physical processes which drive the charged-particle acceleration. The main aim of the present studies was to perform measurements of spatial- and energy-distributions of fusion-reaction protons (about 3 MeV) within a PF facility. Results obtained from energy measurements were compared with the proton-energy spectra computed theoretically. The protons were measured by means of a set of ion pinhole cameras equipped with PM-355 detectors, which were placed at different angles relative to the electrode axis of the PF facility.

Adiabatic flame temperature of sodium combustion and sodium-water reaction

International Nuclear Information System (INIS)

Okano, Y.; Yamaguchi, A.

2001-01-01

In this paper, background information of sodium fire and sodium-water reaction accidents of LMFBR (liquid metal fast breeder reactor) is mentioned at first. Next, numerical analysis method of GENESYS is described in detail. Next, adiabatic flame temperature and composition of sodium combustion are analyzed, and affect of reactant composition, such oxygen and moisture, is discussed. Finally, adiabatic reaction zone temperature and composition of sodium-water reaction are calculated, and affects of reactant composition, sodium vaporization, and pressure are stated. Chemical equilibrium calculation program for generic chemical system (GENESYS) is developed in this study for the research on adiabatic flame temperature of sodium combustion and adiabatic reaction zone temperature of sodium-water reaction. The maximum flame temperature of the sodium combustion is 1,950 K at the standard atmospheric condition, and is not affected by the existence of moisture. The main reaction product is Na 2 O (l) , and in combustion in moist air, with NaOH (g) . The maximum reaction zone temperature of the sodium-water reaction is 1,600 K, and increases with the system pressure. The main products are NaOH (g) , NaOH (l) and H2 (g) . Sodium evaporation should be considered in the cases of sodium-rich and high pressure above 10 bar

HIgh Temperature Photocatalysis over Semiconductors

Science.gov (United States)

Westrich, Thomas A.

Due in large part to in prevalence of solar energy, increasing demand of energy production (from all sources), and the uncertain future of petroleum energy feedstocks, solar energy harvesting and other photochemical systems will play a major role in the developing energy market. This dissertation focuses on a novel photochemical reaction process: high temperature photocatalysis (i.e., photocatalysis conducted above ambient temperatures, T ≥ 100°C). The overarching hypothesis of this process is that photo-generated charge carriers are able to constructively participate in thermo-catalytic chemical reactions, thereby increasing catalytic rates at one temperature, or maintaining catalytic rates at lower temperatures. The photocatalytic oxidation of carbon deposits in an operational hydrocarbon reformer is one envisioned application of high temperature photocatalysis. Carbon build-up during hydrocarbon reforming results in catalyst deactivation, in the worst cases, this was shown to happen in a period of minutes with a liquid hydrocarbon. In the presence of steam, oxygen, and above-ambient temperatures, carbonaceous deposits were photocatalytically oxidized over very long periods (t ≥ 24 hours). This initial experiment exemplified the necessity of a fundamental assessment of high temperature photocatalytic activity. Fundamental understanding of the mechanisms that affect photocatalytic activity as a function of temperatures was achieved using an ethylene photocatalytic oxidation probe reaction. Maximum ethylene photocatalytic oxidation rates were observed between 100 °C and 200 °C; the maximum photocatalytic rates were approximately a factor of 2 larger than photocatalytic rates at ambient temperatures. The loss of photocatalytic activity at temperatures above 200 °C is due to a non-radiative multi-phonon recombination mechanism. Further, it was shown that the fundamental rate of recombination (as a function of temperature) can be effectively modeled as a

An Unexpected Reaction between 5-Hydroxymethylfurfural and Imidazolium-Based Ionic Liquids at High Temperatures

Directory of Open Access Journals (Sweden)

Zongbao K. Zhao

2011-10-01

Full Text Available A new compound was detected during the production of 5-hydroxymethylfurfural (HMF from glucose and cellulose in the ionic liquid 1-butyl-3-methylimidazolium chloride ([Bmim]Cl at high temperatures. Further experiments found that it was derived from the reaction of HMF with [Bmim]Cl. The structure of new compound was established as 1-butyl-2-(5’-methyl-2’-furoylimidazole (BMI based on nuclear magnetic resonance and mass spectrometry analysis, and a possible mechanism for its formation was proposed. Reactions of HMF with other imidazolium-based ionic liquids were performed to check the formation of BMI. Our results provided new insights in terms of side reactions between HMF and imidazolium-based ionic liquids, which should be valuable for designing better processes for the production of furans using biomass and related materials.

Subsequent development of the normal temperature fusion reaction. Joon kakuyugo sonogo no shinten

Energy Technology Data Exchange (ETDEWEB)

Matsumoto, T. (Hokkaido University, Sapporo (Japan). Faculty of Engineering)

1991-04-24

This paper reports on a NATTOH model made public in May 1989 by T. Matsumoto who took notice of abnormality of the normal temperature fusion reaction. The NATTO model is based on a chain reaction by hydrogen with a hydrogen-catalyzed fusion reaction which is the normal temperature fusion reaction as an elementary process. If a high temperature fusion reaction is a small-size simulation of the fusion reaction rising on the surface of the sparkling star like the sun, the normal temperature fusion reaction can be a small-size simulation of the phenomena in the last years of the star in the far distance of the space. This gives reality to the normal temperature fusion reaction. The reaction mechanism of the normal temperature fusion reaction is almost being clarified by a NATTOH model. There remain problems on a possibility of generation of unknown radioactive rays and identification of radioactive wastes, but it seems that a prospect of commercialization can be talked about now. As for the utilization as energy, sea water may be used as it is. 10 ref., 5 figs.

Development of an apparatus to study chemical reactions at high temperature - a progress report

Energy Technology Data Exchange (ETDEWEB)

Sturzenegger, M; Schelling, Th; Steiner, E; Wuillemin, D [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1999-08-01

TREMPER is an apparatus that was devised to study kinetic and thermodynamic aspects of high-temperature reactions under concentrated solar irradiation. The design allows investigations on solid or liquid samples under inert or reactive atmospheres. The working temperature is adjustable; the upper limit that has yet been reached is about 1900 K. TREMPER will facilitate chemical reactivity studies on a temperature level that is difficult to access by other means. First experiments were conducted to study the decomposition of manganese oxide MnO{sub 2}. Chemical analysis of exposed samples confirmed that the parent MnO{sub 2} was decomposed to mixtures of Mn O and Mn{sub 3}O{sub 4}. The amount of Mn O ranged from 60 mol-% in air to 86 mol-% under inert atmosphere. (author) 1 fig., 1 tab., 2 refs.

Calculation of reaction energies and adiabatic temperatures for waste tank reactions

International Nuclear Information System (INIS)

Burger, L.L.

1993-03-01

Continual concern has been expressed over potentially hazardous exothermic reactions that might occur in underground Hanford waste tanks. These tanks contain many different oxidizable compounds covering a wide range of concentrations. Several may be in concentrations and quantities great enough to be considered a hazard in that they could undergo rapid and energetic chemical reactions with nitrate and nitrite salts that are present. The tanks also contain many inorganic compounds inert to oxidation. In this report the computed energy that may be released when various organic and inorganic compounds react is computed as a function of the reaction mix composition and the temperature. The enthalpy, or integrated heat capacity, of these compounds and various reaction products is presented as a function of temperature, and the enthalpy of a given mixture can then be equated to the energy release from various reactions to predict the maximum temperature that may be reached. This is estimated for several different compositions. Alternatively, the amounts of various diluents required to prevent the temperature from reaching a critical value can be estimated

Kinetics of the high-temperature combustion reactions of dibutylether using composite computational methods

KAUST Repository

Rachidi, Mariam El

2015-01-01

This paper investigates the high-temperature combustion kinetics of n-dibutyl ether (n-DBE), including unimolecular decomposition, H-abstraction by H, H-migration, and C{single bond}C/C{single bond}O β-scission reactions of the DBE radicals. The energetics of H-abstraction by OH radicals is also studied. All rates are determined computationally using the CBS-QB3 and G4 composite methods in conjunction with conventional transition state theory. The B3LYP/6-311++G(2df,2pd) method is used to optimize the geometries and calculate the frequencies of all reactive species and transition states for use in ChemRate. Some of the rates calculated in this study vary markedly from those obtained for similar reactions of alcohols or alkanes, particularly those pertaining to unimolecular decomposition and β-scission at the α-β C{single bond}C bond. These variations show that analogies to alkanes and alcohols are, in some cases, inappropriate means of estimating the reaction rates of ethers. This emphasizes the need to establish valid rates through computation or experimentation. Such studies are especially important given that ethers exhibit promising biofuel and fuel additive characteristics. © 2014.

RBS investigations of high-temperature reactions on graphite substrates

Energy Technology Data Exchange (ETDEWEB)

Eloi, C.C. [Kentucky Univ., Lexington, KY (United States). Dept. of Chemistry]|[Center for Applied Energy Research, University of Kentucky, Lexington, KY 40506 (United States); Robertson, J.D. [Kentucky Univ., Lexington, KY (United States). Dept. of Chemistry]|[Center for Applied Energy Research, University of Kentucky, Lexington, KY 40506 (United States); Majidi, V. [Kentucky Univ., Lexington, KY (United States). Dept. of Chemistry

1995-05-01

While graphite furnace atomic absorption spectrometry (GFAAS) is one of the most powerful techniques for ultratrace analysis of Pb, it is often plagued by matrix interferences. These interferences are minimized by the addition of matrix modifiers which stabilize the analyte signal through unknown mechanisms. Using RBS, the high temperature reactions of nitrate salts of Pb were studied on pyrolytically coated graphite with and without matrix modifiers. The addition of an ammonium phosphate modifier was found to stabilize Pb through the formation of a metal oxy-phosphorus compound. Moreover, the depth profiles demonstrated that the pyrolytically coated graphite was not impervious as previously thought. Pre-treatment of the surface with O{sub 2} is also known to cause a delay in the vaporization of Pb. While a surface effect had previously been postulated, the 3.04 MeV resonance {sup 16}O({alpha}, {alpha}){sup 16}O elastic scattering measurements show that it proceeds through the formation of surface bound lead-oxygen species as the number of oxygen atoms chemisorbed and the number of lead atoms, present on the surface prior to vaporization, are nearly equal. (orig.).

Calculation of reaction energies and adiabatic temperatures for waste tank reactions

International Nuclear Information System (INIS)

Burger, L.L.

1995-10-01

Continual concern has been expressed over potentially hazardous exothermic reactions that might occur in Hanford Site underground waste storage tanks. These tanks contain many different oxidizable compounds covering a wide range of concentrations. The chemical hazards are a function of several interrelated factors, including the amount of energy (heat) produced, how fast it is produced, and the thermal absorption and heat transfer properties of the system. The reaction path(s) will determine the amount of energy produced and kinetics will determine the rate that it is produced. The tanks also contain many inorganic compounds inert to oxidation. These compounds act as diluents and can inhibit exothermic reactions because of their heat capacity and thus, in contrast to the oxidizable compounds, provide mitigation of hazardous reactions. In this report the energy that may be released when various organic and inorganic compounds react is computed as a function of the reaction-mix composition and the temperature. The enthalpy, or integrated heat capacity, of these compounds and various reaction products is presented as a function of temperature; the enthalpy of a given mixture can then be equated to the energy release from various reactions to predict the maximum temperature which may be reached. This is estimated for several different compositions. Alternatively, the amounts of various diluents required to prevent the temperature from reaching a critical value can be estimated. Reactions taking different paths, forming different products such as N 2 O in place of N 2 are also considered, as are reactions where an excess of caustic is present. Oxidants other than nitrate and nitrite are considered briefly

Calculation of reaction energies and adiabatic temperatures for waste tank reactions

Energy Technology Data Exchange (ETDEWEB)

Burger, L.L.

1995-10-01

Continual concern has been expressed over potentially hazardous exothermic reactions that might occur in Hanford Site underground waste storage tanks. These tanks contain many different oxidizable compounds covering a wide range of concentrations. The chemical hazards are a function of several interrelated factors, including the amount of energy (heat) produced, how fast it is produced, and the thermal absorption and heat transfer properties of the system. The reaction path(s) will determine the amount of energy produced and kinetics will determine the rate that it is produced. The tanks also contain many inorganic compounds inert to oxidation. These compounds act as diluents and can inhibit exothermic reactions because of their heat capacity and thus, in contrast to the oxidizable compounds, provide mitigation of hazardous reactions. In this report the energy that may be released when various organic and inorganic compounds react is computed as a function of the reaction-mix composition and the temperature. The enthalpy, or integrated heat capacity, of these compounds and various reaction products is presented as a function of temperature; the enthalpy of a given mixture can then be equated to the energy release from various reactions to predict the maximum temperature which may be reached. This is estimated for several different compositions. Alternatively, the amounts of various diluents required to prevent the temperature from reaching a critical value can be estimated. Reactions taking different paths, forming different products such as N{sub 2}O in place of N{sub 2} are also considered, as are reactions where an excess of caustic is present. Oxidants other than nitrate and nitrite are considered briefly.

In Situ Apparatus to Study Gas-Metal Reactions and Wettability at High Temperatures for Hot-Dip Galvanizing Applications

Science.gov (United States)

Koltsov, A.; Cornu, M.-J.; Scheid, J.

2018-02-01

The understanding of gas-metal reactions and related surface wettability at high temperatures is often limited due to the lack of in situ surface characterization. Ex situ transfers at low temperature between annealing furnace, wettability device, and analytical tools induce noticeable changes of surface composition distinct from the reality of the phenomena.Therefore, a high temperature wettability device was designed in order to allow in situ sample surface characterization by x-rays photoelectron spectroscopy after gas/metal and liquid metal/solid metal surface reactions. Such airless characterization rules out any contamination and oxidation of surfaces and reveals their real composition after heat treatment and chemical reaction. The device consists of two connected reactors, respectively, dedicated to annealing treatments and wettability measurements. Heat treatments are performed in an infrared lamp furnace in a well-controlled atmosphere conditions designed to reproduce gas-metal reactions occurring during the industrial recrystallization annealing of steels. Wetting experiments are carried out in dispensed drop configuration with the precise control of the deposited droplets kinetic energies. The spreading of drops is followed by a high-speed CCD video camera at 500-2000 frames/s in order to reach information at very low contact time. First trials have started to simulate phenomena occurring during recrystallization annealing and hot-dip galvanizing on polished pure Fe and FeAl8 wt.% samples. The results demonstrate real surface chemistry of steel samples after annealing when they are put in contact with liquid zinc alloy bath during hot-dip galvanizing. The wetting results are compared to literature data and coupled with the characterization of interfacial layers by FEG-Auger. It is fair to conclude that the results show the real interest of such in situ experimental setup for interfacial chemistry studies.

High-precision (p,t) reactions to determine reaction rates of explosive stellar processes

NARCIS (Netherlands)

Matić, Andrija

2007-01-01

The aim of my study was to investigate the nuclear structure of 22Mg and 26Si. These two nuclei play a significant role in stellar reaction processes at high temperatures. On base of the obtained nuclear structure we calculated the stellar reaction rates for the following reactions: 18Ne(α,p)21Na,

Temperature dependence of three-body ion-molecule reactions

International Nuclear Information System (INIS)

Boehringer, H.; Arnold, F.

1983-01-01

The temperature dependence of the ion-molecule association reactions (i) N 2 + + N 2 + M → N 4 + + M (M=N 2 , He), (ii) O 2 + + O 2 + M → O 4 + + M (M=O 2 , He) and (iii) He + + 2He → He 2 + + He have been studied over an extended temperature range to temperatures as low as 30K with a recently constructed liquid helium-cooled ion drift tube. Over most of the temperature range the threebody reaction rate coefficients show an inverse temperature dependence proportional to Tsup(-n) with n in the range 0.6 to 2.9. This temperature dependence is quite consistent with current theories of ion molecule association. At low temperatures, however, a deviation from the Tsup(-n) dependence was observed for the association reactions (ii). For reactions (i) different temperature dependences were obtained for N 2 and He third bodies indicating an additional temperature dependence of the collisional stabilisation process. (Authors)

High-temperature epoxidation of soybean oil in flow : speeding up elemental reactions wanted and unwanted

NARCIS (Netherlands)

Cortese, B.; Croon, de M.H.J.M.; Hessel, V.

2012-01-01

The soybean oil epoxidation reaction is investigated theoretically through kinetic modeling of temperature effects enabled through flow processing under superheated conditions. Different from previous studies on such processing, here a complex reaction network superimposed by multiphase transport is

Characteristics of liquid product from the pyrolysis of waste plastic mixture at low and high temperatures: Influence of lapse time of reaction

International Nuclear Information System (INIS)

Lee, Kyong-Hwan; Shin, Dae-Hyun

2007-01-01

Pyrolysis of a waste plastic mixture (high-density polyethylene: low-density polyethylene: polypropylene: polystyrene = 3:2:3:1) into a liquid product was carried out in a stirred semi-batch reactor at low (350 deg. C) and high (400 deg. C) temperatures. The effect of lapse time of reaction in the reactor and also degradation temperature on the characteristics of the liquid product from pyrolysis of the mixture was investigated. Liquid products were described by cumulative amount distribution, paraffin, olefin, naphthene and aromatic (PONA) distribution and molecular weight distribution. Their characteristic was quite differed with a lapse time of reaction and also at a low and high degradation temperatures, because of the different physicochemical properties of the plastic types in the mixture. With increase of lapse time of reaction, the order for the main products in PONA components obtained at 350 deg. C was firstly aromatic products and then olefin products, while at 400 deg. C the order was firstly aromatic products, then olefin products and finally paraffin products. The experiments also showed from the molecular weight distribution of liquid PONA components that the paraffin and olefin products had a wide distribution by mainly random scission of polymer, but in the case of olefin products were produced by an end-chain scission mechanism as well as random scission mechanism, as evidenced by much more light olefin products. This phenomenon was evident at a higher degradation temperature. Also, both the light olefin and naphthene products with a molecular weight of around 120, as a main product, showed a similar trend as a function of lapse time, which had a maximum fraction at 343 min (at 350 deg. C) and 83 min (at 400 deg. C). Among PONA components, the highest concentrations of aromatic products were obtained with a molecular weight of around 100 at the fastest lapse time of reaction, regardless of degradation temperature. It was concluded that the

Characteristics of liquid product from the pyrolysis of waste plastic mixture at low and high temperatures: influence of lapse time of reaction.

Science.gov (United States)

Lee, Kyong-Hwan; Shin, Dae-Hyun

2007-01-01

Pyrolysis of a waste plastic mixture (high-density polyethylene: low-density polyethylene: polypropylene: polystyrene = 3:2:3:1) into a liquid product was carried out in a stirred semi-batch reactor at low (350 degrees C) and high (400 degrees C) temperatures. The effect of lapse time of reaction in the reactor and also degradation temperature on the characteristics of the liquid product from pyrolysis of the mixture was investigated. Liquid products were described by cumulative amount distribution, paraffin, olefin, naphthene and aromatic (PONA) distribution and molecular weight distribution. Their characteristic was quite differed with a lapse time of reaction and also at a low and high degradation temperatures, because of the different physicochemical properties of the plastic types in the mixture. With increase of lapse time of reaction, the order for the main products in PONA components obtained at 350 degrees C was firstly aromatic products and then olefin products, while at 400 degrees C the order was firstly aromatic products, then olefin products and finally paraffin products. The experiments also showed from the molecular weight distribution of liquid PONA components that the paraffin and olefin products had a wide distribution by mainly random scission of polymer, but in the case of olefin products were produced by an end-chain scission mechanism as well as random scission mechanism, as evidenced by much more light olefin products. This phenomenon was evident at a higher degradation temperature. Also, both the light olefin and naphthene products with a molecular weight of around 120, as a main product, showed a similar trend as a function of lapse time, which had a maximum fraction at 343 min (at 350 degrees C) and 83 min (at 400 degrees C). Among PONA components, the highest concentrations of aromatic products were obtained with a molecular weight of around 100 at the fastest lapse time of reaction, regardless of degradation temperature. It was

In-operando elucidation of bimetallic CoNi nanoparticles during high-temperature CH 4 /CO 2 reaction

KAUST Repository

Al-Sabban, Bedour

2017-05-02

Dry reforming of methane (DRM) proceeds via CH4 decomposition to leave surface carbon species, followed by their removal with CO2-derived species. Reactivity tuning for stoichiometric CH4/CO2 reactants was attempted by alloying the non-noble metals Co and Ni, which have high affinity with CO2 and high activity for CH4 decomposition, respectively. This study was focused on providing evidence of the capturing surface coverage of the reactive intermediates and the associated structural changes of the metals during DRM at high temperature using in-operando X-ray absorption spectroscopy (XAS). On the Co catalysts, the first-order effects with respect to CH4 pressure and negative-order effects with respect to CO2 pressure on the DRM rate are consistent with the competitive adsorption of the surface oxygen species on the same sites as the CH4 decomposition reaction. The Ni surface provides comparatively higher rates of CH4 decomposition and the resultant DRM than the Co catalyst but leaves some deposited carbon on the catalyst surface. In contrast, the bimetallic CoNi catalyst exhibits reactivity towards the DRM but with kinetic orders resembling Co catalyst, producing negligible carbon deposition by balancing CH4 and CO2 activation. The in-operando X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) measurements confirmed that the Co catalyst was progressively oxidized from the surface to the bulk with reaction time, whereas CoNi and Ni remained relatively reduced during DRM. Density functional theory (DFT) calculation considering the high reaction temperature for DRM confirmed the unselective site arrangement between Co and Ni atoms in both the surface and bulk of the alloy nanoparticle (NP). The calculated heat of oxygen chemisorption became more exothermic in the order of Ni, CoNi, Co, consistent with the catalytic behavior. The comprehensive experimental and theoretical evidence provided herein clearly suggests

High temperature magnetic properties of Co(FeY){sub 2}O{sub 4} synthesized by combustion reaction

Energy Technology Data Exchange (ETDEWEB)

Alves, Thiago Eduardo Pereira, E-mail: thiago.ifgo@gmail.com [Instituto Federal de Educacao, Ciencia e Tecnologia de Goias (IFGO), Goiania (Brazil); Franco Junior, Adolfo [Universidade Federal de Goias (UFG), Goiania (Brazil)

2016-07-01

Full text: Cobalt ferrite is widely studied due to its interesting magnetic behavior at room temperature. However, many technical applications require temperatures that are above that. Thus, it is necessary to understand how some magnetic properties, such as saturation magnetization (Ms), remanent magnetization (Mr), and coercivity (Hc), may behave at high temperatures [1]. Among several methods to synthesize cobalt ferrites, combustion reaction method is intensively used because it is inexpensive, fast and has good control on the stoichiometry. This method is based on the chemistry of propellants and explosives [2]. Therefore, we have prepared a series of nanoparticles of CoFe{sub (2-x)}Y{sub x}O{sub 4}, with x ranging from 0.00 to 0.04, by combustion reaction method. The crystal structure and morphology were characterized by X-ray diffraction (XRD) using Rietveld refinement and transmission electron microscopy (TEM), respectively. Nanocrystalline particles structures in the typical phase of spinel were observed on diffractograms. Micrographies showed high crystalline powders for the particles and particles size within nanoscale range. The magnetic properties were measured by vibrating sample magnetometry (VSM) in broad range of temperature (300-850K). Saturation magnetization (Ms) decreases with Y doping increase, while Hc increases, being about 1.8 higher than the undoped sample. Furthermore, Curie temperature increases with Y doping increase. These magnetic properties were discussed in terms of the particle interactions induced by the thermal fluctuations, cation distribution, and ions exchange between yttrium and cobalt atoms in A-B sites in the cubic structure [3]. References: [1] A. Franco, Jr. and F. C. e Silva, Applied Physics Letters 96, 172505, (2010). 525 [2] S.R. Jain, et al, Combustion and flame 40, 71-79, (1981). [3] A. Franco Jr. et al. Journal of Alloys and Compounds 680, 198-205, (2016). (author)

Initial stages of high temperature metal oxidation

International Nuclear Information System (INIS)

Yang, C.Y.; O'Grady, W.E.

1981-01-01

The application of XPS and UPS to the study of the initial stages of high temperature (> 350 0 C) electrochemical oxidation of iron and nickel is discussed. In the high temperature experiments, iron and nickel electrodes were electrochemically oxidized in contact with a solid oxide electrolyte in the uhv system. The great advantages of this technique are that the oxygen activity at the interface may be precisely controlled and the ability to run the reactions in uhv allows the simultaneous observation of the reactions by XPS

High Pressure Scanning Tunneling Microscopy Studies of Adsorbate Structure and Mobility during Catalytic Reactions. Novel Design of an Ultra High Pressure, High Temperature Scanning Tunneling Microscope System for Probing Catalytic Conversions

International Nuclear Information System (INIS)

Tang, David Chi-Wai

2005-01-01

The aim of the work presented therein is to take advantage of scanning tunneling microscope's (STM) capability for operation under a variety of environments under real time and at atomic resolution to monitor adsorbate structures and mobility under high pressures, as well as to design a new generation of STM systems that allow imaging in situ at both higher pressures (35 atm) and temperatures (350 C). The design of a high pressure, high temperature scanning tunneling microscope system, that is capable of monitoring reactions in situ at conditions from UHV and ambient temperature up to 1 atm and 250 C, is briefly presented along with vibrational and thermal analysis, as this system serves as a template to improve upon during the design of the new ultra high pressure, high temperature STM. Using this existing high pressure scanning tunneling microscope we monitored the co-adsorption of hydrogen, ethylene and carbon dioxide on platinum (111) and rhodium (111) crystal faces in the mTorr pressure range at 300 K in equilibrium with the gas phase. During the catalytic hydrogenation of ethylene to ethane in the absence of CO the metal surfaces are covered by an adsorbate layer that is very mobile on the time scale of STM imaging. We found that the addition of CO poisons the hydrogenation reaction and induces ordered structures on the single crystal surfaces. Several ordered structures were observed upon CO addition to the surfaces pre-covered with hydrogen and ethylene: a rotated (√19 x √19)R23.4 o on Pt(111), and domains of c(4 x 2)-CO+C 2 H 3 , previously unobserved (4 x 2)-CO+3C 2 H 3 , and (2 x 2)-3CO on Rh(111). A mechanism for CO poisoning of ethylene hydrogenation on the metal single crystals was proposed, in which CO blocks surface metal sites and reduces adsorbate mobility to limit adsorption and reaction rate of ethylene and hydrogen. In order to observe heterogeneous catalytic reactions that occur well above ambient pressure and temperature that more closely

Temperature dependence on sodium-water chemical reaction

International Nuclear Information System (INIS)

Tamura, Kenta; Deguchi, Yoshihiro; Suzuki, Koichi; Takata, Takashi; Yamaguchi, Akira; Kikuchi, Shin; Ohshima, Hiroyuki

2012-01-01

In a sodium-cooled fast reactor (SFR), liquid sodium is used as a heat transfer fluid because of its excellent heat transport capability. On the other hand, it has strong chemical reactivity with water vapor. One of the design basis accidents of the SFR is the water leakage into the liquid sodium flow by a breach of heat transfer tubes. This process ends up damages on the heat transport equipment in the SFR. Therefore, the study on sodium-water chemical reactions is of paramount importance for security reasons. This study aims to clarify the sodium-water reaction mechanisms using laser diagnostics. A quasi one-dimensional flame model is also applied to a sodium-water counter-flow reaction field. Temperature, H 2 , H 2 O, OH, Na and Particulate matter were measured using laser induced fluorescence and CARS in the counter-flow reaction field. The temperature of the reaction field was also modified to reduce the condensation of Na in the reaction zone. (author)

High-temperature unimolecular decomposition of ethyl propionate

KAUST Repository

Giri, Binod

2016-10-09

This work reports rate coefficients of the thermal unimolecular decomposition reaction of ethyl propionate (EP) behind reflected shock waves over the temperature range of 976–1300 K and pressures of 825–1875 Torr. The reaction progress was monitored by detecting CH near 10.532 μm using CO gas laser absorption. In addition, G3//MP2/aug-cc-pVDZ and master equation calculations were performed to assess the pressure- and temperature-dependence of the reaction. Our calculations revealed that CH elimination occurs via a six-centered retro-ene transition state. Our measured rate data are close to the high-pressure limit and showed no discernable temperature fall off.

Temperature effects on lithium-nitrogen reaction rates

International Nuclear Information System (INIS)

Ijams, W.J.; Kazimi, M.S.

1985-08-01

A series of experiments have been run with the aim of measuring the reaction rate of lithium and nitrogen over a wide spectrum of lithium pool temperatures. In these experiments, pure nitrogen was blown at a controlled flow rate over a preheated lithium pool. The pool had a surface area of approximately 4 cm 2 and a total volume of approximately 6 cm 3 . The system pressure varied from 0 to 4 psig. The reaction rate was very small - approximately 0.002 to 0.003 g Li min cm 2 for lithium temperatures below 500 0 C. Above 500 0 C the reaction rate began to increase sharply, and reached a maximum of approximately 0.80 g Li min cm 2 above 700 0 C. It dropped off beyond 1000 0 C and seemed to approach zero at 1150 0 C. The maximum reaction rate observed in these forced convection experiments was higher by 60% than those previously observed in experiments where the nitrogen flowed to the reaction site by means of natural convection. During a reaction, a hard nitride layer built up on the surface of the lithium pool - its effect on the reaction rate was observed. The effect of the nitrogen flow rate on the reaction rate was also observed

Experimental determination of the high-temperature rate constant for the reaction of OH with sec-butanol.

Science.gov (United States)

Pang, Genny A; Hanson, Ronald K; Golden, David M; Bowman, Craig T

2012-10-04

The overall rate constant for the reaction of OH with sec-butanol [CH(3)CH(OH)CH(2)CH(3)] was determined from measurements of the near-first-order OH decay in shock-heated mixtures of tert-butylhydroperoxide (as a fast source of OH) with sec-butanol in excess. Three kinetic mechanisms from the literature describing sec-butanol combustion were used to examine the sensitivity of the rate constant determination to secondary kinetics. The overall rate constant determined can be described by the Arrhenius expression 6.97 × 10(-11) exp(-1550/T[K]) cm(3) molecule(-1) s(-1), valid over the temperature range of 888-1178 K. Uncertainty bounds of ±30% were found to adequately account for the uncertainty in secondary kinetics. To our knowledge, the current data represent the first efforts toward an experimentally determined rate constant for the overall reaction of OH with sec-butanol at combustion-relevant temperatures. A rate constant predicted using a structure-activity relationship from the literature was compared to the current data and previous rate constant measurements for the title reaction at atmospheric-relevant temperatures. The structure-activity relationship was found to be unable to correctly predict the measured rate constant at all temperatures where experimental data exist. We found that the three-parameter fit of 4.95 × 10(-20)T(2.66) exp(+1123/T[K]) cm(3) molecule(-1) s(-1) better describes the overall rate constant for the reaction of OH with sec-butanol from 263 to 1178 K.

Catalytic Depolymerization of Lignin and Woody Biomass in Supercritical Ethanol: Influence of Reaction Temperature and Feedstock.

Science.gov (United States)

Huang, Xiaoming; Atay, Ceylanpinar; Zhu, Jiadong; Palstra, Sanne W L; Korányi, Tamás I; Boot, Michael D; Hensen, Emiel J M

2017-11-06

The one-step ethanolysis approach to upgrade lignin to monomeric aromatics using a CuMgAl mixed oxide catalyst is studied in detail. The influence of reaction temperature (200-420 °C) on the product distribution is investigated. At low temperature (200-250 °C), recondensation is dominant, while char-forming reactions become significant at high reaction temperature (>380 °C). At preferred intermediate temperatures (300-340 °C), char-forming reactions are effectively suppressed by alkylation and Guerbet and esterification reactions. This shifts the reaction toward depolymerization, explaining high monomeric aromatics yield. Carbon-14 dating analysis of the lignin residue revealed that a substantial amount of the carbon in the lignin residue originates from reactions of lignin with ethanol. Recycling tests show that the activity of the regenerated catalyst was strongly decreased due to a loss of basic sites due to hydrolysis of the MgO function and a loss of surface area due to spinel oxide formation of the Cu and Al components. The utility of this one-step approach for upgrading woody biomass was also demonstrated. An important observation is that conversion of the native lignin contained in the lignocellulosic matrix is much easier than the conversion of technical lignin.

Study Progress of Physiological Responses in High Temperature Environment

Science.gov (United States)

Li, K.; Zheng, G. Z.; Bu, W. T.; Wang, Y. J.; Lu, Y. Z.

2017-10-01

Certain workers are exposed to high temperatures for a long time. Heat stress will result in a series of physiological responses, and cause adverse effects on the health and safety of workers. This paper summarizes the physiological changes of cardiovascular system, core temperature, skin temperature, water-electrolyte metabolism, alimentary system, neuroendocrine system, reaction time and thermal fatigue in high temperature environments. It can provide a theoretical guidance for labor safety in high temperature environment.

Detailed Reaction Kinetics for CFD Modeling of Nuclear Fuel Pellet Coating for High Temperature Gas-Cooled Reactors

International Nuclear Information System (INIS)

Battaglia, Francine

2008-01-01

The research project was related to the Advanced Fuel Cycle Initiative and was in direct alignment with advancing knowledge in the area of Nuclear Fuel Development related to the use of TRISO fuels for high-temperature reactors. The importance of properly coating nuclear fuel pellets received a renewed interest for the safe production of nuclear power to help meet the energy requirements of the United States. High-temperature gas-cooled nuclear reactors use fuel in the form of coated uranium particles, and it is the coating process that was of importance to this project. The coating process requires four coating layers to retain radioactive fission products from escaping into the environment. The first layer consists of porous carbon and serves as a buffer layer to attenuate the fission and accommodate the fuel kernel swelling. The second (inner) layer is of pyrocarbon and provides protection from fission products and supports the third layer, which is silicon carbide. The final (outer) layer is also pyrocarbon and provides a bonding surface and protective barrier for the entire pellet. The coating procedures for the silicon carbide and the outer pyrocarbon layers require knowledge of the detailed kinetics of the reaction processes in the gas phase and at the surfaces where the particles interact with the reactor walls. The intent of this project was to acquire detailed information on the reaction kinetics for the chemical vapor deposition (CVD) of carbon and silicon carbine on uranium fuel pellets, including the location of transition state structures, evaluation of the associated activation energies, and the use of these activation energies in the prediction of reaction rate constants. After the detailed reaction kinetics were determined, the reactions were implemented and tested in a computational fluid dynamics model, MFIX. The intention was to find a reduced mechanism set to reduce the computational time for a simulation, while still providing accurate results

High temperature synthesis of ceramic composition by directed reaction of molten titanium or zirconium with boron carbide

International Nuclear Information System (INIS)

Johnson, W.B.

1990-01-01

Alternative methods of producing ceramics and ceramic composites include sintering, hot pressing and more recently hot isostatic pressing (HIP) and self-propagating high temperature synthesis (SHS). Though each of these techniques has its advantages, each suffers from several restrictions as well. Sintering may require long times at high temperatures and for most materials requires sintering aids to get full density. These additives can, and generally do, change (often degrade) the properties of the ceramic. Hot pressing and hot isostatic pressing are convenient methods to quickly prepare samples of some materials to full density, but generally are expensive and may damage some types of reinforcements during densification. This paper focuses on the preparation and processing of composites prepared by the directed reaction of molten titanium or zirconium with boron carbide. Advantages and disadvantages of this approach when compared to traditional methods are discussed, with reference to specific examples. Examples of microstructure are properties of these materials are reported

Samarium ion exchanged montmorillonite for high temperature cumene cracking reaction

International Nuclear Information System (INIS)

Binitha, N.N.

2009-01-01

Full text: Nano material Montmorillonite clay is cation exchanged with samarium and its catalytic influence in cumene cracking reaction is investigated. Effect of exchange with sodium ions on further exchange with samarium ions is also noted. Acidity measurements are done using TPD of ammonia. The retention of basic structure is proved from FTIR spectra and XRD patterns. Elemental analysis result shows that samarium exchange has occurred, which is responsible for the higher catalytic activity. Surface area and pore volume remains more or less unaffected upon exchange. Thermogravimetric analysis indicates the enhanced thermal stability on exchanging. Cumene cracking reaction is carried out at atmospheric pressure in a fixed bed glass reactor at 673 K. The predominance of Bronsted acidity is confirmed from high selectivity to benzene. (author)

Kinetics of iron redox reaction in silicate melts: A high temperature Xanes study on an alkali basalt

Energy Technology Data Exchange (ETDEWEB)

Cochain, B; Neuville, D R; Roux, J; Strukelj, E; Richet, P [Physique des Mineraux et Magmas, Geochimie-Cosmochimie, CNRS-IPGP, 4 place Jussieu, 75005 Paris (France); Ligny, D de [Universite Claude Bernard Lyon 1, LPCML, F-69622 Villeurbanne (France); Baudelet, F, E-mail: cochain@ipgp.jussieu.f [Synchrotron SOLEIL, L' Orme des Merisiers, Saint Aubin (France)

2009-11-15

In Earth and Materials sciences, iron is the most important transition element. Glass and melt properties are strongly affected by iron content and redox state with the consequence that some properties (i.e. viscosity, heat capacity, crystallization...) depend not only on the amounts of Fe{sup 2+} and Fe{sup 3+}, but also on the coordination state of these ions. In this work we investigate iron redox reactions through XANES experiments at the K-edge of iron. Using a high-temperature heating device, pre-edge of XANES spectra exhibits definite advantages to make in-situ measurements and to determine the evolution of redox state with time, temperature and composition of synthetic silicate melts. In this study, new kinetics measurements are presented for a basalt melt from the 31,000-BC eruption of the Puy de Lemptegy Volcano in France. These measurements have been made between 773 K and at superliquidus temperatures up to 1923 K.

Kinetics of iron redox reaction in silicate melts: A high temperature Xanes study on an alkali basalt

International Nuclear Information System (INIS)

Cochain, B; Neuville, D R; Roux, J; Strukelj, E; Richet, P; Ligny, D de; Baudelet, F

2009-01-01

In Earth and Materials sciences, iron is the most important transition element. Glass and melt properties are strongly affected by iron content and redox state with the consequence that some properties (i.e. viscosity, heat capacity, crystallization...) depend not only on the amounts of Fe 2+ and Fe 3+ , but also on the coordination state of these ions. In this work we investigate iron redox reactions through XANES experiments at the K-edge of iron. Using a high-temperature heating device, pre-edge of XANES spectra exhibits definite advantages to make in-situ measurements and to determine the evolution of redox state with time, temperature and composition of synthetic silicate melts. In this study, new kinetics measurements are presented for a basalt melt from the 31,000-BC eruption of the Puy de Lemptegy Volcano in France. These measurements have been made between 773 K and at superliquidus temperatures up to 1923 K.

Temperature dependence of muonium reaction rates in the gas phase

International Nuclear Information System (INIS)

Fleming, D.G.; Garner, D.M.; Mikula, R.J.; British Columbia Univ., Vancouver

1981-01-01

A study of the temperature dependence of reaction rates has long been an important tool in establishing reaction pathways in chemical reactions. This is particularly true for the reactions of muonium (in comparison with those of hydrogen) since a measurement of the activation energy for chemical reaction is sensitive to both the height and the position of the potential barrier in the reaction plane. For collision controlled reactions, on the other hand, the reaction rate is expected to exhibit a weak T 1 sup(/) 2 dependence characteristic of the mean collision velocity. These concepts are discussed and their effects illustrated in a comparison of the chemical and spin exchange reaction rates of muonium and hydrogen in the temperature range approx.300-approx.500 K. (orig.)

High-pressure modulation of the structure of the bacterial photochemical reaction center at physiological and cryogenic temperatures

Science.gov (United States)

Timpmann, Kõu; Kangur, Liina; Lõhmus, Ants; Freiberg, Arvi

2017-07-01

The optical absorption and fluorescence response to external high pressure of the reaction center membrane chromoprotein complex from the wild-type non-sulfur photosynthetic bacterium Rhodobacter sphaeroides was investigated using the native pigment cofactors as local molecular probes of the reaction center structure at physiological (ambient) and cryogenic (79 K) temperatures. In detergent-purified complexes at ambient temperature, abrupt blue shift and accompanied broadening of the special pair band was observed at about 265 MPa. These reversible in pressure features were assigned to a pressure-induced rupture of a lone hydrogen bond that binds the photo-chemically active L-branch primary electron donor bacteriochlorophyll cofactor to the surrounding protein scaffold. In native membrane-protected complexes the hydrogen bond rupture appeared significantly restricted and occurred close to about 500 MPa. The free energy change associated with the rupture of the special pair hydrogen bond in isolate complexes was estimated to be equal to about 12 kJ mol-1. In frozen samples at cryogenic temperatures the hydrogen bond remained apparently intact up to the maximum utilized pressure of 600 MPa. In this case, however, heterogeneous spectral response of the cofactors from the L-and M-branches was observed due to anisotropic build-up of the protein structure. While in solid phase, the special pair fluorescence as a function of pressure exactly followed the respective absorption spectrum at a constant Stokes shift, at ambient temperature, the two paths began to deviate strongly from one other at the hydrogen bond rupture pressure. This effect was tentatively interpreted by different emission properties of hydrogen-bound and hydrogen-unbound special pair exciton states.

High temperature ceramic-tubed reformer

Science.gov (United States)

Williams, Joseph J.; Rosenberg, Robert A.; McDonough, Lane J.

1990-03-01

The overall objective of the HiPHES project is to develop an advanced high-pressure heat exchanger for a convective steam/methane reformer. The HiPHES steam/methane reformer is a convective, shell and tube type, catalytic reactor. The use of ceramic tubes will allow reaction temperature higher than the current state-of-the-art outlet temperatures of about 1600 F using metal tubes. Higher reaction temperatures increase feedstock conversion to synthesis gas and reduce energy requirements compared to currently available radiant-box type reformers using metal tubes. Reforming of natural gas is the principal method used to produce synthesis gas (primarily hydrogen and carbon monoxide, H2 and CO) which is used to produce hydrogen (for refinery upgrading), methanol, as well as several other important materials. The HiPHES reformer development is an extension of Stone and Webster's efforts to develop a metal-tubed convective reformer integrated with a gas turbine cycle.

Electrochemical cell and electrode designs for high-temperature/high-pressure kinetic measurements

International Nuclear Information System (INIS)

Nagy, Z.; Yonco, R.M.

1987-05-01

Many corrosion processes of interest to the nuclear power industry occur in high-temperature/high-pressure aqueous systems. The investigation of the kinetics of the appropriate electrode reactions is a serious experimental challenge, partially because of the high temperatures and pressures and partially because many of these reactions are very rapid, requiring fast relaxation measurements. An electrochemical measuring system is described which is suitable for measurements of the kinetics of fast electrode reactions at temperatures extending to at least 300 0 C and pressures to at least 10 MPa (100 atmospheres). The system includes solution preparation and handling equipment, the electrochemical cell, and several electrode designs. One of the new designs is a coaxial working electrode-counter electrode assembly; this electrode can be used with very fast-rising pulses, and it provides a well defined, repeatedly-polishable working surface. Low-impedance reference electrodes are also described, based on electrode concepts responding to the pH or the redox potential of the test solution. Additionally, a novel, long-life primary reference electrode design is reported, based on a modification of the external, pressure-balanced Ag/AgCl reference electrode

Electrochemical cell and electrode designs for high-temperature/high-pressure kinetic measurements

International Nuclear Information System (INIS)

Nagy, Z.; Yonco, R.M.

1988-01-01

Many corrosion processes of interest to the nuclear power industry occur in high-temperature/high-pressure aqueous systems. The investigation of the kinetics of the appropriate electrode reactions is a serious experimental challenge, partially because of the high temperatures and pressures and partially because many of these reactions are very rapid, requiring fast relaxation measurements. An electrochemical measuring system is described which is suitable for measurements of the kinetics of fast electrode reactions at temperatures extending to at least 300 0 C and pressures to at least 10 MPa (100 atmospheres). The system includes solution preparation and handling equipment, the electrochemical cell, and several electrode designs. One of the new designs is a coaxial working electrode-counter electrode assembly; this electrode can be used with very fast-rising pulses, and it provides a well defined, repeatedly-polishable working surface. Low-impedance reference electrodes are also described, based on electrode concepts responding to the pH or the redox potential of the test solution. Additionally, a novel, long-life primary reference electrode design is reported, based on a modification of the external, pressure-balanced Ag/AgCl reference electrode

Oxidation characteristics of MgF2 in air at high temperature

Science.gov (United States)

Chen, H. K.; Jie, Y. Y.; Chang, L.

2017-02-01

High temperature oxidation properties of MgF2 in air were studied. The changes of phase composition, macro surface morphology, weight and elemental composition of MgF2 samples with temperature were investigated by using XRD, EDS and gravimetric analyses. The results show that the oxidation reaction of MgF2 converted to MgO occurred at high temperature, and the reaction was accelerated by the increase of temperature and the presence of impurities. This result clarifies the understanding of the high temperature oxidation behavior of MgF2 in air, and provides a theoretical basis for the reasonable application of MgF2 in optical coating materials, electronic ceramic materials and magnesium melt protection.

An integrated high temperature environmental cell for atom probe tomography studies of gas-surface reactions: Instrumentation and results

International Nuclear Information System (INIS)

Dumpala, S.; Broderick, S.R.; Bagot, P.A.J.; Rajan, K.

2014-01-01

An integrated environmental cell has been designed and developed for the latest generation of Atom Probe Tomography LEAP™ instruments, allowing controlled exposure of samples to gases at high temperatures. Following treatment, samples can be transferred through the LEAP vacuum system for subsequent APT analysis, which provides detailed information on changes to chemical microstructures following the reactions with near-atomic resolution. A full description of the cell is presented, along with some sample results on the oxidation of aluminum and two platinum-group alloys, demonstrating the capability of combining exposure/characterization functionality in a single instrument. - Highlights: • Designed and built atom probe environmental cell for in situ reactions. • Investigated Al oxidation, and demonstrated improvement with new cell. • in situ APT analysis of Pt-alloys showed surface segregation of Rh and Ir

High-temperature shock tube and modeling studies on the reactions of methanol with D-atoms and CH3-radicals.

Science.gov (United States)

Peukert, S L; Michael, J V

2013-10-10

The shock tube technique has been used to study the hydrogen abstraction reactions D + CH3OH → CH2O + H + HD (A) and CH3 + CH3OH → CH2O + H + CH4 (B). For reaction A, the experiments span a T-range of 1016 K ≤ T ≤ 1325 K, at pressures 0.25 bar ≤ P ≤ 0.46 bar. The experiments on reaction B, CH3 + CH3OH, cover a T-range of 1138 K ≤ T ≤ 1270 K, at pressures around 0.40 bar. Reflected shock tube experiments, monitoring the depletion of D-atoms by applying D-atom atomic resonance absorption spectrometry (ARAS), were performed on reaction A using gas mixtures of C2D5I and CH3OH in Kr bath gas. C2D5I was used as precursor for D-atoms. For reaction B, reflected shock tube experiments monitoring H-atom formation with H-ARAS, were carried out using gas mixtures of diacetyl ((CH3CO)2) and CH3OH in Kr bath gas. (CH3CO)2 was used as the source of CH3-radicals. Detailed reaction models were assembled to fit the D-atom and H-atom time profiles in order to obtain experimental rate constants for reactions A and B. Total rate constants from the present experiments on D + CH3OH and CH3 + CH3OH can be represented by the Arrhenius equations kA(T) = 1.51 × 10(-10) exp(-3843 K/T) cm(3) molecules(-1) s(-1) (1016 K ≤ T ≤ 1325 K) and kB(T) = 9.62 × 10(-12) exp(-7477 K/T) cm(3) molecules(-1) s(-1) (1138 K ≤ T ≤ 1270 K). The experimentally obtained rate constants were compared with available rate data from the literature. The results from quantum chemical studies on reaction A were found to be in good agreement with the present results. The present work represents the first direct experimental study on these bimolecular reactions at combustion temperatures and is important to the high-temperature oxidation of CH3OH.

The reaction of OH with H at elevated temperatures

DEFF Research Database (Denmark)

Lundström, T.; Christensen, H.; Sehested, K.

2002-01-01

The temperature dependence of the rate constant for the reaction between OH radicals and H atoms has been determined in Ar-saturated solutions at pH 2. The reaction was studied in the temperature range 5-233degreesC. The rate constants at 20degreesC and 200degreesC are 9.3 x 10(9) and 3.3 x 10...

Iron based superconductors and related compounds synthesized by solid state metathesis and high temperature reactions

International Nuclear Information System (INIS)

Frankovsky, Rainer

2013-01-01

The results of this thesis can be divided into three major topics, which can also be seen as different approaches of solid state chemistry to reveal interesting features of known and unknown compounds and to develop alternative synthesis routes. Firstly, known compounds with related structural motifs to the superconducting iron-arsenides were investigated regarding their structural and physical properties. In case of La 3 Pd 4 Ge 4 the influence of Fe doping on the properties was studied, whereas in the series ZrMAs (M=Ti,V) the physical properties have not yet been reported at all and were investigated for the first time. Secondly, an alternative synthesis route has been developed for the synthesis of superconducting LaFeAsO 1-x F x . This solid state metathesis reaction distinctly increased the quality of the samples compared to conventionally prepared products. Furthermore, the reaction pathway was investigated and clarified, which helps to understand the processes during high temperature solid state metathesis reactions in general. Thirdly, this alternative synthesis route was expanded to other systems and new compounds like co-substituted LaFe 1-x Mn x AsO 1-y F y were prepared and thoroughly investigated. This led to a complex study of the interplay of magnetism, electronic and structural conditions and the occurrence of superconducting properties. The investigation and understanding of such complex coherences will probably be decisive for the further understanding of the superconducting mechanism in iron based superconductors.

An atmospheric pressure high-temperature laminar flow reactor for investigation of combustion and related gas phase reaction systems.

Science.gov (United States)

Oßwald, Patrick; Köhler, Markus

2015-10-01

A new high-temperature flow reactor experiment utilizing the powerful molecular beam mass spectrometry (MBMS) technique for detailed observation of gas phase kinetics in reacting flows is presented. The reactor design provides a consequent extension of the experimental portfolio of validation experiments for combustion reaction kinetics. Temperatures up to 1800 K are applicable by three individually controlled temperature zones with this atmospheric pressure flow reactor. Detailed speciation data are obtained using the sensitive MBMS technique, providing in situ access to almost all chemical species involved in the combustion process, including highly reactive species such as radicals. Strategies for quantifying the experimental data are presented alongside a careful analysis of the characterization of the experimental boundary conditions to enable precise numeric reproduction of the experimental results. The general capabilities of this new analytical tool for the investigation of reacting flows are demonstrated for a selected range of conditions, fuels, and applications. A detailed dataset for the well-known gaseous fuels, methane and ethylene, is provided and used to verify the experimental approach. Furthermore, application for liquid fuels and fuel components important for technical combustors like gas turbines and engines is demonstrated. Besides the detailed investigation of novel fuels and fuel components, the wide range of operation conditions gives access to extended combustion topics, such as super rich conditions at high temperature important for gasification processes, or the peroxy chemistry governing the low temperature oxidation regime. These demonstrations are accompanied by a first kinetic modeling approach, examining the opportunities for model validation purposes.

An atmospheric pressure high-temperature laminar flow reactor for investigation of combustion and related gas phase reaction systems

Energy Technology Data Exchange (ETDEWEB)

Oßwald, Patrick; Köhler, Markus [Institute of Combustion Technology, German Aerospace Center (DLR), Pfaffenwaldring 38-40, D-70569 Stuttgart (Germany)

2015-10-15

A new high-temperature flow reactor experiment utilizing the powerful molecular beam mass spectrometry (MBMS) technique for detailed observation of gas phase kinetics in reacting flows is presented. The reactor design provides a consequent extension of the experimental portfolio of validation experiments for combustion reaction kinetics. Temperatures up to 1800 K are applicable by three individually controlled temperature zones with this atmospheric pressure flow reactor. Detailed speciation data are obtained using the sensitive MBMS technique, providing in situ access to almost all chemical species involved in the combustion process, including highly reactive species such as radicals. Strategies for quantifying the experimental data are presented alongside a careful analysis of the characterization of the experimental boundary conditions to enable precise numeric reproduction of the experimental results. The general capabilities of this new analytical tool for the investigation of reacting flows are demonstrated for a selected range of conditions, fuels, and applications. A detailed dataset for the well-known gaseous fuels, methane and ethylene, is provided and used to verify the experimental approach. Furthermore, application for liquid fuels and fuel components important for technical combustors like gas turbines and engines is demonstrated. Besides the detailed investigation of novel fuels and fuel components, the wide range of operation conditions gives access to extended combustion topics, such as super rich conditions at high temperature important for gasification processes, or the peroxy chemistry governing the low temperature oxidation regime. These demonstrations are accompanied by a first kinetic modeling approach, examining the opportunities for model validation purposes.

Ammonia oxidation at high pressure and intermediate temperatures

DEFF Research Database (Denmark)

Song, Yu; Hashemi, Hamid; Christensen, Jakob Munkholt

2016-01-01

Ammonia oxidation experiments were conducted at high pressure (30 bar and 100 bar) under oxidizing and stoichiometric conditions, respectively, and temperatures ranging from 450 to 925 K. The oxidation of ammonia was slow under stoichiometric conditions in the temperature range investigated. Under...... oxidizing conditions the onset temperature for reaction was 850–875 K at 30 bar, while at 100 bar it was about 800 K, with complete consumption of NH3 at 875 K. The products of reaction were N2 and N2O, while NO and NO2 concentrations were below the detection limit even under oxidizing conditions. The data...... was satisfactory. The main oxidation path for NH3 at high pressure under oxidizing conditions is NH3⟶+OH NH2⟶+HO2,NO2 H2NO⟶+O2 HNO⟶+O2 NO ⟶+NH2 N2. The modeling predictions are most sensitive to the reactions NH2 + NO = NNH + OH and NH2 + HO2 = H2NO + OH, which promote the ammonia consumption by forming OH...

High Temperature Phenomena in Shock Waves

CERN Document Server

2012-01-01

The high temperatures generated in gases by shock waves give rise to physical and chemical phenomena such as molecular vibrational excitation, dissociation, ionization, chemical reactions and inherently related radiation. In continuum regime, these processes start from the wave front, so that generally the gaseous media behind shock waves may be in a thermodynamic and chemical non-equilibrium state. This book presents the state of knowledge of these phenomena. Thus, the thermodynamic properties of high temperature gases, including the plasma state are described, as well as the kinetics of the various chemical phenomena cited above. Numerous results of measurement and computation of vibrational relaxation times, dissociation and reaction rate constants are given, and various ionization and radiative mechanisms and processes are presented. The coupling between these different phenomena is taken into account as well as their interaction with the flow-field. Particular points such as the case of rarefied flows an...

Hydrothermal Liquefaction of Dried Distillers Grains with solubles: A reaction temperature study

DEFF Research Database (Denmark)

Mørup, Anders; Christensen, Per Runge; Aarup, David Friis

2012-01-01

provides rapid heating of biomass feeds and the option of performing multiple sequential repetitions. This bypasses long, uncontrollable temperature gradients and unintended changes in the reaction chemistry. The product, a crude bio-oil, was characterized in terms of yield, elemental composition......The effect of the reaction temperature on hydrothermal liquefaction of dried distillers grains with solubles (DDGS) was investigated using a novel stop-flow reactor system at varying temperatures (300–400 °C), fixed pressure (250 bar), and fixed reaction time (15 min). The stop-flow reactor......, and chemical composition. Higher reaction temperatures resulted in improved bio-oil yields, less char formation, and higher heating values of the bio-oil. A supercritical reaction temperature of 400 °C was found to produce bio-oil in the highest yields and of the best quality....

PLA recycling by hydrolysis at high temperature

Energy Technology Data Exchange (ETDEWEB)

Cristina, Annesini Maria; Rosaria, Augelletti; Sara, Frattari, E-mail: sara.frattari@uniroma1.it; Fausto, Gironi [Department of Chemical Engineering Materials Environment, University of Rome “La Sapienza”, Via Eudossiana 18– 00184 Roma (Italy)

2016-05-18

In this work the process of PLA hydrolysis at high temperature was studied, in order to evaluate the possibility of chemical recycling of this polymer bio-based. In particular, the possibility to obtain the monomer of lactic acid from PLA degradation was investigated. The results of some preliminary tests, performed in a laboratory batch reactor at high temperature, are presented: the experimental results show that the complete degradation of PLA can be obtained in relatively low reaction times.

Computational study of chain transfer to monomer reactions in high-temperature polymerization of alkyl acrylates.

Science.gov (United States)

Moghadam, Nazanin; Liu, Shi; Srinivasan, Sriraj; Grady, Michael C; Soroush, Masoud; Rappe, Andrew M

2013-03-28

This article presents a computational study of chain transfer to monomer (CTM) reactions in self-initiated high-temperature homopolymerization of alkyl acrylates (methyl, ethyl, and n-butyl acrylate). Several mechanisms of CTM are studied. The effects of the length of live polymer chains and the type of monoradical that initiated the live polymer chains on the energy barriers and rate constants of the involved reaction steps are investigated theoretically. All calculations are carried out using density functional theory. Three types of hybrid functionals (B3LYP, X3LYP, and M06-2X) and four basis sets (6-31G(d), 6-31G(d,p), 6-311G(d), and 6-311G(d,p)) are applied to predict the molecular geometries of the reactants, products and transition sates, and energy barriers. Transition state theory is used to estimate rate constants. The results indicate that abstraction of a hydrogen atom (by live polymer chains) from the methyl group in methyl acrylate, the methylene group in ethyl acrylate, and methylene groups in n-butyl acrylate are the most likely mechanisms of CTM. Also, the rate constants of CTM reactions calculated using M06-2X are in good agreement with those estimated from polymer sample measurements using macroscopic mechanistic models. The rate constant values do not change significantly with the length of live polymer chains. Abstraction of a hydrogen atom by a tertiary radical has a higher energy barrier than abstraction by a secondary radical, which agrees with experimental findings. The calculated and experimental NMR spectra of dead polymer chains produced by CTM reactions are comparable. This theoretical/computational study reveals that CTM occurs most likely via hydrogen abstraction by live polymer chains from the methyl group of methyl acrylate and methylene group(s) of ethyl (n-butyl) acrylate.

Extrapolation of rate constants of reactions producing H2 and O2 in radiolysis of water at high temperatures

International Nuclear Information System (INIS)

Leblanc, R.; Ghandi, K.; Hackman, B.; Liu, G.

2014-01-01

One target of our research is to extrapolate known data on the rate constants of reactions and add corrections to estimate the rate constants at the higher temperatures reached by the SCWR reactors. The focus of this work was to extrapolate known data on the rate constants of reactions that produce Hydrogen or Oxygen with a rate constant below 10 10 mol -1 s -1 at room temperature. The extrapolation is done taking into account the change in the diffusion rate of the interacting species and the cage effect with thermodynamic conditions. The extrapolations are done over a wide temperature range and under isobaric conditions. (author)

Design and Application of a High-Temperature Linear Ion Trap Reactor

Science.gov (United States)

Jiang, Li-Xue; Liu, Qing-Yu; Li, Xiao-Na; He, Sheng-Gui

2018-01-01

A high-temperature linear ion trap reactor with hexapole design was homemade to study ion-molecule reactions at variable temperatures. The highest temperature for the trapped ions is up to 773 K, which is much higher than those in available reports. The reaction between V2O6 - cluster anions and CO at different temperatures was investigated to evaluate the performance of this reactor. The apparent activation energy was determined to be 0.10 ± 0.02 eV, which is consistent with the barrier of 0.12 eV calculated by density functional theory. This indicates that the current experimental apparatus is prospective to study ion-molecule reactions at variable temperatures, and more kinetic details can be obtained to have a better understanding of chemical reactions that have overall barriers. [Figure not available: see fulltext.

Reaction of yttria-stabilized zirconia with zirconium, silicon and Zircaloy-4 at high temperature: a compatibility study for cermet fuels

International Nuclear Information System (INIS)

Arima, T.; Tateyama, T.; Idemitsu, K.; Inagaki, Y.

2003-01-01

Compatibility studies for cermet (ceramic and metal) fuels have been completed for a temperature range of 1073-1423 K. A reaction between yttria-stabilized zirconia (YSZ), as a simulated fuel, and Zr, as a candidate for a metallic matrix, has been observed at temperatures ≥1273 K, which means the formation of a metallic reaction layer at the interface between YSZ and Zr and the occurrence of metallic phases inside the YSZ. Similar results were observed for the YSZ-Zry4 (cladding) system. On the other hand, the degree of reaction was relatively large for the YSZ-Si (metallic matrix) system, and Si diffused into the YSZ. However, the maximum fuel center-line temperature can be predicted to be less than ∼1273 K for cermet fuels. Therefore, compatibility between the ceramic fuel and the metallic matrix should be good under normal reactor operational conditions. Furthermore, since the temperature of the fuel-cladding gap is lower, the cermet fuel and the cladding material are compatible

Moderate temperature gas purification system: Application to high calorific coal-derived fuel

Energy Technology Data Exchange (ETDEWEB)

Kobayashi, M.; Shirai, H.; Nunokawa, M. [Central Research Institute of Electric Power Industry, Kanagawa (Japan)

2008-01-15

Simultaneous removal of dust, alkaline and alkaline-earth metals, halides and sulfur compounds is required to enlarge application of coal-derived gas to the high-temperature fuel cells and the fuel synthesis through chemical processing. Because high calorific fuel gas, such as oxygen-blown coal gas, has high carbon monoxide content, high-temperature (above 450{sup o}C) gas purification system is always subjected to the carbon deposition. We suggest moderate temperature (around 300{sup o}C) operation of the gas purification system to avoid the harmful disproportionation reaction and efficient removal of the various contaminants. Because the reaction rate is predominant to the performance of contaminant removal in the moderate temperature gas purification system, we evaluated the chemical removal processes; performance of the removal processes for halides and sulfur compounds was experimentally evaluated. The halide removal process with sodium aluminate sorbent had potential performance at around 300{sup o}C. The sulfur removal process with zinc ferrite sorbent was also applicable to the temperature range, though the reaction kinetics of the sorbent is essential to be approved.

Elementary reaction rate measurements at high temperatures by tunable-laser flash-absorption

Energy Technology Data Exchange (ETDEWEB)

Hessler, J.P. [Argonne National Laboratory, IL (United States)

1993-12-01

The major objective of this program is to measure thermal rate coefficients and branching ratios of elementary reactions. To perform these measurements, the authors constructed an ultrahigh-purity shock tube to generate temperatures between 1000 and 5500 K. The tunable-laser flash-absorption technique is used to measure the rate of change of the concentration of species which absorb below 50,000 cm{sup {minus}1} e.g.: OH, CH, and CH{sub 3}. This technique is being extended into the vacuum-ultraviolet spectral region where one can measure atomic species e.g.: H, D, C, O, and N; and diatomic species e.g.: O{sub 2}, CO, and OH.

Determining Role of the Chain Mechanism in the Temperature Dependence of the Gas-Phase Rate of Combustion Reactions

Science.gov (United States)

Azatyan, V. V.; Bolod'yan, I. A.; Kopylov, N. P.; Kopylov, S. N.; Prokopenko, V. M.; Shebeko, Yu. N.

2018-05-01

It is shown that the strong dependence of the rate of gas-phase combustion reactions on temperature is determined by the high values of the reaction rate constants of free atoms and radicals. It is established that with a branched chain mechanism, a special role in the reaction rate temperature dependence is played by positive feedback between the concentrations of active intermediate species and the rate of their change. The role of the chemical mechanism in the temperature dependence of the process rate with and without inhibitors is considered.

Nonmonotonic Temperature Dependence of the Pressure-Dependent Reaction Rate Constant and Kinetic Isotope Effect of Hydrogen Radical Reaction with Benzene Calculated by Variational Transition-State Theory.

Science.gov (United States)

Zhang, Hui; Zhang, Xin; Truhlar, Donald G; Xu, Xuefei

2017-11-30

The reaction between H and benzene is a prototype for reactions of radicals with aromatic hydrocarbons. Here we report calculations of the reaction rate constants and the branching ratios of the two channels of the reaction (H addition and H abstraction) over a wide temperature and pressure range. Our calculations, obtained with an accurate potential energy surface, are based on variational transition-state theory for the high-pressure limit of the addition reaction and for the abstraction reaction and on system-specific quantum Rice-Ramsperger-Kassel theory calibrated by variational transition-state theory for pressure effects on the addition reaction. The latter is a very convenient way to include variational effects, corner-cutting tunneling, and anharmonicity in falloff calculations. Our results are in very good agreement with the limited experimental data and show the importance of including pressure effects in the temperature interval where the mechanism changes from addition to abstraction. We found a negative temperature effect of the total reaction rate constants at 1 atm pressure in the temperature region where experimental data are missing and accurate theoretical data were previously missing as well. We also calculated the H + C 6 H 6 /C 6 D 6 and D + C 6 H 6 /C 6 D 6 kinetic isotope effects, and we compared our H + C 6 H 6 results to previous theoretical data for H + toluene. We report a very novel nonmonotonic dependence of the kinetic isotope effect on temperature. A particularly striking effect is the prediction of a negative temperature dependence of the total rate constant over 300-500 K wide temperature ranges, depending on the pressure but generally in the range from 600 to 1700 K, which includes the temperature range of ignition in gasoline engines, which is important because aromatics are important components of common fuels.

Moderate temperature gas purification system: application to high calorific coal derived fuel

Energy Technology Data Exchange (ETDEWEB)

M. Kobayashi; H. Shirai; M. Nunokawa [Central Research Institute of Electric Power Industry (CRIEPI), Kanagawa (Japan)

2005-07-01

Simultaneous removal of dust, alkaline and alkaline-earth metals, halides and sulfur compounds is required to enlarge application of coal-derived gas to the high temperature fuel cells and the fuel synthesis through chemical processing. Because high calorific fuel gas, such as oxygen-blown coal gas, has high carbon monoxide content, high temperature gas purification system is always subjected to the carbon deposition and slippage of contaminant of high vapor pressure. It was suggested that moderate temperature operation of the gas purification system is applied to avoid the harmful disproportionation reaction and efficient removal of the various contaminants. To establish the moderate temperature gas purification system, the chemical-removal processes where the reaction rate is predominant to the performance of contaminant removal should be evaluated. Performance of the removal processes for halides and sulfur compounds were experimentally evaluated. The halide removal process with sodium based sorbent had potential good performance at around 300{sup o}C. The sulfur removal process was also applicable to the temperature range, although the improvement of the sulfidation reaction rate is considered to be essential. 11 refs., 8 figs., 1 tab.

The effect of reaction temperature on the room temperature ferromagnetic property of sol-gel derived tin oxide nanocrystal

Science.gov (United States)

Sakthiraj, K.; Hema, M.; Balachandra Kumar, K.

2018-06-01

In the present study, nanocrystalline tin oxide materials were prepared using sol-gel method with different reaction temperatures (25 °C, 50 °C, 75 °C & 90 °C) and the relation between the room temperature ferromagnetic property of the sample with processing temperature has been analysed. The X-ray diffraction pattern and infrared absorption spectra of the as-prepared samples confirm the purity of the samples. Transmission electron microscopy images visualize the particle size variation with respect to reaction temperature. The photoluminescence spectra of the samples demonstrate that luminescence process in materials is originated due to the electron transition mediated by defect centres. The room temperature ferromagnetic property is observed in all the samples with different amount, which was confirmed using vibrating sample magnetometer measurements. The saturation magnetization value of the as-prepared samples is increased with increasing the reaction temperature. From the photoluminescence & magnetic measurements we accomplished that, more amount of surface defects like oxygen vacancy and tin interstitial are created due to the increase in reaction temperature and it controls the ferromagnetic property of the samples.

Development of Bi-base high-temperature Pb-free solders with second-phase dispersion: Thermodynamic calculation, microstructure, and interfacial reaction

Science.gov (United States)

Takaku, Yoshikazu; Ohnuma, Ikuo; Kainuma, Ryosuke; Yamada, Yasushi; Yagi, Yuji; Nishibe, Yuji; Ishida, Kiyohito

2006-11-01

Bismuth and its alloys are candidates for Pb-free high-temperature solders that can be substituted for conventional Pb-rich Pb-Sn solders (melting point (mp) = 573 583 K). However, inferior properties such as brittleness and weak bonding strength should be improved for practical use. To that end, BiCu-X (X=Sb, Sn, and Zn) Pb-free high-temperature solders are proposed. Miscibility gaps in liquid BiCu-X alloys were surveyed using the thermodynamic database ADAMIS (alloy database for micro-solders), and compositions of the BiCu-X solders were designed on the basis of calculation. In-situ composite solders that consist of a Bi-base matrix with fine intermetallic compound (IMC) particles were produced by gas-atomizing and melt-spinning methods. The interfacial reaction between in-situ composite solders and Cu or Ni substrates was investigated. The IMCs at the interface formed a thin, uniform layer, which is an appropriate morphology for a reliable solder joint.

Decay Time Measurement for Different Energy Depositions of Plastic Scintillator Fabricated by High Temperature Polymerization Reaction

Energy Technology Data Exchange (ETDEWEB)

Lee, Cheol Ho; Son, Jaebum; Lee, Sangmin; Kim, Tae Hoon; Kim, Yong-Kyun [Hanyang University, Seoul (Korea, Republic of)

2016-10-15

Plastic scintillators are based on organic fluorite. They have many advantages such as fast rise and decay time, high optical transmission, ease of manufacturing, low cost, and large available size. For these reasons they are widely used for particle identification. Also, protection of people against a variety of threats (such as nuclear, radiological, and explosive) represents a true challenge along with the continuing development of science and technology. The plastic scintillator is widely used in various devise, which serves for nuclear, photonics, quantum, and high-energy physics. The plastic scintillator is probably the most widely used organic detector, and polystyrene is one of the most widely used materials in the making of the plastic scintillator detector. Thus, a styrene monomer as a solvent was used to fabricate the plastic scintillator by using high temperature polymerization reaction, and then the emission wavelength and the decay times for different energy depositions were measured by using the fabricated plastic scintillator. A plastic scintillator was fabricated to measure decay time for different energy depositions using the high temperature polymerization. Emission wavelength was measured of 426.05 nm to confirm a scintillator property using the spectrophotometer. Four gamma-ray sources (Cs-137, Co-60, Na-22, and Ba-133) were used to evaluate effect for decay time of different energy depositions. The average decay time of the fabricated plastic scintillator was measured to approximately 4.72 ns slightly higher more than commercial plastic scintillator. In future, light output and linearity will be measured to evaluate other property compared with the commercial scintillator.

Decay Time Measurement for Different Energy Depositions of Plastic Scintillator Fabricated by High Temperature Polymerization Reaction

International Nuclear Information System (INIS)

Lee, Cheol Ho; Son, Jaebum; Lee, Sangmin; Kim, Tae Hoon; Kim, Yong-Kyun

2016-01-01

Plastic scintillators are based on organic fluorite. They have many advantages such as fast rise and decay time, high optical transmission, ease of manufacturing, low cost, and large available size. For these reasons they are widely used for particle identification. Also, protection of people against a variety of threats (such as nuclear, radiological, and explosive) represents a true challenge along with the continuing development of science and technology. The plastic scintillator is widely used in various devise, which serves for nuclear, photonics, quantum, and high-energy physics. The plastic scintillator is probably the most widely used organic detector, and polystyrene is one of the most widely used materials in the making of the plastic scintillator detector. Thus, a styrene monomer as a solvent was used to fabricate the plastic scintillator by using high temperature polymerization reaction, and then the emission wavelength and the decay times for different energy depositions were measured by using the fabricated plastic scintillator. A plastic scintillator was fabricated to measure decay time for different energy depositions using the high temperature polymerization. Emission wavelength was measured of 426.05 nm to confirm a scintillator property using the spectrophotometer. Four gamma-ray sources (Cs-137, Co-60, Na-22, and Ba-133) were used to evaluate effect for decay time of different energy depositions. The average decay time of the fabricated plastic scintillator was measured to approximately 4.72 ns slightly higher more than commercial plastic scintillator. In future, light output and linearity will be measured to evaluate other property compared with the commercial scintillator

Containerless high temperature property measurements by atomic fluorescence

Science.gov (United States)

Schiffman, R. A.; Walker, C. A.

1984-01-01

Laser induced fluorescence (LIF) techniques for containerless study of high temperature processes and material properties was studied. Gas jet and electromagnetic levitation and electromagnetic and laser heating techniques are used with LIF in earth-based containerless high temperature experiments. Included are the development of an apparatus and its use in the studies of (1) chemical reactions on Al2O3, molybdenum, tungsten and LaB6 specimens, (2) methods for noncontact specimen temperature measurement, (3) levitation jet properties and (4) radiative lifetime and collisional energy transfer rates for electronically excited atoms.

Electrodeless, multi-megawatt reactor for room-temperature, lithium-6/deuterium nuclear reactions

International Nuclear Information System (INIS)

Drexler, J.

1993-01-01

This paper describes a reactor design to facilitate a room-temperature nuclear fusion/fission reaction to generate heat without generating unwanted neutrons, gamma rays, tritium, or other radioactive products. The room-temperature fusion/fission reaction involves the sequential triggering of billions of single-molecule, 6 LiD 'fusion energy pellets' distributed in lattices of a palladium ion accumulator that also acts as a catalyst to produce the molecules of 6 LiD from a solution comprising D 2 O, 6 LiOD with D 2 gas bubbling through it. The D 2 gas is the source of the negative deuterium ions in the 6 LiD molecules. The next step is to trigger a first nuclear fusion/fission reaction of some of the 6 LiD molecules, according to the well-known nuclear reaction: 6 Li + D → 2 4 He + 22.4 MeV. The highly energetic alpha particles ( 4 He nuclei) generated by this nuclear reaction within the palladium will cause shock and vibrations in the palladium lattices, leading to compression of other 6 LiD molecules and thereby triggering a second series of similar fusion/fission reactions, leading to a third series, and so on. The absorption of the kinetic energy in the palladium will, in turn, generate a continuous flow of heat into the heavy water carrier, which would be removed with a heat exchanger. (author)

Ceramics for high temperature applications

International Nuclear Information System (INIS)

Mocellin, A.

1977-01-01

Problems related to materials, their fabrication, properties, handling, improvements are examined. Silicium nitride and silicium carbide are obtained by vacuum hot-pressing, reaction sintering and chemical vapour deposition. Micrographs are shown. Mechanical properties i.e. room and high temperature strength, creep resistance fracture mechanics and fatigue resistance. Recent developments of pressureless sintered Si C and the Si-Al-O-N quaternary system are mentioned

A combined high-temperature experimental and theoretical kinetic study of the reaction of dimethyl carbonate with OH radicals

KAUST Repository

Khaled, Fathi; Giri, Binod; Szőri, Milá n; Mai, Tam V.-T.; Huynh, Lam K.; Farooq, Aamir

2017-01-01

The reaction kinetics of dimethyl carbonate (DMC) and OH radicals were investigated behind reflected shock waves over the temperature range of 872-1295 K and at pressures near 1.5 atm. Reaction progress was monitored by detecting OH radicals at 306.69 nm using a UV laser absorption technique. The rate coefficients for the reaction of DMC with OH radicals were extracted using a detailed kinetic model developed by Glaude et al. (Proc. Combust. Inst. 2005, 30(1), 1111-1118). The experimental rate coefficients can be expressed in Arrhenius form as: kexpt'l = 5.15 × 10(13) exp(-2710.2/T) cm(3) mol(-1) s(-1). To explore the detailed chemistry of the DMC + OH reaction system, theoretical kinetic analyses were performed using high-level ab initio and master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) calculations. Geometry optimization and frequency calculations were carried out at the second-order Møller-Plesset (MP2) perturbation level of theory using Dunning's augmented correlation consistent-polarized valence double-ζ basis set (aug-cc-pVDZ). The energy was extrapolated to the complete basis set using single point calculations performed at the CCSD(T)/cc-pVXZ (where X = D, T) level of theory. For comparison purposes, additional ab initio calculations were also carried out using composite methods such as CBS-QB3, CBS-APNO, G3 and G4. Our calculations revealed that the H-abstraction reaction of DMC by OH radicals proceeds via an addition elimination mechanism in an overall exothermic process, eventually forming dimethyl carbonate radicals and H2O. Theoretical rate coefficients were found to be in excellent agreement with those determined experimentally. Rate coefficients for the DMC + OH reaction were combined with literature rate coefficients of four straight chain methyl ester + OH reactions to extract site-specific rates of H-abstraction from methyl esters by OH radicals.

The reactions of magnesium and its alloys with moist gases at high temperatures

International Nuclear Information System (INIS)

Darras, R.

1963-02-01

The kinetics and mechanisms of the reaction of pure or low alloyed magnesium with various gas saturated by water vapor: oxygen, argon, nitrogen, air, carbon dioxide, have been studied and compared in the temperature range 350-600 deg C. After picturing the large chemical reactivity of magnesium surface, the more or less properties of the oxide film, always made of magnesia, have been shown depending on the nature of the gas carrying water vapor; in fact, metal sublimation occurs the more easily as the surrounding atmosphere is less oxidizing. Moreover, an activation energy change is systematic, but at a temperature which depends also on the latter. In the case of the alloys, the linear oxidation rate is generally obtained only after short induction periods, parabolic in nature. Two possibilities of corrosion inhibition of magnesium by water vapor are then demonstrated and explained: either by a partial superficial fluoridation, or when the carrier gas is carbon dioxide. Also, the extreme conditions of oxidation were studied, that is the ignition processes that occur at a particular temperature in every gas mixture. Finally, it is tried to evolve the fundamental and practical significance of all the results. (author) [fr

Safety Philosophy in Process Heat Plants Coupled to High Temperature Reactors

International Nuclear Information System (INIS)

Brown, Nicholas R.; Revankar, Shripad T.

2011-01-01

With the future availability of fossil fuel resources in doubt, high temperature nuclear reactors have the potential to be an important technology in the near term. Due to a high coolant outlet temperature, high temperature reactors (HTR) can be used to drive chemical plants that directly utilize process heat. Additionally, the high temperature improves the thermodynamic efficiency of the energy utilization. Many applications of high temperature reactors exist as a thermal driving vector for endothermic chemical process plants. Hydrogen generation using the General Atomics (GA) sulfur iodine (SI) cycle is one promising application of high temperature nuclear heat. The main chemical reactions in the SI cycle are: 1. I 2 +SO 2 + 2H 2 O → 2HI + H 2 SO 4 (Bunsen reaction) 2. H 2 SO 4 → H 2 O + SO 2 + 1/2O 2 (Sulfuric acid decomposition) 3. 2HI → H 2 + I 2 (Hydrogen Iodide decomposition). With the exception of hydrogen and oxygen, all relevant reactants are recycled within the process. However, there are many unresolved safety and operational issues related to implementation of such a coupled plant

High Temperature Polymer Electrolyte Fuel Cells

DEFF Research Database (Denmark)

Fleige, Michael

This thesis presents the development and application of electrochemical half-cell setups to study the catalytic reactions taking place in High Temperature Polymer Electrolyte Fuel Cells (HTPEM-FCs): (i) a pressurized electrochemical cell with integrated magnetically coupled rotating disk electrode...... oxidation of ethanol is in principle a promising concept to supply HTPEM-FCs with a sustainable and on large scale available fuel (ethanol from biomass). However, the intermediate temperature tests in the GDE setup show that even on Pt-based catalysts the reaction rates become first significant...... at potentials, which approach the usual cathode potentials of HTPEM-FCs. Therefore, it seems that H3PO4-based fuel cells are not much suited to efficiently convert ethanol in accordance with findings in earlier research papers. Given that HTPEM-FCs can tolerate CO containing reformate gas, focusing research...

Reaction of LiD with moisture by temperature programmed reaction (TPR)

International Nuclear Information System (INIS)

Dinh, L N; Balooch, M; Cecala, C M; Leckey, J H

2000-01-01

The temperature programmed reaction technique was performed on LiOH powders and LiD single crystals previously exposed to different moisture levels. Our results show that the LiOH decomposition process has an activation energy barrier of 30 to 33.1 kcal/mol. The LiOH structure is stable at 320 K for 100 years. However, LiOH structures formed on the surface of LiD during moisture exposure at low dosages may have multiple activation energy barriers, some of which may be much lower than 30 kcal/mol. We attribute the lowering of the activation energy barrier for the LiOH decomposition to the existence of dangling bonds, cracks, and other long range disorders in the LiOH structures formed at low levels of moisture exposure. These defective LiOH structures may decompose significantly over the next 100 years of storage even at room temperature. At high moisture exposure levels, LiOH.H 2 O formation is observed. The release of H 2 O molecules from LiOH.H 2 O structure has small activation energy barriers in the range of 13.8 kcal/mol to 16.0 kcal/mol. The loosely bonded H 2 O molecules in the LiOH.H 2 O structure can be easily pumped away at room temperature in a reasonable amount of time. Our experiments also suggest that handling LiD single crystals at an elevated temperature of 340 K or more reduces the growth of LiOH and LiOH.H 2 O significantly

Kinetics and mechanisms of iron redox reactions in silicate melts: The effects of temperature and alkali cations

Energy Technology Data Exchange (ETDEWEB)

Magnien, V.; Pinet, O. [CEA VALRHO, SCDV/LEBV, F-30207 Bagnols Sur Ceze, (France); Magnien, V.; Neuville, D. R.; Roux, J.; Richet, P. [IPGP, CNRS, Physique des Mineraux et Magmas, F-75252 Paris 05, (France); Cormier, L. [Univ Paris 06, IMPMC, F-75015 Paris, (France); Hazemann, J. L. [CNRS, Inst Neel, F-38043 Grenoble, (France); De Ligny, D. [Univ Lyon 1, LMLC, CNRS, UMR 5620, F-69622 Villeurbanne, (France); Pascarelli, S. [European Synchrotron Radiat Facil, F-38043 Grenoble, (France); Vickridge, I. [Univ Paris 06, INSP, F-75015 Paris, (France)

2008-07-01

The kinetics and the mechanisms of iron redox reactions in molten Fe-bearing pyroxene compositions have been investigated by Raman spectroscopy and X-ray absorption Near Edge Structure (XANES) experiments at the iron K-edge. The former experiments have been made only near the glass transition whereas the latter have also been performed from about 1300 to 2100 K. The same kinetics are observed with both techniques. They are described by characteristic times that depend primarily on temperature and not on the initial redox state. At high temperatures, where both kinds of reactions could be investigated, these times are similar for oxidation and reduction. From these characteristic times we have calculated as a function of temperature and composition a parameter termed effective redox diffusivity. For a given melt, the diffusivities follow two distinct Arrhenius laws, which indicate that the mechanisms of the redox reaction are not the same near the glass transition and at high temperatures. As is now well established, diffusion of divalent cations is the dominant mechanism at low temperatures but the enhanced kinetics observed for alkali-bearing melts indicate that Li{sup +} and Na{sup +} also participate in ionic transport. At super-liquidus temperatures, in contrast, diffusion of oxygen represents the dominant mechanism. (authors)

Proceedings of the meeting on tunneling reaction and low temperature chemistry, 97 October. Tunneling reaction and quantum medium

Energy Technology Data Exchange (ETDEWEB)

Miyazaki, Tetsuo; Aratono, Yasuyuki; Ichikawa, Tsuneki; Shiotani, Masaru [eds.

1998-02-01

Present report is the proceedings of the 3rd Meeting on Tunneling Reaction and Low Temperature Chemistry held in Oct. 13 and 14, 1997. The main subject of the meeting is `Tunneling Reaction and Quantum Medium`. In the meeting, the physical and chemical phenomena in the liquid helium such as quantum nucleation, spectroscopy of atoms and molecules, and tunneling abstraction reaction of tritium atom were discussed as the main topics as well as the tunneling reactions in the solid hydrogen and organic compounds. Through the meetings held in 1995, 1996, and 1997, the tunneling phenomena proceeding at various temperatures (room temperature to mK) in the wide fields of chemistry, biology, and physics were discussed intensively and the importance of the tunneling phenomena in the science has been getting clear. The 12 of the presented papers are indexed individually. (J.P.N.)

Proceedings of the meeting on tunneling reaction and low temperature chemistry, 97 October. Tunneling reaction and quantum medium

International Nuclear Information System (INIS)

Miyazaki, Tetsuo; Aratono, Yasuyuki; Ichikawa, Tsuneki; Shiotani, Masaru

1998-02-01

Present report is the proceedings of the 3rd Meeting on Tunneling Reaction and Low Temperature Chemistry held in Oct. 13 and 14, 1997. The main subject of the meeting is 'Tunneling Reaction and Quantum Medium'. In the meeting, the physical and chemical phenomena in the liquid helium such as quantum nucleation, spectroscopy of atoms and molecules, and tunneling abstraction reaction of tritium atom were discussed as the main topics as well as the tunneling reactions in the solid hydrogen and organic compounds. Through the meetings held in 1995, 1996, and 1997, the tunneling phenomena proceeding at various temperatures (room temperature to mK) in the wide fields of chemistry, biology, and physics were discussed intensively and the importance of the tunneling phenomena in the science has been getting clear. The 12 of the presented papers are indexed individually. (J.P.N.)

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)

The ReactorSTM: Atomically resolved scanning tunneling microscopy under high-pressure, high-temperature catalytic reaction conditions

Energy Technology Data Exchange (ETDEWEB)

Herbschleb, C. T.; Tuijn, P. C. van der; Roobol, S. B.; Navarro, V.; Bakker, J. W.; Liu, Q.; Stoltz, D.; Cañas-Ventura, M. E.; Verdoes, G.; Spronsen, M. A. van; Bergman, M.; Crama, L.; Taminiau, I.; Frenken, J. W. M., E-mail: frenken@physics.leidenuniv.nl [Huygens-Kamerlingh Onnes Laboratory, Leiden University, P.O. box 9504, 2300 RA Leiden (Netherlands); Ofitserov, A.; Baarle, G. J. C. van [Leiden Probe Microscopy B.V., J.H. Oortweg 21, 2333 CH Leiden (Netherlands)

2014-08-15

To enable atomic-scale observations of model catalysts under conditions approaching those used by the chemical industry, we have developed a second generation, high-pressure, high-temperature scanning tunneling microscope (STM): the ReactorSTM. It consists of a compact STM scanner, of which the tip extends into a 0.5 ml reactor flow-cell, that is housed in a ultra-high vacuum (UHV) system. The STM can be operated from UHV to 6 bars and from room temperature up to 600 K. A gas mixing and analysis system optimized for fast response times allows us to directly correlate the surface structure observed by STM with reactivity measurements from a mass spectrometer. The in situ STM experiments can be combined with ex situ UHV sample preparation and analysis techniques, including ion bombardment, thin film deposition, low-energy electron diffraction and x-ray photoelectron spectroscopy. The performance of the instrument is demonstrated by atomically resolved images of Au(111) and atom-row resolution on Pt(110), both under high-pressure and high-temperature conditions.

Catalytic depolymerization of lignin and woody biomass in supercritical Ethanol: influence of reaction temperature and feedstock : Influence of reaction temperature and feedstock

NARCIS (Netherlands)

Huang, X.; Atay, C.; Zhu, J.; Palstra, S.W.L.; Korányi, T.I.; Boot, M.D.; Hensen, E.J.M.

2017-01-01

The one-step ethanolysis approach to upgrade lignin to monomeric aromatics using a CuMgAl mixed oxide catalyst is studied in detail. The influence of reaction temperature (200-420 °C) on the product distribution is investigated. At low temperature (200-250 °C), recondensation is dominant, while

Nasal reaction to changes in whole body temperature.

Science.gov (United States)

Lundqvist, G R; Pedersen, O F; Hilberg, O; Nielsen, B

1993-11-01

The changes in nasal patency following a 1.5 degrees C decrease or increase in whole body temperature were measured in 8 healthy young males, during and after 30 min of immersion in a 15 degrees C cold or a 40 degrees C warm bath, breathing air at the same temperature, in a cross-over experimental design. The nasal reactions were traced by consecutive measurements of changes in nasal cavity volumes by acoustic rhinometry. Swelling of the mucosa during cooling and an almost maximal shrinkage of the mucosa during heating were indicated by respectively a decrease and an increase in nasal cavity volumes. The reactions were determined predominantly by the whole body thermal balance, but were also influenced by the temperature of the inhaled air, either enhanced, reduced or temporarily reversed. The greatest change occurred in the nasal cavity, left or right, which differed most from the final state at the beginning of exposure due to the actual state of nasal cycle.

Corrosion of silicon nitride in high temperature alkaline solutions

Energy Technology Data Exchange (ETDEWEB)

Qiu, Liyan, E-mail: liyan.qiu@cnl.ca; Guzonas, Dave A.; Qian, Jing

2016-08-01

The corrosion of silicon nitride (Si{sub 3}N{sub 4}) in alkaline solutions was studied at temperatures from 60 to 300 °C. Si{sub 3}N{sub 4} experienced significant corrosion above 100 °C. The release rates of silicon and nitrogen follow zero order reaction kinetics and increase with increasing temperature. The molar ratio of dissolved silicon and nitrogen species in the high temperature solutions is the same as that in the solid phase (congruent dissolution). The activation energy for silicon and nitrogen release rates is 75 kJ/mol which agrees well with that of silica dissolution. At 300 °C, the release of aluminum is observed and follows first order reaction kinetics while other minor constituents including Ti and Y are highly enriched on the corrosion films due to the low solubility of their oxides.

Anisotropic diamond etching through thermochemical reaction between Ni and diamond in high-temperature water vapour.

Science.gov (United States)

Nagai, Masatsugu; Nakanishi, Kazuhiro; Takahashi, Hiraku; Kato, Hiromitsu; Makino, Toshiharu; Yamasaki, Satoshi; Matsumoto, Tsubasa; Inokuma, Takao; Tokuda, Norio

2018-04-27

Diamond possesses excellent physical and electronic properties, and thus various applications that use diamond are under development. Additionally, the control of diamond geometry by etching technique is essential for such applications. However, conventional wet processes used for etching other materials are ineffective for diamond. Moreover, plasma processes currently employed for diamond etching are not selective, and plasma-induced damage to diamond deteriorates the device-performances. Here, we report a non-plasma etching process for single crystal diamond using thermochemical reaction between Ni and diamond in high-temperature water vapour. Diamond under Ni films was selectively etched, with no etching at other locations. A diamond-etching rate of approximately 8.7 μm/min (1000 °C) was successfully achieved. To the best of our knowledge, this rate is considerably greater than those reported so far for other diamond-etching processes, including plasma processes. The anisotropy observed for this diamond etching was considerably similar to that observed for Si etching using KOH.

Passivation Of High-Temperature Superconductors

Science.gov (United States)

Vasquez, Richard P.

1991-01-01

Surfaces of high-temperature superconductors passivated with native iodides, sulfides, or sulfates formed by chemical treatments after superconductors grown. Passivating compounds nearly insoluble in and unreactive with water and protect underlying superconductors from effects of moisture. Layers of cuprous iodide and of barium sulfate grown. Other candidate passivating surface films: iodides and sulfides of bismuth, strontium, and thallium. Other proposed techniques for formation of passivating layers include deposition and gas-phase reaction.

The effect of high curing temperature on the reaction kinetics in MK/lime and MK-blended cement matrices at 60 deg. C

International Nuclear Information System (INIS)

Rojas, Moises Frias; Sanchez de Rojas, M.I.

2003-01-01

It is well known that the pozzolanic reaction between metakaolin (MK) and calcium hydroxide produces CSH, C 2 ASH 8 (stratlingite), C 4 AH 13 and C 3 ASH 6 (hydrogarnet). However, the presence or absence of these hydrated phases depends on different parameters, such as curing temperature, matrix used, etc. This paper shows the results of a study in order to know the effect of high curing temperature (60 deg. C) on the kinetics of the pozzolanic reaction in different matrices. MK/lime (calcium hydroxide) and MK-blended cement matrices were studied in samples stored and cured at 60 deg. C and up to 123 days of hydration. The nature, sequence and crystallinity of the hydrated phases were analysed using differential thermal analysis (DTA) and X-ray diffraction (XRD) techniques. Results showed that the sequence and formation of the hydrated phases was different in both matrices cured at 60 deg. C. In an MK/lime matrix, C 2 ASH 8 , C 4 AH 13 and C 3 ASH 6 were the main hydrated phases; while in an MK-blended cement, stratlingite was the sole hydrated phase issued from pozzolanic reaction. The DTA and XRD data also reveal an important fact: there is no evidence of the presence of hydrogarnet in blended cements

The analysis of energy efficiency in water electrolysis under high temperature and high pressure

Science.gov (United States)

Hourng, L. W.; Tsai, T. T.; Lin, M. Y.

2017-11-01

This paper aims to analyze the energy efficiency of water electrolysis under high pressure and high temperature conditions. The effects of temperature and pressure on four different kinds of reaction mechanisms, namely, reversible voltage, activation polarization, ohmic polarization, and concentration polarization, are investigated in details. Results show that the ohmic and concentration over-potentials are increased as temperature is increased, however, the reversible and activation over-potentials are decreased as temperature is increased. Therefore, the net efficiency is enhanced as temperature is increased. The efficiency of water electrolysis at 350°C/100 bars is increased about 17%, compared with that at 80°C/1bar.

A combined high-temperature experimental and theoretical kinetic study of the reaction of dimethyl carbonate with OH radicals

KAUST Repository

Khaled, Fathi

2017-02-08

The reaction kinetics of dimethyl carbonate (DMC) and OH radicals were investigated behind reflected shock waves over the temperature range of 872-1295 K and at pressures near 1.5 atm. Reaction progress was monitored by detecting OH radicals at 306.69 nm using a UV laser absorption technique. The rate coefficients for the reaction of DMC with OH radicals were extracted using a detailed kinetic model developed by Glaude et al. (Proc. Combust. Inst. 2005, 30(1), 1111-1118). The experimental rate coefficients can be expressed in Arrhenius form as: kexpt\\'l = 5.15 × 10(13) exp(-2710.2/T) cm(3) mol(-1) s(-1). To explore the detailed chemistry of the DMC + OH reaction system, theoretical kinetic analyses were performed using high-level ab initio and master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) calculations. Geometry optimization and frequency calculations were carried out at the second-order Møller-Plesset (MP2) perturbation level of theory using Dunning\\'s augmented correlation consistent-polarized valence double-ζ basis set (aug-cc-pVDZ). The energy was extrapolated to the complete basis set using single point calculations performed at the CCSD(T)/cc-pVXZ (where X = D, T) level of theory. For comparison purposes, additional ab initio calculations were also carried out using composite methods such as CBS-QB3, CBS-APNO, G3 and G4. Our calculations revealed that the H-abstraction reaction of DMC by OH radicals proceeds via an addition elimination mechanism in an overall exothermic process, eventually forming dimethyl carbonate radicals and H2O. Theoretical rate coefficients were found to be in excellent agreement with those determined experimentally. Rate coefficients for the DMC + OH reaction were combined with literature rate coefficients of four straight chain methyl ester + OH reactions to extract site-specific rates of H-abstraction from methyl esters by OH radicals.

A high-temperature high-pressure calorimeter for determining heats of solution up to 623 K.

Science.gov (United States)

Djamali, Essmaiil; Turner, Peter J; Murray, Richard C; Cobble, James W

2010-07-01

A high-temperature high-pressure isoperibol calorimeter for determining the heats of solution and reaction of very dilute substances in water (10(-4) m) at temperatures up to 623 K is described. The energies of vaporization of water at steam saturation pressure were measured as a function of temperature and the results agree with the corresponding values from steam tables to better than 0.08+/-0.18%. The novelties of the present instrument relative to flow type heat capacity calorimeters are that measurements can be made at orders of magnitude lower concentrations and that measurement of heat of reaction involving solids or gases or in the presence of high concentrations of supporting electrolytes, acids, and bases is possible. Furthermore, the advantage of using enthalpy data over heat capacity data for calculations of the standard state Gibbs free energies of electrolytes is that the experimental heat data of this research need only be integrated once to derive higher temperature free energy data from lower temperatures. The derived heat capacities can be used mathematically to obtain free energies by double integration. However, the resulting errors are much smaller than if experimental aqueous heat capacities were used for the integrations.

Extrapolation of rate constants of reactions producing H{sub 2} and O{sub 2} in radiolysis of water at high temperatures

Energy Technology Data Exchange (ETDEWEB)

Leblanc, R.; Ghandi, K.; Hackman, B.; Liu, G. [Mount Allison Univ., Sackville, NB (Canada)

2014-07-01

One target of our research is to extrapolate known data on the rate constants of reactions and add corrections to estimate the rate constants at the higher temperatures reached by the SCWR reactors. The focus of this work was to extrapolate known data on the rate constants of reactions that produce Hydrogen or Oxygen with a rate constant below 10{sup 10} mol{sup -1} s{sup -1} at room temperature. The extrapolation is done taking into account the change in the diffusion rate of the interacting species and the cage effect with thermodynamic conditions. The extrapolations are done over a wide temperature range and under isobaric conditions. (author)

The reaction of hydrogen atoms with hydrogen peroxide as a function of temperature

DEFF Research Database (Denmark)

Lundström, T.; Christensen, H.; Sehested, K.

2001-01-01

The temperature dependence for the reaction of H atoms with H2O2 at pH 1 has been determined using pulse radiolysis technique. The reaction was studied in the temperature range 10-120 degreesC. The rate constant at 25 degreesC was found to be 5.1 +/- 0.5 x 10(7) dm(3) mol(-1) s(-1) and the activa......The temperature dependence for the reaction of H atoms with H2O2 at pH 1 has been determined using pulse radiolysis technique. The reaction was studied in the temperature range 10-120 degreesC. The rate constant at 25 degreesC was found to be 5.1 +/- 0.5 x 10(7) dm(3) mol(-1) s(-1...

H + CH{sub 2}CO {yields} CH{sub 3} + CO at high temperature : a high pressure chemical activation reaction with positive barrier.

Energy Technology Data Exchange (ETDEWEB)

Hranisavljevic, J.; Kumaran, S. S.; Michael, J. V.

1997-12-08

The Laser Photolysis-Shock Tube (LP-ST) technique coupled with H-atom atomic resonance absorption spectrometry (ARAS) has been used to study reaction, H + CH{sub 2}CO {r_arrow} CH{sub 3} + CO, over the temperature range, 863-1400 K. The results can be represented by the Arrhenius expression, k = (4.85 {+-} 0.70) x 10{sup {minus}11} exp({minus}2328 {+-} 155 K/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. The present data have been combined with the earlier low temperature flash photolysis-resonance fluorescence measurements to yield a joint three parameter expression, k = 5.44 x 10{sup {minus}14} T{sup 0.8513} exp({minus}1429 K/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. This is a chemical activation process that proceeds through vibrationally excited acetyl radicals. However, due to the presence of a low lying forward dissociation channel to CH{sub 3} + CO, the present results refer to the high pressure limiting rate constants. Hence, transition state theory with Eckart tunneling is used to explain the data.

Topics in the numerical simulation of high temperature flows

International Nuclear Information System (INIS)

Cheret, R.; Dautray, R.; Desgraz, J.C.; Mercier, B.; Meurant, G.; Ovadia, J.; Sitt, B.

1984-06-01

In the fields of inertial confinement fusion, astrophysics, detonation, or other high energy phenomena, one has to deal with multifluid flows involving high temperatures, high speeds and strong shocks initiated e.g. by chemical reactions or even by thermonuclear reactions. The simulation of multifluid flows is reviewed: first are Lagrangian methods which have been successfully applied in the past. Then we describe our experience with newer adaptive mesh methods, originally designed to increase the accuracy of Lagrangian methods. Finally, some facts about Eulerian methods are recalled, with emphasis on the EAD scheme which has been recently extended to the elasto-plastic case. High temperature flows is then considered, described by the equations of radiation hydrodynamics. We show how conservation of energy can be preserved while solving the radiative transfer equation via the Monte Carlo method. For detonation, some models, introduced to describe the initiation of detonation in heterogeneous explosives. Finally we say a few words about instability of these flows

A New Multichelating Acid System for High-Temperature Sandstone Reservoirs

Directory of Open Access Journals (Sweden)

Nianyin Li

2015-01-01

Full Text Available Sandstone reservoir acidizing is a complex and heterogeneous acid-rock reaction process. If improper acid treatment is implemented, further damage can be induced instead of removing the initial plug, particularly in high-temperature sandstone reservoirs. An efficient acid system is the key to successful acid treatment. High-temperature sandstone treatment with conventional mud acid system faces problems including high acid-rock reaction rate, short acid effective distance, susceptibility to secondary damage, and serious corrosion to pipelines. In this paper, a new multichelating acid system has been developed to overcome these shortcomings. The acid system is composed of ternary weak acid, organic phosphonic chelating agent, anionic polycarboxylic acid chelating dispersant, fluoride, and other assisted additives. Hydrogen ion slowly released by multistage ionization in ternary weak acid and organic phosphonic within the system decreases the concentration of HF to achieve retardation. Chelating agent and chelating dispersant within the system inhibited anodic and cathodic reaction, respectively, to protect the metal from corrosion, while chelating dispersant has great chelating ability on iron ions, restricting the depolarization reaction of ferric ion and metal. The synergic effect of chelating agent and chelating dispersant removes sulfate scale precipitation and inhibits or decreases potential precipitation such as CaF2, silica gel, and fluosilicate. Mechanisms of retardation, corrosion-inhibition, and scale-removing features have been discussed and evaluated with laboratory tests. Test results indicate that this novel acid system has good overall performance, addressing the technical problems and improving the acidizing effect as well for high-temperature sandstone.

Divertor, thermonuclear device and method of neutralizing high temperature plasma

International Nuclear Information System (INIS)

Ikegami, Hideo.

1995-01-01

The thermonuclear device comprises a thermonuclear reactor for taking place fusion reactions to emit fusion plasmas, and a divertor made of a hydrogen occluding material, and the divertor is disposed at a position being in contact with the fusion plasmas after nuclear fusion reaction. The divertor is heated by fusion plasmas after nuclear fusion reaction, and hydrogen is released from the hydrogen occluding material as a constituent material. A gas blanket is formed by the released hydrogen to cool and neutralize the supplied high temperature nuclear fusion plasmas. This prevents the high temperature plasmas from hitting against the divertor, elimination of the divertor by melting and evaporation, and solve a problem of processing a divertor activated by neutrons. In addition, it is possible to utilize hydrogen isotopes of fuels effectively and remove unnecessary helium. Inflow of impurities from out of the system can also be prevented. (N.H.)

Hydroxide Self-Feeding High-Temperature Alkaline Direct Formate Fuel Cells.

Science.gov (United States)

Li, Yinshi; Sun, Xianda; Feng, Ying

2017-05-22

Conventionally, both the thermal degradation of the anion-exchange membrane and the requirement of additional hydroxide for fuel oxidation reaction hinder the development of the high-temperature alkaline direct liquid fuel cells. The present work addresses these two issues by reporting a polybenzimidazole-membrane-based direct formate fuel cell (DFFC). Theoretically, the cell voltage of the high-temperature alkaline DFFC can be as high as 1.45 V at 90 °C. It has been demonstrated that a proof-of-concept alkaline DFFC without adding additional hydroxide yields a peak power density of 20.9 mW cm -2 , an order of magnitude higher than both alkaline direct ethanol fuel cells and alkaline direct methanol fuel cells, mainly because the hydrolysis of formate provides enough OH - ions for formate oxidation reaction. It was also found that this hydroxide self-feeding high-temperature alkaline DFFC shows a stable 100 min constant-current discharge at 90 °C, proving the conceptual feasibility. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of transesterification reaction temperature on biodiesel production

Energy Technology Data Exchange (ETDEWEB)

Pighinelli, Anna Leticia Montenegro Turtelli; Zorzeto, Thais Queiroz; Park, Kil Jin [Universidade Estadual de Campinas (FEAGRI/UNICAMP), SP (Brazil). Fac. de Engenharia Agricola], E-mail: annalets@agr.unicamp.br; Bevilaqua, Gabriela [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Inst. de Quimica

2008-07-01

Brazilian government policy has authorized the introduction of biodiesel into the national energy matrix, law no.11.097 of January 13th, 2005. It is necessary, like any new product, to invest in research which is able to cover its entire production chain (planting of oilseeds, vegetable oils extraction and chemical reactions), providing data and relevant information in order to optimize the process and solve critical issues. The objective of this work was to study the effects of temperature on crude sunflower transesterification reaction with ethanol. A central composite experimental design with five variation levels (25 deg, 32 deg, 47.5 deg, 64 deg and 70 deg C) was used and response surface methodology applied for the data analysis. The statistical analysis of the results showed that the production suffered the influence of temperature (linear and quadratic effects) and reaction time (linear and quadratic). The generated models did not show significant regression. The model generated was not well suited to the experimental data and the value of the coefficient of determination (R{sup 2}=0.52) was low. Consequently it was not possible to build the response surface. (author)

Spectroscopy and kinetics of combustion gases at high temperatures

Energy Technology Data Exchange (ETDEWEB)

Hanson, R.K.; Bowman, C.T. [Stanford Univ., CA (United States)

1993-12-01

This program involves two complementary activities: (1) development and application of cw ring dye laser absorption methods for sensitive detection of radical species and measurement of fundamental spectroscopic parameters at high temperatures; and (2) shock tube studies of reaction kinetics relevant to combustion. Species currently under investigation in the spectroscopic portion of the research include NO and CH{sub 3}; this has necessitated the continued operated at wavelengths in the range 210-230 nm. Shock tube studies of reaction kinetics currently are focussed on reactions involving CH{sub 3} radicals.

High temperature defect equilibrium in ZnS:Cu single crystals

Energy Technology Data Exchange (ETDEWEB)

Lott, K.; Shinkarenko, S.; Tuern, L.; Nirk, T.; Oepik, A. [Department of Materials Science, Tallinn University of Technology, Tallinn (Estonia); Kallavus, U. [Centre for Materials Research, Tallinn University of Technology, Tallinn (Estonia); Gorokhova, E. [Scientific Research and Technological Institute of Optical Material Science, S. I. Vavilov State Optical Institute, All-Russia Science Center, St. Petersburg (Russian Federation); Grebennik, A.; Vishnjakov, A. [Department of Physical Chemistry, D. Mendelejev University of Chemical Technology of Russia, Moscow (Russian Federation)

2010-07-15

High temperature investigations in ZnS:Cu crystals were performed under defined conditions. High temperature electrical conductivity and copper solubility data were obtained under different component vapour pressures and under different sample temperatures. The experimental data at sulphur vapour pressure can be explained by the inclusion of abnormal site occupation i.e. by antistructural disorder. Compensating association of copper with this antistructure defect may occur. Antistructure disorder disappears with increasing of zinc vapour pressure and with increasing role of holes in bipolar conductivity. The method for solving the system of quasichemical reactions without approximation was used to model high temperature defect equilibrium. This model contains antistructure disorder and copper solubility limitation. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

The irradiation behavior of atomized U-Mo alloy fuels at high temperature

Science.gov (United States)

Park, Jong-Man; Kim, Ki-Hwan; Kim, Chang-Kyu; Meyer, M. K.; Hofman, G. L.; Strain, R. V.

2001-04-01

Post-irradiation examinations of atomized U-10Mo, U-6Mo, and U-6Mo-1.7Os dispersion fuels from the RERTR-3 experiment irradiated in the Advanced Test Reactor (ATR) were carried out in order to investigate the fuel behavior of high uranium loading (8 gU/cc) at a high temperature (higher than 200°C). It was observed after about 40 at% BU that the U-Mo alloy fuels at a high temperature showed similar irradiation bubble morphologies compared to those at a lower temperature found in the RERTR-1 irradiation result, but there was a thick reaction layer with the aluminum matrix which was found to be greatly affected by the irradiation temperature and to a lesser degree by the fuel composition. In addition, the chemical analysis for the irradiated U-Mo fuels using the Electron Probe Micro Analysis (EPMA) method were conducted to investigate the compositional changes during the formation of the reaction product.

A high-temperature, ambient-pressure ultra-dry operando reactor cell for Fourier-transform infrared spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Köck, Eva-Maria; Kogler, Michaela; Pramsoler, Reinhold; Klötzer, Bernhard; Penner, Simon, E-mail: simon.penner@uibk.ac.at [Institute of Physical Chemistry, University of Innsbruck, Innrain 80-82, A-6020 Innsbruck (Austria)

2014-08-15

The construction of a newly designed high-temperature, high-pressure FT-IR reaction cell for ultra-dry in situ and operando operation is reported. The reaction cell itself as well as the sample holder is fully made of quartz glass, with no hot metal or ceramic parts in the vicinity of the high-temperature zone. Special emphasis was put on chemically absolute water-free and inert experimental conditions, which includes reaction cell and gas-feeding lines. Operation and spectroscopy up to 1273 K is possible, as well as pressures up to ambient conditions. The reaction cell exhibits a very easy and variable construction and can be adjusted to any available FT-IR spectrometer. Its particular strength lies in its possibility to access and study samples under very demanding experimental conditions. This includes studies at very high temperatures, e.g., for solid-oxide fuel cell research or studies where the water content of the reaction mixtures must be exactly adjusted. The latter includes all adsorption studies on oxide surfaces, where the hydroxylation degree is of paramount importance. The capability of the reaction cell will be demonstrated for two selected examples where information and in due course a correlation to other methods can only be achieved using the presented setup.

A study on structural analysis of highly corrosive melts at high temperature

CERN Document Server

Ohtori, N

2002-01-01

When sodium is burned at high temperature in the atmosphere, it reacts simultaneously with H sub 2 O in the atmosphere so that it can produce high temperature melt of sodium hydroxide as a solvent. If this melt includes peroxide ion (O sub 2 sup 2 sup -), it will be a considerably active and corrosive for iron so that several sodium iron double oxides will be produced as corrosion products after the reaction with steel structures. The present study was carried out in order to investigate the ability of presence of peroxide ion in sodium hydroxide solvent at high temperature and that of identification of the several corrosion products using laser Raman spectroscopy. The measurement system with ultraviolet laser was developed simultaneously in the present work to improve the ability of the measurement at high temperature. As results from the measurements, the possibility of the presence of peroxide ion was shown up to 823K in sodium peroxide and 823K in the melt of sodium hydroxide mixed with sodium peroxide. A...

Phenomenon of quantum low temperature limit of chemical reaction rates

International Nuclear Information System (INIS)

Gol'danskij, V.I.

1975-01-01

The influence of quantum-mechanical effects on one of the fundamental laws of chemical kinetics - the Arrhenius law - is considered. Criteria characterising the limits of the low-temperature region where the extent of quantum-mechanical tunnelling transitions exceeds exponentially the transitions over the barrier are quoted. Studies of the low-temperature tunnelling of electrons and hydrogen atoms are briefly mentioned and the history of research on low-temperature radiation-induced solid-phase polymerisation, the development of which led to the discovery of the phenomenon of the low-temperature quantum-mechanical limit for the rates of chemical reactions in relation to the formaldehyde polymerisation reaction, is briefly considered. The results of experiments using low-inertia calorimeters, whereby it is possible to determine directly the average time (tau 0 ) required to add one new link to the polymer chain of formaldehyde during its polymerisation by radiation and during postpolymerisation and to establish that below 80K the increase of tau 0 slows down and that at T approximately equal to 10-4K the time tau 0 reaches a plateau (tau 0 approximately equals 0.01s), are described. Possible explanations of the observed low-temperature limit for the rate of a chemical reaction are critically examined and a semiquantitative explanation is given for this phenomenon, which may be particularly common in combined electronic-confirmational transitions in complex biological molecules and may play a definite role in chemical and biological evolution (cold prehistory of life)

Phenomenon of quantum low temperature limit of chemical reaction rates

Energy Technology Data Exchange (ETDEWEB)

Gol' danskii, V I [AN SSSR, Moscow. Inst. Khimicheskoj Fiziki

1975-12-01

The influence of quantum-mechanical effects on one of the fundamental laws of chemical kinetics - the Arrhenius Law - is considered. Criteria characterising the limits of the low-temperature region where the extent of quantum-mechanical tunnelling transitions exceeds exponentially the transitions over the barrier are quoted. Studies of the low-temperature tunnelling of electrons and hydrogen atoms are briefly mentioned and the history of research on low-temperature radiation-induced solid-phase polymerization, the development of which led to the discovery of the phenomenon of the low-temperature quantum-mechanical limit for the rates of chemical reactions in relation to the formaldehyde polymerization reaction, is briefly considered. The results of experiments using low-inertia calorimeters, whereby it is possible to determine directly the average time (tau/sub 0/) required to add one new link to the polymer chain of formaldehyde during its polymerization by radiation and during postpolymerization and to establish that below 80K the increase of tau/sub 0/ slows down and that at T approximately equal to 10-4K the time tau/sub 0/ reaches a plateau (tau/sub 0/ approximately equals 0.01s), are described. Possible explanations of the observed low-temperature limit for the rate of a chemical reaction are critically examined and a semiquantitative explanation is given for this phenomenon, which may be particularly common in combined electronic-confirmational transitions in complex biological molecules and may play a definite role in chemical and biological evolution (cold prehistory of life).

Generating high temperature tolerant transgenic plants: Achievements and challenges.

Science.gov (United States)

Grover, Anil; Mittal, Dheeraj; Negi, Manisha; Lavania, Dhruv

2013-05-01

Production of plants tolerant to high temperature stress is of immense significance in the light of global warming and climate change. Plant cells respond to high temperature stress by re-programming their genetic machinery for survival and reproduction. High temperature tolerance in transgenic plants has largely been achieved either by over-expressing heat shock protein genes or by altering levels of heat shock factors that regulate expression of heat shock and non-heat shock genes. Apart from heat shock factors, over-expression of other trans-acting factors like DREB2A, bZIP28 and WRKY proteins has proven useful in imparting high temperature tolerance. Besides these, elevating the genetic levels of proteins involved in osmotic adjustment, reactive oxygen species removal, saturation of membrane-associated lipids, photosynthetic reactions, production of polyamines and protein biosynthesis process have yielded positive results in equipping transgenic plants with high temperature tolerance. Cyclic nucleotide gated calcium channel proteins that regulate calcium influxes across the cell membrane have recently been shown to be the key players in induction of high temperature tolerance. The involvement of calmodulins and kinases in activation of heat shock factors has been implicated as an important event in governing high temperature tolerance. Unfilled gaps limiting the production of high temperature tolerant transgenic plants for field level cultivation are discussed. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

Interaction of chemical reactions and radiant heat transfer with temperature turbulent pulsations and its effect on heat traner in high-temperature gas flows

International Nuclear Information System (INIS)

Petukhov, B.S.; Zal'tsman, I.G.; Shikov, V.K.

1980-01-01

Methods of taking account of mutual effect of chemical transformations, radiation and turbulence in the calculations of heat transfer in gas flows are considered. Exponential functions of medium parameters are used to describe chemical sources and optical properties of media. It is shown using as an example the dissociation reaction C 2 reversible 2C that the effect of temperature and composition pulsations on recombination rates is negligibly small. It is also shown on the example of turbulent flow of hot molecular gas in a flat channel with cold walls that at moderate temperatures the effect of temperature pulsations on heat radiation flow can be significant (30-40%). The calculational results also show that there is a region in a turbulent boundary layer where the radiation greatly affects the coefficient of turbulent heat transfer

Des-acyl ghrelin prevents heatstroke-like symptoms in rats exposed to high temperature and high humidity.

Science.gov (United States)

Inoue, Yoshiyuki; Hayashi, Yujiro; Kangawa, Kenji; Suzuki, Yoshihiro; Murakami, Noboru; Nakahara, Keiko

2016-02-26

We have shown previously that des-acyl ghrelin decreases body temperature in rats through activation of the parasympathetic nervous system. Here we investigated whether des-acyl ghrelin ameliorates heatstroke in rats exposed to high temperature. Peripheral administration of des-acyl ghrelin significantly attenuated hyperthermia induced by exposure to high-temperature (35°C) together with high humidity (70-80%). Although biochemical analysis revealed that exposure to high temperature significantly increased hematocrit and the serum levels of aspartate amino transferase (AST), alanine transaminase (ALT), blood urea nitrogen (BUN), creatinine and electrolytes (Na(+), K(+), Cl(-)), most of these heatstroke-associated reactions were significantly reduced by treatment with des-acyl ghrelin. The level of des-acyl ghrelin in plasma was also found to be significantly increased under high-temperature conditions. These results suggest that des-acyl ghrelin could be useful for preventing heatstroke under high temperature condition. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

The rate of the reaction between CN and C2H2 at interstellar temperatures

Science.gov (United States)

Woon, D. E.; Herbst, E.

1997-01-01

The rate coefficient for the important interstellar reaction between CN and C2H2 has been calculated as a function of temperature between 10 and 300 K. The potential surface for this reaction has been determined through ab initio quantum chemical techniques; the potential exhibits no barrier in the entrance channel but does show a small exit channel barrier, which lies below the energy of reactants. Phase-space calculations for the reaction dynamics, which take the exit channel barrier into account, show the same unusual temperature dependence as determined by experiment, in which the rate coefficient at first increases as the temperature is reduced below room temperature and then starts to decrease as the temperature drops below 50-100 K. The agreement between theory and experiment provides strong confirmation that the reaction occurs appreciably at cool interstellar temperatures.

Solid-state interfacial reaction in molybdenum-carbide systems at high temperature-pressure, and its application to bonding technique

International Nuclear Information System (INIS)

Horiguchi, Akihiro; Suganuma, Katsuaki; Miyamoto, Yoshinari; Koizumi, Mitsue; Shimada, Masahiko.

1986-01-01

Diffusion couples of molybdenum with several carbides, i.e. SiC, B 4 C, TiC, ZrC, HfC and TaC, were heated at various temperatures ranging from 1500 to 1840 deg C under high pressures of 3 GPa and 100 MPa for up to 4 hr. The couples were then examined for the composition of reaction products, the growth rate of reaction layers, interfacial structures, and tensile strength. In case of Mo-transition metal carbides, Mo 2 C layer was mainly formed, so that the carbides, which had supplied carbon, resulted in having the nonstoichiometric composition near the interface. The activation energy for the growth of Mo 2 C layer in Mo-TiC system was 332 kJ/mol, and that in Mo-TaC system was 366 kJ/mol. In Mo-SiC system, Mo 2 C layer, the mixed phase of Mo 2 C and Mo 5 Si 3 , and Mo 5 Si 3 C layer were formed in order from the Mo side. In Mo-B 4 C system, the mixed phase of Mo 2 B and MoB, and Mo 2 BC layer appeared. The decomposed graphite from B 4 C was also observed between B 4 C and Mo 2 BC phase. The activation energy for the growth of total reaction layer in Mo-SiC system was 531 kJ/mol, and that in Mo-B 4 C system was 183 kJ/mol. It can be said that the growth of reaction layers is controlled by diffusion. The orientation of crystals was observed in all reaction products except for Mo 2 BC phase in Mo-B 4 C system and (Mo, Ta) 2 C phase in Mo-TaC system. In HIPed couples, the magnitude of tensile strength was dependent on the difference in thermal expansion coefficient between Mo and carbides. HIPed Mo-TaC couple had the best weldability among the systems examined in the present investigation. (author)

Thermodynamic evaluation of highly exothermic reactions for the fabrication of ceramic metal composites

International Nuclear Information System (INIS)

Rodrigues, J.A.; Pandolfelli, V.C.; Botta Filho, W.J.; Tomasi, R.; Stevens, R.; Brook, R.J.

1990-01-01

Highly exothermic reactions allow the synthesis or production of materials. Which present advantages regarding to energy saving, simplicity of process and higher purity of the products. Considering adiabatic conditions these reactions give off a large amount of heat which will raise the temperature of the system, allowing the production of highly refractory materials. This paper presents a thermodynamic forecast of reactants are Nb2O5, Al e Zr. The objective is to produce high toughness alumina matrix composites containing ZrO2 particles and Nb metal. (author)

Photocatalytic Degradation of Chlorobenzene by TiO2 in High-Temperature and High-Pressure Water

Directory of Open Access Journals (Sweden)

N. Kometani

2008-01-01

Full Text Available A fluidized-bed-type flow reactor available for the photocatalytic treatment of the suspension of model soil under high-temperature, high-pressure conditions was designed. An aqueous suspension containing hydrogen peroxide (H2O2 as an oxidizer and inorganic oxides as a model soil, titania (TiO2, silica (SiO2, or kaoline (Al2Si2O5(OH4 was continuously fed into the reactor with the temperature and the pressure controlled to be T=20–400∘C and P = 30 MPa, respectively. The degradation of chlorobenzene (CB in water was chosen as a model oxidation reaction. It appeared that most of the model soils are not so harmful to the SCWO treatment of CB in solutions. When the TiO2 suspension containing H2O2 was irradiated with near-UV light, the promotion of the degradation caused by photocatalytic actions of TiO2 was observed at all temperatures. Persistence of the photocatalytic activity in the oxidation reaction in high-temperature, high-pressure water would open up a possibility of the development of the hybrid process based on the combination of SCWO process and TiO2 photocatalysis for the treatment of environmental pollutants in soil and water, which are difficult to handle by conventional SCWO process or catalytic SCWO process alone.

Temperature-Dependent Rate Coefficients for the Reaction of CH2OO with Hydrogen Sulfide.

Science.gov (United States)

Smith, Mica C; Chao, Wen; Kumar, Manoj; Francisco, Joseph S; Takahashi, Kaito; Lin, Jim Jr-Min

2017-02-09

The reaction of the simplest Criegee intermediate CH 2 OO with hydrogen sulfide was measured with transient UV absorption spectroscopy in a temperature-controlled flow reactor, and bimolecular rate coefficients were obtained from 278 to 318 K and from 100 to 500 Torr. The average rate coefficient at 298 K and 100 Torr was (1.7 ± 0.2) × 10 -13 cm 3 s -1 . The reaction was found to be independent of pressure and exhibited a weak negative temperature dependence. Ab initio quantum chemistry calculations of the temperature-dependent reaction rate coefficient at the QCISD(T)/CBS level are in reasonable agreement with the experiment. The reaction of CH 2 OO with H 2 S is 2-3 orders of magnitude faster than the reaction with H 2 O monomer. Though rates of CH 2 OO scavenging by water vapor under atmospheric conditions are primarily controlled by the reaction with water dimer, the H 2 S loss pathway will be dominated by the reaction with monomer. The agreement between experiment and theory for the CH 2 OO + H 2 S reaction lends credence to theoretical descriptions of other Criegee intermediate reactions that cannot easily be probed experimentally.

The reactions of magnesium and its alloys with moist gases at high temperatures; Les reactions du magnesium et de ses alliages avec les gaz humides aux temperatures elevees

Energy Technology Data Exchange (ETDEWEB)

Darras, R [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1963-02-15

The kinetics and mechanisms of the reaction of pure or low alloyed magnesium with various gas saturated by water vapor: oxygen, argon, nitrogen, air, carbon dioxide, have been studied and compared in the temperature range 350-600 deg C. After picturing the large chemical reactivity of magnesium surface, the more or less properties of the oxide film, always made of magnesia, have been shown depending on the nature of the gas carrying water vapor; in fact, metal sublimation occurs the more easily as the surrounding atmosphere is less oxidizing. Moreover, an activation energy change is systematic, but at a temperature which depends also on the latter. In the case of the alloys, the linear oxidation rate is generally obtained only after short induction periods, parabolic in nature. Two possibilities of corrosion inhibition of magnesium by water vapor are then demonstrated and explained: either by a partial superficial fluoridation, or when the carrier gas is carbon dioxide. Also, the extreme conditions of oxidation were studied, that is the ignition processes that occur at a particular temperature in every gas mixture. Finally, it is tried to evolve the fundamental and practical significance of all the results. (author) [French] On a etudie et compare par voie thermogravimetrique, micrographique et radiocristallographique, les cinetiques et les mecanismes de reaction du magnesium et de certains de ses alliages avec diverses atmospheres saturees en vapeur d'eau: oxygene, argon, azote, air, gaz carbonique, dans un domaine de temperatures s'etendant de 350 a 600 deg C, Apres avoir illustre l'extreme sensibilite chimique de la surface du magnesium, on a tout d'abord montre que la valeur plus ou moins protectrice de la couche d'oxyde formee, pourtant toujours constituee de magnesie normale, depend de la nature du gaz porteur de la vapeur d'eau; en effet, la sublimation du metal intervient d'autant plus facilement que les atmospheres en presence sont moins oxydantes. De plus

High Temperature and Pressure Alkaline Electrochemical Reactor for Conversion of Power to Chemicals

DEFF Research Database (Denmark)

Chatzichristodoulou, Christodoulos

2016-01-01

forces. Raising the operating temperature offers a means to boost performance, as both ionic transport and reaction kinetics are exponentially activated with temperature. Indeed, we have demonstrated alkaline electrolysis cells operating at 200-250 °C and 20-50 bar at very high efficiencies and power...... been established enabling experiments with gaseous or liquids reactants/products at cell sizes of up to 25 cm2. Efforts are currently directed towards the investigation of the intrinsic activity of mixed oxides for the oxygen evolution reaction at elevated temperatures and pressures...

Propargyl Recombination: Estimation of the High Temperature, Low Pressure Rate Constant from Flame Measurements

DEFF Research Database (Denmark)

Rasmussen, Christian Lund; Skjøth-Rasmussen, Martin Skov; Jensen, Anker

2005-01-01

The most important cyclization reaction in hydrocarbon flames is probably recombination of propargyl radicals. This reaction may, depending on reaction conditions, form benzene, phenyl or fulvene, as well as a range of linear products. A number of rate measurements have been reported for C3H3 + C3H......3 at temperatures below 1000 K, while data at high temperature and low pressure only can be obtained from flames. In the present work, an estimate of the rate constant for the reaction at 1400 +/- 50 K and 20 Torr is obtained from analysis of the fuel-rich acetylene flame of Westmoreland, Howard...

PETIs as High-Temperature Resin-Transfer-Molding Materials

Science.gov (United States)

Connell, John N.; Smith, Joseph G., Jr.; Hergenrother, Paul M.

2005-01-01

Compositions of, and processes for fabricating, high-temperature composite materials from phenylethynyl-terminated imide (PETI) oligomers by resin-transfer molding (RTM) and resin infusion have been developed. Composites having a combination of excellent mechanical properties and long-term high-temperature stability have been readily fabricated. These materials are particularly useful for the fabrication of high-temperature structures for jet-engine components, structural components on highspeed aircraft, spacecraft, and missiles. Phenylethynyl-terminated amide acid oligomers that are precursors of PETI oligomers are easily made through the reaction of a mixture of aromatic diamines with aromatic dianhydrides at high stoichiometric offsets and 4-phenylethynylphthalic anhydride (PEPA) as an end-capper in a polar solvent such as N-methylpyrrolidinone (NMP). These oligomers are subsequently cyclodehydrated -- for example, by heating the solution in the presence of toluene to remove the water by azeotropic distillation to form low-molecular-weight imide oligomers. More precisely, what is obtained is a mixture of PETI oligomeric species, spanning a range of molecular weights, that exhibits a stable melt viscosity of less than approximately 60 poise (and generally less than 10 poise) at a temperature below 300 deg C. After curing of the oligomers at a temperature of 371 deg C, the resulting polymer can have a glass-transition temperature (Tg) as high as 375 C, the exact value depending on the compositions.

High-Temperature Structural Analysis of a Small-Scale Prototype of a Process Heat Exchanger (IV) - Macroscopic High-Temperature Elastic-Plastic Analysis -

International Nuclear Information System (INIS)

Song, Kee Nam; Hong, Sung Deok; Park, Hong Yoon

2011-01-01

A PHE (Process Heat Exchanger) is a key component required to transfer heat energy of 950 .deg. C generated in a VHTR (Very High Temperature Reactor) to a chemical reaction that yields a large quantity of hydrogen. A small-scale PHE prototype made of Hastelloy-X was scheduled for testing in a small-scale gas loop at the Korea Atomic Energy Research Institute. In this study, as a part of the evaluation of the high-temperature structural integrity of the PHE prototype, high-temperature structural analysis modeling, and macroscopic thermal and elastic-plastic structural analysis of the PHE prototype were carried out under the gas-loop test conditions as a preliminary qwer123$ study before carrying out the performance test in the gas loop. The results obtained in this study will be used to design the performance test setup for the modified PHE prototype

Kinetic and thermodynamic studies of reactional system (X-I-O-H) by high temperature mass spectrometry

International Nuclear Information System (INIS)

Roki, F.Z.

2009-01-01

High temperature mass spectrometry is used for analysis of vapors coming from iodine reaction with fission products in case of a severe nuclear accident in a pressurized water reactor. Two main ways are used, - (i) thermodynamic analysis of vaporization processes of CsOH, CsI and mixtures CsI-CsOH. - (ii) building a dedicated reactor for kinetic analysis of the recombination of atoms into these stables molecular species. The present study confirms the existence of Cs 2 IOH(g) molecule. Vapor pressures of gaseous molecules CsOH(g), Cs 2 O 2 H 2 (g) and Cs 2 IOH(g) have been determined. Molecular parameters of the mixed molecule have been estimated on the basis of the pure dimmers Cs 2 O 2 H 2 (g) and Cs 2 I 2 (g) and its enthalpy of formation are established. The acquisition of kinetic data needs a new reactor, the conception of which is presented in this work as well as qualification tests: thermal, flow regimes and pressure calibration tests. (author)

Modeling thermal spike driven reactions at low temperature and application to zirconium carbide radiation damage

Science.gov (United States)

Ulmer, Christopher J.; Motta, Arthur T.

2017-11-01

The development of TEM-visible damage in materials under irradiation at cryogenic temperatures cannot be explained using classical rate theory modeling with thermally activated reactions since at low temperatures thermal reaction rates are too low. Although point defect mobility approaches zero at low temperature, the thermal spikes induced by displacement cascades enable some atom mobility as it cools. In this work a model is developed to calculate "athermal" reaction rates from the atomic mobility within the irradiation-induced thermal spikes, including both displacement cascades and electronic stopping. The athermal reaction rates are added to a simple rate theory cluster dynamics model to allow for the simulation of microstructure evolution during irradiation at cryogenic temperatures. The rate theory model is applied to in-situ irradiation of ZrC and compares well at cryogenic temperatures. The results show that the addition of the thermal spike model makes it possible to rationalize microstructure evolution in the low temperature regime.

Optimization of Si–C reaction temperature and Ge thickness in C-mediated Ge dot formation

Energy Technology Data Exchange (ETDEWEB)

Satoh, Yuhki, E-mail: yu-ki@ecei.tohoku.ac.jp; Itoh, Yuhki; Kawashima, Tomoyuki; Washio, Katsuyoshi

2016-03-01

To form Ge dots on a Si substrate, the effect of thermal reaction temperature of sub-monolayer C with Si (100) was investigated and the deposited Ge thickness was optimized. The samples were prepared by solid-source molecular beam epitaxy with an electron-beam gun for C sublimation and a Knudsen cell for Ge evaporation. C of 0.25 ML was deposited on Si (100) at a substrate temperature of 200 °C, followed by a high-temperature treatment at the reaction temperature (T{sub R}) of 650–1000 °C to create Si–C bonds. Ge equivalent to 2 to 5 nm thick was subsequently deposited at 550 °C. Small and dense dots were obtained for T{sub R} = 750 °C but the dot density decreased and the dot diameter varied widely in the case of lower and higher T{sub R}. A dot density of about 2 × 10{sup 10} cm{sup −2} was achieved for Ge deposition equivalent to 3 to 5 nm thick and a standard deviation of dot diameter was the lowest of 10 nm for 5 nm thick Ge. These results mean that C-mediated Ge dot formation was strongly influenced not only by the c(4 × 4) reconstruction condition through the Si–C reaction but also the relationship between the Ge deposition thickness and the exposed Si (100)-(2 × 1) surface area. - Highlights: • The effect of Si–C reaction temperature on Ge dot formation was investigated. • Small and dense dots were obtained for T{sub R} = 750 °C. • The dot density of about 2 × 10{sup 10} cm{sup −2} was achieved for Ge = 3 to 5 nm. • The standard deviation of dot diameter was the lowest of 10 nm at Ge = 5 nm.

Effect of Temperature Profile on Reaction Violence in Heated, Self-Ignited, PBX-9501

Science.gov (United States)

Asay, Blaine; Dickson, Peter; Henson, Bryan; Smilowitz, Laura; Tellier, Larry

2001-06-01

Historically, the location of ignition in heated explosives has been implicated in the violence of subsequent reactions. This is based on the observation that typically, when an explosive is heated quickly, ignition occurs at the surface, leading to premature failure of confinement, a precipitous drop in pressure, and failure of the reaction. During slow heating, reaction usually occurs near the center of the charge, and more violent reactions are observed. Many safety protocols use these global results in determining safety envelopes and procedures. We have conducted instrumented experiments with cylindrical symmetry and precise thermal boundary conditions which have shown that the temperature profile in the explosive, along with the time spent at critical temperatures, and not the location of ignition, are responsible for the level of violence observed. Microwave interferometry was used to measure case expansion velocities and reaction violence. We are using the data in a companion study to develop better kinetic models for HMX and PBX 9501. Additionally, the spatially- and temporally-resolved temperature data are being made available for those who would like to use them.

Solid-state reactions to synthesize nanostructured lead selenide semiconductor powders by high-energy milling

Energy Technology Data Exchange (ETDEWEB)

Rojas-Chavez, H., E-mail: uu_gg_oo@yahoo.com.mx [Centro de Investigacion e Innovacion Tecnologica - IPN, Cerrada de CECATI s/n, Col. Santa Catarina, Del. Azcapotzalco (Mexico) and Centro de Investigacion en Ciencia Aplicada y Tecnologia Avanzada - IPN, Legaria 694, Col. Irrigacion, Del. Miguel Hidalgo (Mexico); Reyes-Carmona, F. [Facultad de Quimica - UNAM, Circuito de la Investigacion Cientifica s/n, C.U. Del. Coyoacan (Mexico); Jaramillo-Vigueras, D. [Centro de Investigacion e Innovacion Tecnologica - IPN, Cerrada de CECATI s/n, Col. Santa Catarina, Del. Azcapotzalco (Mexico)

2011-10-15

Highlights: {yields} PbSe synthesized from PbO instead of Pb powder do not require an inert atmosphere. {yields} During high-energy milling oxygen has to be chemically reduced from the lead oxide. {yields} Solid-state and solid-gas chemical reactions promote both solid and gaseous products. -- Abstract: Both solid-solid and gas-solid reactions have been traced during high-energy milling of Se and PbO powders under vial (P, T) conditions in order to synthesize the PbSe phase. Chemical and thermodynamic arguments are postulated to discern the high-energy milling mechanism to transform PbO-Se micropowders onto PbSe-nanocrystals. A set of reactions were evaluated at around room temperature. Therefore an experimental campaign was designed to test the nature of reactions in the PbO-Se system during high-energy milling.

Solid-state reactions to synthesize nanostructured lead selenide semiconductor powders by high-energy milling

International Nuclear Information System (INIS)

Rojas-Chavez, H.; Reyes-Carmona, F.; Jaramillo-Vigueras, D.

2011-01-01

Highlights: → PbSe synthesized from PbO instead of Pb powder do not require an inert atmosphere. → During high-energy milling oxygen has to be chemically reduced from the lead oxide. → Solid-state and solid-gas chemical reactions promote both solid and gaseous products. -- Abstract: Both solid-solid and gas-solid reactions have been traced during high-energy milling of Se and PbO powders under vial (P, T) conditions in order to synthesize the PbSe phase. Chemical and thermodynamic arguments are postulated to discern the high-energy milling mechanism to transform PbO-Se micropowders onto PbSe-nanocrystals. A set of reactions were evaluated at around room temperature. Therefore an experimental campaign was designed to test the nature of reactions in the PbO-Se system during high-energy milling.

High concentration agglomerate dynamics at high temperatures.

Science.gov (United States)

Heine, M C; Pratsinis, S E

2006-11-21

The dynamics of agglomerate aerosols are investigated at high solids concentrations that are typical in industrial scale manufacture of fine particles (precursor mole fraction larger than 10 mol %). In particular, formation and growth of fumed silica at such concentrations by chemical reaction, coagulation, and sintering is simulated at nonisothermal conditions and compared to limited experimental data and commercial product specifications. Using recent chemical kinetics for silica formation by SiCl4 hydrolysis and neglecting aerosol polydispersity, the evolution of the diameter of primary particles (specific surface area, SSA), hard- and soft-agglomerates, along with agglomerate effective volume fraction (volume occupied by agglomerate) is investigated. Classic Smoluchowski theory is fundamentally limited for description of soft-agglomerate Brownian coagulation at high solids concentrations. In fact, these high concentrations affect little the primary particle diameter (or SSA) but dominate the soft-agglomerate diameter, structure, and volume fraction, leading to gelation consistent with experimental data. This indicates that restructuring and fragmentation should affect product particle characteristics during high-temperature synthesis of nanostructured particles at high concentrations in aerosol flow reactors.

Reactions of the CN Radical with Benzene and Toluene: Product Detection and Low-Temperature Kinetics

Energy Technology Data Exchange (ETDEWEB)

Trevitt, Adam J.; Goulay, Fabien; Taatjes, Craig A.; Osborn, David L.; Leone, Stephen R.

2009-12-23

Low temperature rate coefficients are measured for the CN + benzene and CN + toluene reactions using the pulsed Laval nozzle expansion technique coupled with laser-induced fluorescence detection. The CN + benzene reaction rate coefficient at 105, 165 and 295 K is found to be relatively constant over this temperature range, 3.9 - 4.9 x 10-10 cm3 molecule-1 s-1. These rapid kinetics, along with the observed negligible temperature dependence, are consistent with a barrierless reaction entrance channel and reaction efficiencies approaching unity. The CN + toluene reaction is measured to have a slower rate coefficient of 1.3 x 10-10 cm3 molecule-1 s-1 at 105 K. At room temperature, non-exponential decay profiles are observed for this reaction that may suggest significant back-dissociation of intermediate complexes. In separate experiments, the products of these reactions are probed at room temperature using synchrotron VUV photoionization mass spectrometry. For CN + benzene, cyanobenzene (C6H5CN) is the only product recorded with no detectable evidence for a C6H5 + HCN product channel. In the case of CN + toluene, cyanotoluene (NCC6H4CH3) constitutes the only detected product. It is not possible to differentiate among the ortho, meta and para isomers of cyanotoluene because of their similar ionization energies and the ~;; 40 meV photon energy resolution of the experiment. There is no significant detection of benzyl radicals (C6H5CH2) that would suggest a H-abstraction or a HCN elimination channel is prominent at these conditions. As both reactions are measured to be rapid at 105 K, appearing to have barrierless entrance channels, it follows that they will proceed efficiently at the temperatures of Saturn?s moon Titan (~;;100 K) and are also likely to proceed at the temperature of interstellar clouds (10-20 K).

Predictive Finite Rate Model for Oxygen-Carbon Interactions at High Temperature

Science.gov (United States)

Poovathingal, Savio

An oxidation model for carbon surfaces is developed to predict ablation rates for carbon heat shields used in hypersonic vehicles. Unlike existing empirical models, the approach used here was to probe gas-surface interactions individually and then based on an understanding of the relevant fundamental processes, build a predictive model that would be accurate over a wide range of pressures and temperatures, and even microstructures. Initially, molecular dynamics was used to understand the oxidation processes on the surface. The molecular dynamics simulations were compared to molecular beam experiments and good qualitative agreement was observed. The simulations reproduced cylindrical pitting observed in the experiments where oxidation was rapid and primarily occurred around a defect. However, the studies were limited to small systems at low temperatures and could simulate time scales only of the order of nanoseconds. Molecular beam experiments at high surface temperature indicated that a majority of surface reaction products were produced through thermal mechanisms. Since the reactions were thermal, they occurred over long time scales which were computationally prohibitive for molecular dynamics to simulate. The experiments provided detailed dynamical data on the scattering of O, O2, CO, and CO2 and it was found that the data from molecular beam experiments could be used directly to build a model. The data was initially used to deduce surface reaction probabilities at 800 K. The reaction probabilities were then incorporated into the direct simulation Monte Carlo (DSMC) method. Simulations were performed where the microstructure was resolved and dissociated oxygen convected and diffused towards it. For a gas-surface temperature of 800 K, it was found that despite CO being the dominant surface reaction product, a gas-phase reaction forms significant CO2 within the microstructure region. It was also found that surface area did not play any role in concentration of

High Temperature Chemistry of Aromatic Hydrocarbons. Final Technical Report

Energy Technology Data Exchange (ETDEWEB)

Scott, Lawrence T. [Boston College, Chestnut Hill, MA (United States). Merkert Chemistry Center, Dept. of Chemistry

2017-05-15

The primary goal of this research was to uncover the principal reaction channels available to polycyclic aromatic hydrocarbons (PAHs) at high temperatures in the gas phase and to establish the factors that determine which channels will be followed in varying circumstances. New structure-property relationships for PAHs were also studied. The efficient production of clean energy from fossil fuels will remain a major component of the DOE mission until alternative sources of energy eventually displace coal and petroleum. Hydrocarbons constitute the most basic class of compounds in all of organic chemistry, and as the dominant species in fossil fuels, they figure prominently into the programs of the DOE. Much is already known about the normal chemistry of hydrocarbons under ambient conditions, but far less is known about their intrinsic chemistry at temperatures close to those reached during combustion. An understanding of the fundamental molecular transformations, rearrangements, and interconversions of PAHs at high temperatures in the gas phase, as revealed by careful studies on small, well-designed, molecular systems, provides insights into the underlying chemistry of many important processes that are more complex, such as the generation of energy by the combustion of fossil fuels, the uncatalyzed gasification and liquefaction of coal, the production of fullerenes in fuel-rich flames, and the formation of soot and carcinogenic pollutants in smoke (e.g., benzo[a]pyrene). The rational control of any of these processes, whether it be the optimization of a desirable process or the minimization of an undesirable one, requires a clear knowledge of the basic chemistry that governs the fate of the species involved. Advances in chemistry at the most fundamental level come about primarily from the discovery of new reactions and from new insights into how reactions occur. Harnessing that knowledge is the key to new technologies. The recent commercialization of a combustion

Chemical kinetics studies at high temperatures using shock tubes

OpenAIRE

Rajakumar, B; Anandraj, D; Reddy, KPJ; Arunan, E

2002-01-01

Shock tube is an unique facility to create temperature gradients exceeding million degrees Kelvin per second. We have established two shock tubes for measuring the kinetic reaction rates at high temperatures with two different but complementary detection techniques. The first one is a single pulse shock tube, in which the reflected shock is used to heat the molecules. The equilibrated products are analyzed by gas chromatograph and infrared spectrometer. The second one uses laser-schlieren sys...

High-temperature chemistry of HCl and Cl2

DEFF Research Database (Denmark)

Pelucchi, Matteo; Frassoldati, Alessio; Faravelli, Tiziano

2015-01-01

The high temperature chlorine chemistry was updated and the inhibition mechanisms involving HCl and Cl2 were re-examined. The thermochemistry was obtained using the Active Thermochemical Tables (ATcT) approach, resulting in improved data for chlorine-containing species of interest. The HCl/Cl2....... The validation was carried out on selected experimental data from laminar flames, shock tubes and plug flow reactors. Systems containing Cl2 showed high sensitivity to Cl2 +M⇌Cl+Cl+M; the rate constant for this reaction has a significant uncertainty and there is a need for an accurate high...... chemistry discussed in the paper was based on reference and experimental measurements of rate constants available in the literature. By coupling the new HCl/Cl2 subset with the Politecnico di Milano (POLIMI) syngas mechanism a kinetic mechanism consisting of 25 species and 102 reactions was obtained...

Preparation of ultra-fine calcium carbonate by a solvent-free reaction using supersonic airflow and low temperatures

OpenAIRE

Cai, Yan-Hua; Ma, Dong-Mei; Peng, Ru-Fang; Chu, Shi-Jin

2008-01-01

The treatment of calcium chloride with sodium carbonate under solvent-free conditions with a supersonic airflow and at a low heating temperature leads to the synthesis of ultra-fine calcium carbonate. The reaction not only involves mild conditions, a simple operation, and high yields but also gives a high conversion rate.

Reaction of hydroxyl radicals with ammonia in liquid water at elevated temperatures

DEFF Research Database (Denmark)

Hickel, B.; Sehested, K.

1992-01-01

The reaction of hydroxyl radical with ammonia in aqueous solutions has been studied by pulse radiolysis in the temperature range 20-200-degrees-C. The rate constant of the reaction was determined by monitoring the decay of the OH radical absorption at 260 nm for different concentrations of ammonia....... At room temperature the rate constant is (9.7 +/- 1) x 10(7) dm3 mol-1 s-1. In the whole range of temperatures the Tate constant follows Arrhenius law with an activation energy of (5.7 +/- 1) kJ mol-1. The protective effect of dissolved hydrogen on the radiolytic decomposition of ammon a is discussed....

KINETICS OF THE REACTION OF ELEMENTAL FLUORINE WITH ZIRCONIUM CARBIDE AND ZIRCONIUM DIBORIDE AT HIGH TEMPERATURES

Energy Technology Data Exchange (ETDEWEB)

Kuriakose, A. K.; Margrave, J. L.

1963-09-15

The reaction between ZrC and F/sub 2/ was investigated at 278 to 410 deg C, using 31 mm HgF/syb 2/. The reaction was found to be linear with time, and linear rate constants were computed. The activation energy was determined to be 22.1 plus or minus 1.6 kcal/mole. ZrB/sub 2/ is not attacked by 31 mm HgF/sub 2/ below 500 deg C. The weight losses from reaction of ZrB/sub 2/ with F/sub 2/ at 600 to 900 deg C and of ZrC with F/sub 2/ at 700 to 950 deg C, were rneasured for a F/sub 2/ pressure of 2.7 mm Hg. Zero-time linear rate constants were calculated and found not to be strongly temperature-dependent above 600 deg C, and the activation energies are essentially zero for both ZrB/sub 2/ and ZrC. For ZrC at 350 deg C and for ZrB/sub 2/ at 700 deg C, the rate is approximately proportional to the square root of F/sub 2/ partial pressure, while for ZrC at 700 deg C, it is proportional to the 1.5 power of F/sub 2/ partial pressure. (D.L.C.)

A high-temperature shock tube kinetic study for the branching ratios of isobutene+OH reaction

KAUST Repository

Khaled, Fathi; Giri, Binod; Farooq, Aamir

2016-01-01

Isobutene is an important intermediate formed during the oxidation of branched alkanes. It also appears as a byproduct during the combustion of methyl-tert-butyl-ether (MTBE) which is used as octane enhancer in gasolines. To understand better the oxidation kinetics of isobutene, we have measured the rate coefficients for the reaction of OH radicals with isobutene (HCC(CH)) behind reflected shock waves over the temperature range of 830-1289K and pressures near 1.5atm. The reaction progress was followed by measuring mole fraction of OH radicals near 306.7nm using UV laser absorption technique. Three deuterated isotopes, isobutene-1-d2 (DCC(CH)), isobutene-3-d6 (HCC(CD)) and isobutene-d8 (DCC(CD)) were employed to elucidate branching ratios of the allylic and vinylic H-abstraction from isobutene by OH radicals. H-abstraction from the allylic sites was found to be dominant and constituted about 75% of the total rate in the entire temperature range of the current work. The derived three-parameter Arrhenius expressions for site-specific H- and D- abstraction rates over 830-1289K are (units:cm mol s):k3,H=6.98×106(TK)1.77exp(-136.6KT) k3,D=4.42×106(TK)1.8exp(-361.7KT) k1,H=6.25×105(TK)2.16exp(-711.6KT) k1,D=3.13×107(TK)1.67exp(-1814KT) The subscript of . k identifies the position of H or D atom in isobutene according to the IUPAC nomenclature of alkenes.

A high-temperature shock tube kinetic study for the branching ratios of isobutene+OH reaction

KAUST Repository

Khaled, Fathi

2016-10-11

Isobutene is an important intermediate formed during the oxidation of branched alkanes. It also appears as a byproduct during the combustion of methyl-tert-butyl-ether (MTBE) which is used as octane enhancer in gasolines. To understand better the oxidation kinetics of isobutene, we have measured the rate coefficients for the reaction of OH radicals with isobutene (HCC(CH)) behind reflected shock waves over the temperature range of 830-1289K and pressures near 1.5atm. The reaction progress was followed by measuring mole fraction of OH radicals near 306.7nm using UV laser absorption technique. Three deuterated isotopes, isobutene-1-d2 (DCC(CH)), isobutene-3-d6 (HCC(CD)) and isobutene-d8 (DCC(CD)) were employed to elucidate branching ratios of the allylic and vinylic H-abstraction from isobutene by OH radicals. H-abstraction from the allylic sites was found to be dominant and constituted about 75% of the total rate in the entire temperature range of the current work. The derived three-parameter Arrhenius expressions for site-specific H- and D- abstraction rates over 830-1289K are (units:cm mol s):k3,H=6.98×106(TK)1.77exp(-136.6KT) k3,D=4.42×106(TK)1.8exp(-361.7KT) k1,H=6.25×105(TK)2.16exp(-711.6KT) k1,D=3.13×107(TK)1.67exp(-1814KT) The subscript of . k identifies the position of H or D atom in isobutene according to the IUPAC nomenclature of alkenes.

Structural instabilities of high temperature alloys and their use in advanced high temperature gas cooled reactors

International Nuclear Information System (INIS)

Schuster, H.; Ennis, P.J.; Nickel, H.; Czyrska-Filemonowicz, A.

1989-01-01

High-temperature, iron-nickel and nickel based alloys are the candidate heat exchanger materials for advanced high temperature gas-cooled reactors supplying process heat for coal gasification, where operation temperatures can reach 850-950 deg. C and service lives of more than 100,000 h are necessary. In the present paper, typical examples of structural changes which occur in two representative alloys (Alloy 800 H, Fe-32Ni-20Cr and Alloy 617, Ni-22Cr-12Co-9Mo-1Al) during high temperature exposure will be given and the effects on the creep rupture properties discussed. At service temperatures, precipitation of carbides occurs which has a significant effect on the creep behaviour, especially in the early stages of creep when the precipitate particles are very fine. During coarsening of the carbides, carbides at grain boundaries restrict grain boundary sliding which retards the development of creep damage. In the service environments, enhanced carbide precipitation may occur due to the ingress of carbon from the environment (carburization). Although the creep rate is not adversely affected, the ductility of the carburized material at low and intermediate temperatures is very low. During simulated service exposures, the formation of surface corrosion scales, the precipitation of carbides and the formation of internal oxides below the surface leads to depletion of the matrix in the alloying elements involved in the corrosion processes. In thin-walled tubes the depletion of Cr due to Cr 2 O 3 formation on the surface can lead to a loss of creep strength. An additional depletion effect resulting from environmental-metal reactions is the loss of carbon (decarburization) which may occur in specific environments. The compositions of the cooling gases which decarburize the material have been determined; they are to be avoided during reactor operation

Temperature dependence of third order ion molecule reactions. The reaction H+3 + 2H2 = H+5 + H2

International Nuclear Information System (INIS)

Hiraoka, K.; Kebarle, P.

1975-01-01

The rate constants k 1 for Reaction (1): H + 3 +2H 2 = H + 5 +H 2 were measured in the temperature range 100--300 degreeK. The temperature dependence of k 1 has the form k 1 proportionalT - /subn/, where n=2.3. Pierce and Porter have reported a much stronger negative temperature dependence with n=4.6. The difference arises from a determination of k 1 at 300 degreeK obtained by Arifov and used by Porter. The present k 1 (300 degreeK) =9times10 -30 (cm 6 molecules -2 center-dotsec -1 ). This is more than an order of magnitude larger than the Arifov value. The temperature dependence of third body dependent association reactions like (1) is examined on the basis of the energy transfer theory and the recently proposed trimolecular complex transition state theory by Meot-Ner, Solomon, Field, and Gershinowitz. The temperature dependence of the rate constant for the reverse reaction (-1) is obtained from k 1 and the previously determined temperature dependence of the equilibria (1). k/sub -//sub 1/ gives a good straight line Arrhenius plot leading to k/sub -//sub 1/ =8.7times10 -6 exp(-8.4/RT) cm 3 molecules -1 center-dotsec -1 . The activation energy is in kcal/mole. The preexponential factor is much larger than the rate constant for Langevin collisions. This is typical for pyrolysis of ions involving second order activation

Temperature dependence on plasma-induced damage and chemical reactions in GaN etching processes using chlorine plasma

Science.gov (United States)

Liu, Zecheng; Ishikawa, Kenji; Imamura, Masato; Tsutsumi, Takayoshi; Kondo, Hiroki; Oda, Osamu; Sekine, Makoto; Hori, Masaru

2018-06-01

Plasma-induced damage (PID) on GaN was optimally reduced by high-temperature chlorine plasma etching. Energetic ion bombardments primarily induced PID involving stoichiometry, surface roughness, and photoluminescence (PL) degradation. Chemical reactions under ultraviolet (UV) irradiation and chlorine radical exposure at temperatures higher than 400 °C can be controlled by taking into account the synergism of simultaneous photon and radical irradiations to effectively reduce PID.

Ethanol electrooxidation on a carbon-supported Pt catalyst at elevated temperature and pressure: A high-temperature/high-pressure DEMS study

Science.gov (United States)

Sun, S.; Halseid, M. Chojak; Heinen, M.; Jusys, Z.; Behm, R. J.

The electrooxidation of ethanol on a Pt/Vulcan catalyst was investigated in model studies by on-line differential electrochemical mass spectrometry (DEMS) over a wide range of reaction temperatures (23-100 °C). Potentiodynamic and potentiostatic measurements of the Faradaic current and the CO 2 formation rate, performed at 3 bar overpressure under well-defined transport and diffusion conditions reveal significant effects of temperature, potential and ethanol concentration on the total reaction activity and on the selectivity for the pathway toward complete oxidation to CO 2. The latter pathway increasingly prevails at higher temperature, lower concentration and lower potentials (∼90% current efficiency for CO 2 formation at 100 °C, 0.01 M, 0.48 V), while at higher ethanol concentrations (0.1 M), higher potentials or lower temperatures the current efficiency for CO 2 formation drops, reaching values of a few percent at room temperature. These trends result in a significantly higher apparent activation barrier for complete oxidation to CO 2 (68 ± 2 kJ mol -1 at 0.48 V, 0.1 M) compared to that of the overall ethanol oxidation reaction determined from the Faradaic current (42 ± 2 kJ mol -1 at 0.48 V, 0.1 M). The mechanistic implications of these results and the importance of relevant reaction and mass transport conditions in model studies for reaction predictions in fuel cell applications are discussed.

Ethanol electrooxidation on a carbon-supported Pt catalyst at elevated temperature and pressure: A high-temperature/high-pressure DEMS study

Energy Technology Data Exchange (ETDEWEB)

Sun, S.; Halseid, M. Chojak; Heinen, M.; Jusys, Z.; Behm, R.J. [Institute of Surface Chemistry and Catalysis, Ulm University, D-89069 Ulm (Germany)

2009-05-01

The electrooxidation of ethanol on a Pt/Vulcan catalyst was investigated in model studies by on-line differential electrochemical mass spectrometry (DEMS) over a wide range of reaction temperatures (23-100 C). Potentiodynamic and potentiostatic measurements of the Faradaic current and the CO{sub 2} formation rate, performed at 3 bar overpressure under well-defined transport and diffusion conditions reveal significant effects of temperature, potential and ethanol concentration on the total reaction activity and on the selectivity for the pathway toward complete oxidation to CO{sub 2}. The latter pathway increasingly prevails at higher temperature, lower concentration and lower potentials ({proportional_to}90% current efficiency for CO{sub 2} formation at 100 C, 0.01 M, 0.48 V), while at higher ethanol concentrations (0.1 M), higher potentials or lower temperatures the current efficiency for CO{sub 2} formation drops, reaching values of a few percent at room temperature. These trends result in a significantly higher apparent activation barrier for complete oxidation to CO{sub 2} (68 {+-} 2 kJ mol{sup -1} at 0.48 V, 0.1 M) compared to that of the overall ethanol oxidation reaction determined from the Faradaic current (42 {+-} 2 kJ mol{sup -1} at 0.48 V, 0.1 M). The mechanistic implications of these results and the importance of relevant reaction and mass transport conditions in model studies for reaction predictions in fuel cell applications are discussed. (author)

Rate coefficients for the reactions of ions with polar molecules at interstellar temperatures

International Nuclear Information System (INIS)

Adams, N.G.; Smith, D.; Clary, D.C.

1985-01-01

A theory has been developed recently which predicts that the rate coefficients, k, for the reactions of ions with polar molecules at low temperatures will be much greater than the canonical value of 10 -9 cm 3 s -1 . The new theory indicates that k is greatest for low-lying rotational sates and increases rapidly with decreasing temperature. We refer to recent laboratory measurements which validate the theory, present calculated values of k for the reactions of H + 3 ions with several polar molecules, and discuss their significance to interstellar chemistry. For the reactions of ions with molecules having large dipole moments, we recommend that k values as large as 10 -7 cm 3 s -1 should be used in ion-chemical models of low-temperature interstellar clouds

Co-Liquefaction of Elbistan Lignite with Manure Biomass; Part 3 - Effect of Reaction Time and Temperature

Science.gov (United States)

Koyunoglu, Cemil; Karaca, Hüseyin

2017-12-01

Most of the liquefaction process were carried out in a batch reactor, in which the residence time of the liquefaction products is long enough to favour the retrogressive reactions. To minimize retrogressive reactions, the liquefaction of coal was carried out in a flowing solvent reactor in which a fixed bed of coal is continuously permeated by hot solvent. Solvent flowing through the coal bed carries the liquefaction products out of the reactor. Unlike experiments carried out under similar conditions in a batch reactor no increase in solid residue is observed during long time high temperature runs in the flowing solvent reactor. There is a greater appreciation of the importance of retrograde, or polymerization, reactions. If the free radicals formed when coal breaks down are not quickly capped with hydrogen, they react with each other to form large molecules that are much harder to break down than the original coal. Reaction time impacts both the co-liquefaction cost and the product yield. So as to study this idea, the experiments of Elbistan Lignite (EL) with manure co-liquefaction carried out by changing the reaction time from 30 to 120 minutes. As a result, the greatest oil products yields obtained at 60 minutes. Therefore, by thinking about the oil products yield values acquired, the optimal reaction time was obtained to be 60 minutes for Elbistan lignite (EL) with manure liquefied with the temperature of 350°C and 400°C. Above 425°C did not examine because solvent (tetraline) loses its function after 425 °C. The obtained optimum temperature found 400°C due to higher total conversion of liquefaction products and also oil+gas yields.

HTP kinetics studies on isolated elementary combustion reactions over wide temperature ranges

Energy Technology Data Exchange (ETDEWEB)

Fontijn, A.; Adusei, G.Y.; Hranisavlevic, J.; Bajaj, P.N. [Rensselaer Polytechnic Institute, Troy, NY (United States)

1993-12-01

The goals of this project are to provide accurate data on the temperature dependence of the kinetics of elementary combustion reactions, (i) for use by combustion modelers, and (ii) to gain a better fundamental understanding of, and hence predictive ability for, the chemistry involved. Experimental measurements are made mainly by using the pseudo-static HTP (high-temperature photochemistry) technique. While continuing rate coefficient measurements, further aspects of kinetics research are being explored. Thus, starting from the data obtained, a method for predicting the temperature dependence of rate coefficients of oxygen-atom olefin experiment and confirms the underlying mechanistic assumptions. Mechanistic information of another sort, i.e. by product analysis, has recently become accessible with the inauguration of our heated flow tube mass spectrometer facility; early results are reported here. HTP experiments designed to lead to measurements of product channels by resonance fluorescence have started.

Optimisation and application of electrochemical techniques for high temperature aqueous environments

International Nuclear Information System (INIS)

Bojinov, M.; Laitinen, B. T.; Maekelae, K.; Maekelae, M; Saario, T.; Sirkiae, P.; Beverskog, B.

1999-01-01

Different localised corrosion phenomena may pose a serious hazard to construction materials employed in high-temperature aqueous environments. The operating temperatures in electric power production have been increased to improve plant efficiencies. This has lead to the demand for new, further improved engineering materials. The applicability of these materials in the operating power plant environments largely depends on the existence of a protective surface oxide film. Extensive rupture of these films can lead to increased reaction of the underlying metal with environment. Therefore by modifying the composition of the base metal the properties of the surface oxides can be optimised to withstand the new operational environments of interest. To mitigate the risk of detrimental corrosion phenomena of structural materials, mechanistic understanding of the contributing processes is required. This calls for more experimental information and necessitates the development of new experimental techniques and procedures capable of operating in situ in high temperature aqueous environments. The low conductivity of the aqueous medium complicates electrochemical studies on construction and fuel cladding materials carried out in simulated LWR coolant conditions or in actual plant conditions, especially in typical BWR environments. To obtain useful information of reactions and transport processes occurring on and within oxide films on different materials, an electrochemical arrangement based on a thin-layer electrode (TLEC) concept was developed. In this presentation the main results are shown from work carried out to optimise further the geometry of the TLEC arrangement and to propose recommendations for how to use this arrangement in different low-conductivity environments. Results will be also given from the test in which the TLEC arrangement was equipped with a detector electrode. The detector electrode allows detecting soluble products and reaction intermediates at

The rate of the reaction between C2H and C2H2 at interstellar temperatures

Science.gov (United States)

Herbst, E.; Woon, D. E.

1997-01-01

The reaction between the radical C2H and the stable hydrocarbon C2H2 is one of the simplest neutral-neutral hydrocarbon reactions in chemical models of dense interstellar clouds and carbon-rich circumstellar shells. Although known to be rapid at temperatures > or = 300 K, the reaction has yet to be studied at lower temperatures. We present here ab initio calculations of the potential surface for this reaction and dynamical calculations to determine its rate at low temperature. Despite a small potential barrier in the exit channel, the calculated rate is large, showing that this reaction and, most probably, more complex analogs contribute to the formation of complex organic molecules in low-temperature sources.

Localized temperature and chemical reaction control in nanoscale space by nanowire array.

Science.gov (United States)

Jin, C Yan; Li, Zhiyong; Williams, R Stanley; Lee, K-Cheol; Park, Inkyu

2011-11-09

We introduce a novel method for chemical reaction control with nanoscale spatial resolution based on localized heating by using a well-aligned nanowire array. Numerical and experimental analysis shows that each individual nanowire could be selectively and rapidly Joule heated for local and ultrafast temperature modulation in nanoscale space (e.g., maximum temperature gradient 2.2 K/nm at the nanowire edge; heating/cooling time chemical reactions such as polymer decomposition/cross-linking and direct and localized hydrothermal synthesis of metal oxide nanowires were demonstrated.

Nuclear reactor application for high temperature power industrial processes

International Nuclear Information System (INIS)

Dollezhal', N.A.; Zaicho, N.D.; Alexeev, A.M.; Baturov, B.B.; Karyakin, Yu.I.; Nazarov, E.K.; Ponomarev-Stepnoj, N.N.; Protzenko, A.M.; Chernyaev, V.A.

1977-01-01

This report gives the results of considerations on industrial heat and technology processes (in chemistry, steelmaking, etc.) from the point of view of possible ways, technical conditions and nuclear safety requirements for the use of high temperature reactors in these processes. Possible variants of energy-technological diagrams of nuclear-steelmaking, methane steam-reforming reaction and other processes, taking into account the specific character of nuclear fuel are also given. Technical possibilities and economic conditions of the usage of different types of high temperature reactors (gas cooled reactors and reactors which have other means of transport of nuclear heat) in heat processes are examined. The report has an analysis of the problem, that arises with the application of nuclear reactors in energy-technological plants and an evaluation of solutions of this problem. There is a reason to suppose that we will benefit from the use of high temperature reactors in comparison with the production based on high quality fossil fuel [ru

High temperature interaction between Zircaloy-4 and stainless steel type 304

International Nuclear Information System (INIS)

Nagase, Fumihisa; Otomo, Takashi; Uetsuka, Hiroshi

2001-03-01

The chemical interactions between Zircaloy-4 and stainless steel type 304 were investigated in the temperature range from 1273 to 1573 K to obtain the basic information on the melt progress in the fuel bundle during an LWR severe accident. Reaction layers were formed at the contact interface and grew as the temperature and the time increase. The Zircaloy was preferentially dissolved by the reaction. The SEM/EDX analyses showed that the main process of the reaction was diffusion of Fe, Cr and Ni into the Zircaloy which resulted in the formation of a Zr-rich eutectic through the tested temperature range. Reaction rates for decrease in the materials thickness were evaluated and the reaction generally obeyed a parabolic rate law. The reaction rate constant was determined at every examined temperature and Arrhenius type rate equations were estimated for the temperature range. (author)

Reaction rate constants of HO2 + O3 in the temperature range 233-400 K

Science.gov (United States)

Wang, Xiuyan; Suto, Masako; Lee, L. C.

1988-01-01

The reaction rate constants of HO2 + O3 were measured in the temperature range 233-400 K using a discharge flow system with photofragment emission detection. In the range 233-253 K, the constants are approximately a constant value, and then increase with increasing temperature. This result suggests that the reaction may have two different channels. An expression representing the reaction rate constants is presented.

Kinetic calorimetry in the study of the mechanism of low-temperature chemical reactions

Science.gov (United States)

Barkalov, I. M.; Kiryukhin, D. P.

schemes are described [1-5]. However, despite the high working characteristics of modern calorimeters (Perkin-Elmer, Du Pont, LKB, etc.), all of them have one principal disadvantage: a cell with a sample is placed in them at room temperature. In cryochemical investigation, when the sample has metastable formations, the loading is made `from nitrogen to nitrogen', i.e. the sample prepared at 77 K should be loaded into a calorimeter at 77 K. Besides, the existing installations do not allow measurements at the temperatures Cryochemistry and Radiation Chemistry at the Institute of Chemical Physics in Chernogolovka has created original calorimetric techniques which allow: (1) the carrying out phase analysis and the determination of the main thermodynamic characteristic of individual substances and complicated systems in the temperature range 5 300 K. Sample loading can be conducted at 77 K that allows us to study the systems containing: tetrafiuoroethylene, hexafluoropropylene, ethylene, carbon monoxide, nitrogen, methane, hydrogen, oxygen, ozone, formaldehyde and many other gaseous substances; (2) the study of the dynamics of chemical reactions and to measure the main kinetic parameters of the processes-the elementary rate constants and the activation energies. The experiment can be conducted both under direct action of radiation and UV light and in the post-effect mode [5,6].

High temperature interaction between UO2 and Zircaloy-4/silver mixture

International Nuclear Information System (INIS)

Uetsuka, Hiroshi; Nagase, Fumihisa; Otomo, Takashi

1995-12-01

The reaction between UO 2 and Zircaloy is a main material interaction in the reactor core during a severe accident of LWR. With a view of examining the influence of the core materials having low melting temperatures on the reaction, the effect of silver that is main component of PWR control rod alloy was investigated in the temperature range from 1373 to 1703K. Zircaloy was completely liquefied by the same weight of liquid silver at tested temperatures. The reaction between UO 2 and (Zircaloy+silver) mixture roughly obeyed a parabolic rate law. The determined reaction rate below about 1600K was much lower than that obtained by Hofmann et al. for the reaction between UO 2 and Zircaloy. However, it sharply increased with temperature and became comparable with the rate of UO 2 /Zircaloy reaction at about 1700K. Metallurgical examination including EPMA analysis revealed that Zr(O) layer formed at the reaction interface only for the tests below about 1600K correlated with the discontinuity of the temperature dependence of reaction rate. (author)

High-temperature thermal-chemical analysis of nuclear fuel channels

Energy Technology Data Exchange (ETDEWEB)

Nekhamkin, Y; Rosenband, V; Hasan, D; Elias, E; Wacholder, E; Gany, A [Technion-Israel Inst. of Tech., Haifa (Israel)

1996-12-01

In a severe accident situation, e.g., a postulated loss of coolant accident with a coincident loss of emergency core cooling (LOCA/LOECC), the core may become partially uncovered and steam may become the only coolant available. The thermodynamic conditions in the core, in this case, depend on ability of the steam to effectively remove the fuel decay heat and the heat generated by the exothermic steam/Zircaloy reaction., Therefore, it is important to understand the high-temperature behavior of an oxidizing fuel channel. The main objective of this work is to develop a methodology for calculating the clad temperature and rate of oxidation of a partially covered fuel pin. A criterion is derived to define the importance of the chemical reaction in the overall heat balance. The main parameters affecting the fuel thermal behavior are outlined (authors).

The effects of reactants ratios, reaction temperatures and times on Maillard reaction products of the L-ascorbic acid/L-glutamic acid system

Directory of Open Access Journals (Sweden)

Yong-Yan ZHOU

2016-01-01

Full Text Available Abstract The transformation law of the Maillard reaction products with three different reactants ratios - equimolar reactants, excess L-glutamic acid and excess L-ascorbic acid reaction respectively, five different temperatures, and different time conditions for the L-ascorbic acid / L-glutamic acid system were investigated. Results showed that, the increase of the reaction time and temperature led to the increase of the browning products, uncoloured intermediate products, as well as aroma compounds. Compared with the equimolar reaction system, the excess L-ascorbic acid reaction system produced more browning products and uncoloured intermediate products, while the aroma compounds production remained the same. In the excess L-glutamic acid system, the uncoloured intermediate products increased slightly, the browning products remained the same, while the aroma compounds increased.

An optics-based variable-temperature assay system for characterizing thermodynamics of biomolecular reactions on solid support

Energy Technology Data Exchange (ETDEWEB)

Fei, Yiyan; Landry, James P.; Zhu, X. D., E-mail: xdzhu@physics.ucdavis.edu [Department of Physics, University of California, One Shields Avenue, Davis, California 95616 (United States); Li, Yanhong; Yu, Hai; Lau, Kam; Huang, Shengshu; Chokhawala, Harshal A.; Chen, Xi [Department of Chemistry, University of California, One Shields Avenue, Davis, California 95616 (United States)

2013-11-15

A biological state is equilibrium of multiple concurrent biomolecular reactions. The relative importance of these reactions depends on physiological temperature typically between 10 °C and 50 °C. Experimentally the temperature dependence of binding reaction constants reveals thermodynamics and thus details of these biomolecular processes. We developed a variable-temperature opto-fluidic system for real-time measurement of multiple (400–10 000) biomolecular binding reactions on solid supports from 10 °C to 60 °C within ±0.1 °C. We illustrate the performance of this system with investigation of binding reactions of plant lectins (carbohydrate-binding proteins) with 24 synthetic glycans (i.e., carbohydrates). We found that the lectin-glycan reactions in general can be enthalpy-driven, entropy-driven, or both, and water molecules play critical roles in the thermodynamics of these reactions.

Synthesis of single-crystal perovskite PbCrO3 through a new reaction route at high pressure

Science.gov (United States)

Han, Yunxia; Wang, Shanmin; Liu, Yinjuan; Ma, Dejiang; He, Duanwei; Zhao, Yusheng

2018-04-01

As a new member in the family of Mott system, perovskite PbCrO3 has recently been uncovered to exhibit fantastic structural transition under pressure, coupled with magnetic, electronic, and ferromagnetic transitions, which provide many opportunities for understanding of correlated system. However, it is still challenging to synthesize high-quality single-crystal PbCrO3, leading to the limited exploration of this Mott compound. In this work, we formulate a new high-pressure reaction route for preparation of high-quality PbCrO3 crystals between PbCl2 and Na2CrO4 at high pressure of 5-10 GPa and at high temperature of 750-1500°C. Because of the formation of reaction byproduct NaCl, the final product can readily be separated by washing with water. The obtained sample is in the form of single crystal with crystallite size up to 200 μm. In addition, combined with X-ray diffraction measurement, a tentative pressure-temperature synthesis diagram of PbCrO3 is mapped out from the reaction between PbCl2 and Na2CrO4 and the reaction mechanism is also explored in detail.

A reactor/receiver-concept for liquid-phase high-temperature processes

Energy Technology Data Exchange (ETDEWEB)

Schmidt-Traub, H.; Hahm, T. [Dortmund Univ. (Germany). Dept. of Chemical Engineering

1997-12-31

Besides the conversion of solar light to electricity solar energy can be used directly in photo- and thermochemistry. In the temperature range from 1000 to 2000 K there is a high demand for industrial process heat offering a variety of possibilities for solar thermal applications. Especially in the field of liquid-phase high-temperature processes there are hardly no solar thermal applications which exceed the stage of laboratory experiments. It was therefore the aim of two projects financed by the AG Solar of North Rhine-Westphalia, Germany, to develop concepts for commercial scale solar thermal plants and to judge them economically and ecologically. Some general problems have to be overcome to realize a commercial scale solar thermal plant for liquid-phase processes. The concept developed consists of a heliostat field, a tower reflector and an open receiver with a closed reaction chamber. The feasibility of a solar thermal plant for high-temperature liquid-phase processes has been shown in principle. The projected plant consists of a 4400 m{sup 2} heliostat field, a tower plus reflecting mirrors with a total area of 220 m{sup 2} and an open receiver with a closed annular reaction zone. For temperatures below 1700 K the overall efficiency is high enough to yield energetic amortization times of less than 1 year. For a further improvement and a verification of the calculation a closer look at the reactor/receiver and its heat transfer processes is necessary. This is done by using a mixed strategy of experiments and simulation. First experiments were carried out with a semitransparent salt and an opaque metal. The first stage of the experiments will end during the next weeks and their results have to be compared with the simulation. The simulation will then be extended to transparent melts. The second stage of the experiments which include the reaction chamber will start in 1997. An improvement of the reactor might be achieved using nonimaging concentrators to further

Hydrogen/Oxygen Reactions at High Pressures and Intermediate Temperatures: Flow Reactor Experiments and Kinetic Modeling

DEFF Research Database (Denmark)

Hashemi, Hamid; Christensen, Jakob Munkholt; Glarborg, Peter

A series of experimental and numerical investigations into hydrogen oxidation at high pressures and intermediate temperatures has been conducted. The experiments were carried out in a high pressure laminar flow reactor at 50 bar pressure and a temperature range of 600–900 K. The equivalence ratio......, the mechanism is used to simulate published data on ignition delay time and laminar burning velocity of hydrogen. The flow reactor results show that at reducing, stoichiometric, and oxidizing conditions, conversion starts at temperatures of 750–775 K, 800–825 K, and 800–825 K, respectively. In oxygen atmosphere......, ignition occurs at the temperature of 775–800 K. In general, the present model provides a good agreement with the measurements in the flow reactor and with recent data on laminar burning velocity and ignition delay time....

Substitution of conventional high-temperature syntheses of inorganic compounds by near-room-temperature syntheses in ionic liquids

KAUST Repository

Groh, Matthias Friedrich

2013-01-01

The high-temperature syntheses of the low-valent halogenides P2I4, Te2Br, α-Te4I4, Te4(Al2Cl7)2, Te4(Bi6Cl20), Te8(Bi4Cl14),Bi8(AlCl4)2, Bi6Cl7,and Bi6Br7, as well as of WSCl4 andWOCl4 have been replaced by resource-efficient low-temperature syntheses in room temperature ionic liquids (RTILs). The simple one-pot syntheses generally do not require elaborate equipment such as twozone furnaces or evacuated silica ampoules. Compared to the published conventional approaches, reduction of reaction time (up to 80%) and temperature (up to 500 K) and, simultaneously, an increase in yield were achieved. In the majority of cases, the solid products were phase-pure. X-Ray diffraction on single crystals (redetermination of 11 crystal structures) has demonstrated that the quality of the crystals from RTILs is comparable to that of products obtained by chemical transport reactions. © 2013 Verlag der Zeitschrift für Naturforschung, Tübingen.

Investigation into boron reaction with titanium at extreme temperature gradients

International Nuclear Information System (INIS)

Korchagin, M.A.; Gusenko, S.N.; Aleksandrov, V.V.; Neronov, V.A.

1981-01-01

The mechanism of self-propagation high-temperature synthesis of titanium boride is studied using the translucent electron microscopy. Titanium interaction with boron film (approximately 1000 A thick) starts with the metal partial melting. A twozone layer of the reaction products, separating the reagents, is formed. In the zone adjacent to B, Ti 3 B 4 and fusible liquid phases are present. The second zone consists of TiB. The subsequent interaction is realized by Means of the dissolving and absorption by titanium of the layer of products during its continuous increase in boron. TiB 2 formation takes place at subsequent stages of interaction inside Ti liquid particles during their saturation by boron from the products absorbed [ru

Proceedings of the meeting on tunneling reaction and low temperature chemistry, 98 August. Tunneling reaction and its theory

Energy Technology Data Exchange (ETDEWEB)

Miyazaki, Tetsuo; Aratono, Yasuyuki; Ichikawa, Tsuneki; Shiotani, Masaru [eds.

1998-10-01

Present report is the proceedings of the 4th Meeting on Tunneling Reaction and Low Temperature Chemistry held in August 3 and 4, 1998. The main subject of the meeting is `Tunneling Reaction and Its Theory`. In the present meeting the theoretical aspects of tunneling phenomena in the chemical reaction were discussed intensively as the main topics. Ten reports were presented on the quantum diffusion of muon and proton in the metal and H{sub 2}{sup -} anion in the solid para-hydrogen, the theory of tunnel effect in the nuclear reaction and the tunneling reaction in the organic compounds. One special lecture was presented by Prof. J. Kondo on `Proton Tunneling in Solids`. The 11 of the presented papers are indexed individually. (J.P.N.)

NEDO project reports. High performance industrial furnace development project - High temperature air combustion

Energy Technology Data Exchange (ETDEWEB)

NONE

2000-03-21

For the purpose of reducing energy consumption, a NEDO project 'Developmental research on high efficiency industrial furnaces' was carried out from FY 1993 to FY 1999 by The Japan Industrial Furnaces Manufacturers Association, and the paper outlined the details of the project. Industrial furnaces handled in this R and D can bring 30% reduction of the energy consumption and approximately 50% NOx reduction, and were given the 9th Nikkei global environmental technology prize. In the study of combustion phenomena of high temperature air combustion, the paper arranged characteristics of flame, the base of gaseous fuel flame, the base of liquid fuel flame, the base of solid fuel flame, etc. Concerning high temperature air combustion models for simulation, fluid dynamics and heat transfer models, and reaction and NOx models, etc. As to impacts of high temperature air combustion on performance of industrial furnaces, energy conservation, lowering of pollution, etc. In relation to a guide for the design of high efficiency industrial furnaces, flow charts, conceptual design, evaluation method for heat balance and efficiency using charts, combustion control system, applicability of high efficiency industrial furnaces, etc. (NEDO)

NEDO project reports. High performance industrial furnace development project - High temperature air combustion

Energy Technology Data Exchange (ETDEWEB)

NONE

2000-03-21

For the purpose of reducing energy consumption, a NEDO project 'Developmental research on high efficiency industrial furnaces' was carried out from FY 1993 to FY 1999 by The Japan Industrial Furnaces Manufacturers Association, and the paper outlined the details of the project. Industrial furnaces handled in this R and D can bring 30% reduction of the energy consumption and approximately 50% NOx reduction, and were given the 9th Nikkei global environmental technology prize. In the study of combustion phenomena of high temperature air combustion, the paper arranged characteristics of flame, the base of gaseous fuel flame, the base of liquid fuel flame, the base of solid fuel flame, etc. Concerning high temperature air combustion models for simulation, fluid dynamics and heat transfer models, and reaction and NOx models, etc. As to impacts of high temperature air combustion on performance of industrial furnaces, energy conservation, lowering of pollution, etc. In relation to a guide for the design of high efficiency industrial furnaces, flow charts, conceptual design, evaluation method for heat balance and efficiency using charts, combustion control system, applicability of high efficiency industrial furnaces, etc. (NEDO)

High temperature CO2 capture using calcium oxide sorbent in a fixed-bed reactor

International Nuclear Information System (INIS)

Dou Binlin; Song Yongchen; Liu Yingguang; Feng Cong

2010-01-01

The gas-solid reaction and breakthrough curve of CO 2 capture using calcium oxide sorbent at high temperature in a fixed-bed reactor are of great importance, and being influenced by a number of factors makes the characterization and prediction of these a difficult problem. In this study, the operating parameters on reaction between solid sorbent and CO 2 gas at high temperature were investigated. The results of the breakthrough curves showed that calcium oxide sorbent in the fixed-bed reactor was capable of reducing the CO 2 level to near zero level with the steam of 10 vol%, and the sorbent in CaO mixed with MgO of 40 wt% had extremely low capacity for CO 2 capture at 550 deg. C. Calcium oxide sorbent after reaction can be easily regenerated at 900 deg. C by pure N 2 flow. The experimental data were analyzed by shrinking core model, and the results showed reaction rates of both fresh and regeneration sorbents with CO 2 were controlled by a combination of the surface chemical reaction and diffusion of product layer.

Feasibility study on silicon doping using high temperature test engineering reactor

International Nuclear Information System (INIS)

Seki, Masaya; Takaki, Naoyuki; Goto, Minoru; Shimakawa, Satoshi

2011-01-01

The feasibility study on silicon doping using the High Temperature engineering Test Reactor (HTTR) is performed by numerical simulations. The HTTR is a High Temperature Gas-cooled Reactor (HTGR) situated at JAEA Oarai research and development center. It has a 30MW thermal power and the outlet coolant temperature is 950degC. The objective of this study is to evaluate the following issues, 1. The impact of loading Si-ingots into the core on the criticality, 2. The uniformity of the neutron capture reaction rate in Si-ingots, and 3. The production rate of silicon semiconductor. In this study, six Si-ingots are loaded into the irradiation area which is located in the peripheral region of the core. They are irradiated with rotation movement around the axial direction to obtain uniform neutron capture reaction rate in the radial direction. Additionally, the neutron filter, which is made of graphite containing boron, is used to obtain uniform neutron capture reaction rate in the axial direction. The evaluations were conducted by performing the HTTR whole core calculations with the Monte Carlo code MVP-2.0. In the calculations, several tally regions were defined on the Si-ingots to investigate the uniformity of the neutron capture reaction rate. As a result, loading the Si-ingots into the core causes negative reactivity by about 0.7%dk/k. Uniform neutron capture reaction rate of Si-ingot is obtained 98% in the radial and the axial direction. In case of the target of semiconductor resistivity is set to 50 Ωcm, the required irradiation time becomes 10 hours. The HTTR is able to produce silicon semiconductor of 540kg in one-time irradiation. This study was conducted as a joint research with JAEA, Nuclear Fuel Industries, LTD, Toyota Tsusho Corporation and Tokai University. (author)

Room temperature synthesis and high temperature frictional study of silver vanadate nanorods

Energy Technology Data Exchange (ETDEWEB)

Singh, D P; Aouadi, S M [Department of Physics, Southern Illinois University, Carbondale-62901 (United States); Polychronopoulou, K [Department of Chemistry, University of Cyprus, Nicosia, 1678 (Cyprus); Rebholz, C, E-mail: dineshpsingh@gmail.com, E-mail: saouadi@physics.siu.edu [Department of Mechanical and Manufacturing Engineering, University of Cyprus, Nicosia, 1678 (Cyprus)

2010-08-13

We report the room temperature (RT) synthesis of silver vanadate nanorods (consisting of mainly {beta}-AgV O{sub 3}) by a simple wet chemical route and their frictional study at high temperatures (HT). The sudden mixing of ammonium vanadate with silver nitrate solution under constant magnetic stirring resulted in a pale yellow coloured precipitate. Structural/microstructural characterization of the precipitate through x-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) revealed the high yield and homogeneous formation of silver vanadate nanorods. The length of the nanorods was 20-40 {mu}m and the thickness 100-600 nm. The pH variation with respect to time was thoroughly studied to understand the formation mechanism of the silver vanadate nanorods. This synthesis process neither demands HT, surfactants nor long reaction time. The silver vanadate nanomaterial showed good lubrication behaviour at HT (700 deg. C) and the friction coefficient was between 0.2 and 0.3. HT-XRD revealed that AgV O{sub 3} completely transformed into silver vanadium oxide (Ag{sub 2}V{sub 4}O{sub 11}) and silver with an increase in temperature from RT to 700 deg. C.

Room temperature synthesis and high temperature frictional study of silver vanadate nanorods.

Science.gov (United States)

Singh, D P; Polychronopoulou, K; Rebholz, C; Aouadi, S M

2010-08-13

We report the room temperature (RT) synthesis of silver vanadate nanorods (consisting of mainly beta-AgV O(3)) by a simple wet chemical route and their frictional study at high temperatures (HT). The sudden mixing of ammonium vanadate with silver nitrate solution under constant magnetic stirring resulted in a pale yellow coloured precipitate. Structural/microstructural characterization of the precipitate through x-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) revealed the high yield and homogeneous formation of silver vanadate nanorods. The length of the nanorods was 20-40 microm and the thickness 100-600 nm. The pH variation with respect to time was thoroughly studied to understand the formation mechanism of the silver vanadate nanorods. This synthesis process neither demands HT, surfactants nor long reaction time. The silver vanadate nanomaterial showed good lubrication behaviour at HT (700 degrees C) and the friction coefficient was between 0.2 and 0.3. HT-XRD revealed that AgV O(3) completely transformed into silver vanadium oxide (Ag(2)V(4)O(11)) and silver with an increase in temperature from RT to 700 degrees C.

High-temperature unimolecular decomposition of ethyl propionate

KAUST Repository

Giri, Binod; Alabbad, Mohammed; Farooq, Aamir

2016-01-01

This work reports rate coefficients of the thermal unimolecular decomposition reaction of ethyl propionate (EP) behind reflected shock waves over the temperature range of 976–1300 K and pressures of 825–1875 Torr. The reaction progress was monitored

NOvel Refractory Materials for High Alkali, High Temperature Environments

Energy Technology Data Exchange (ETDEWEB)

Hemrick, J.G.; Griffin, R. (MINTEQ International, Inc.)

2011-08-30

Refractory materials can be limited in their application by many factors including chemical reactions between the service environment and the refractory material, mechanical degradation of the refractory material by the service environment, temperature limitations on the use of a particular refractory material, and the inability to install or repair the refractory material in a cost effective manner or while the vessel was in service. The objective of this project was to address the need for new innovative refractory compositions by developing a family of novel MgO-Al2O3 spinel or other similar magnesia/alumina containing unshaped refractory composition (castables, gunnables, shotcretes, etc) utilizing new aggregate materials, bond systems, protective coatings, and phase formation techniques (in-situ phase formation, altered conversion temperatures, accelerated reactions, etc). This family of refractory compositions would then be tailored for use in high-temperature, highalkaline industrial environments like those found in the aluminum, chemical, forest products, glass, and steel industries. A research team was formed to carry out the proposed work led by Oak Ridge National Laboratory (ORNL) and was comprised of the academic institution Missouri University of Science and Technology (MS&T), and the industrial company MINTEQ International, Inc. (MINTEQ), along with representatives from the aluminum, chemical, glass, and forest products industries. The two goals of this project were to produce novel refractory compositions which will allow for improved energy efficiency and to develop new refractory application techniques which would improve the speed of installation. Also methods of hot installation were sought which would allow for hot repairs and on-line maintenance leading to reduced process downtimes and eliminating the need to cool and reheat process vessels.

Some problems on materials tests in high temperature hydrogen base gas mixture

International Nuclear Information System (INIS)

Shikama, Tatsuo; Tanabe, Tatsuhiko; Fujitsuka, Masakazu; Yoshida, Heitaro; Watanabe, Ryoji

1980-01-01

Some problems have been examined on materials tests (creep rupture tests and corrosion tests) in high temperature mixture gas of hydrogen (80%H 2 + 15%CO + 5%CO 2 ) simulating the reducing gas for direct steel making. H 2 , CO, CO 2 and CH 4 in the reducing gas interact with each other at elevated temperature and produce water vapor (H 2 O) and carbon (soot). Carbon deposited on the walls of retorts and the water condensed at pipings of the lower temperature gas outlet causes blocking of gas flow. The gas reactions have been found to be catalyzed by the retort walls, and appropriate selection of the materials for retorts has been found to mitigate the problems caused by water condensation and carbon deposition. Quartz has been recognized to be one of the most promising materials for minimizing the gas reactions. And ceramic coating, namely, BN (born nitride) on the heat resistant superalloy, MO-RE II, has reduced the amounts of water vapor and deposited carbon (sooting) produced by gas reactions and has kept dew points of outlet gas below room temperature. The well known emf (thermo-electromotive force) deterioration of Alumel-Chromel thermocouples in the reducing gases at elevated temperatures has been also found to be prevented by the ceramic (BN) coating. (author)

Effect of reaction temperature on biodiesel production from waste cooking oil using lipase as biocatalyst

Science.gov (United States)

Istiningrum, Reni Banowati; Aprianto, Toni; Pamungkas, Febria Lutfi Udin

2017-12-01

This study aims to determine the effect of temperature on conversion of biodiesel from waste cooking oil enzymatically using lipase extracted from rice bran. The feedstock was simulated waste cooking oil and lipase enzyme was extracted with buffer pH variation. The enzyme activity was titrimetrically determined and the optimum pH buffer was used to study the effect of temperature on the transesterification reaction. Temperature effects were assessed in the range of 45-60 °C and the content of methyl esters in biodiesel was determined by GC-MS. The reaction temperature significantly influences the transesterification reaction with optimum biodiesel conversion occurred at 55 °C with methyl ester content of 81.19%. The methyl ester composition in the resulting biodiesel is methyl palmitate, methyl oleate and methyl stearate.

Multiscale Informatics for Low-Temperature Propane Oxidation: Further Complexities in Studies of Complex Reactions

Energy Technology Data Exchange (ETDEWEB)

Burke, Michael P.; Goldsmith, C. Franklin; Klippenstein, Stephen J.; Welz, Oliver; Huang, Haifeng; Antonov, Ivan O.; Savee, John D.; Osborn, David L.; Zádor, Judit; Taatjes, Craig A.; Sheps, Leonid

2015-07-16

We have developed a multi-scale approach (Burke, M. P.; Klippenstein, S. J.; Harding, L. B. Proc. Combust. Inst. 2013, 34, 547–555.) to kinetic model formulation that directly incorporates elementary kinetic theories as a means to provide reliable, physics-based extrapolation to unexplored conditions. Here, we extend and generalize the multi-scale modeling strategy to treat systems of considerable complexity – involving multi-well reactions, potentially missing reactions, non-statistical product branching ratios, and non-Boltzmann (i.e. non-thermal) reactant distributions. The methodology is demonstrated here for a subsystem of low-temperature propane oxidation, as a representative system for low-temperature fuel oxidation. A multi-scale model is assembled and informed by a wide variety of targets that include ab initio calculations of molecular properties, rate constant measurements of isolated reactions, and complex systems measurements. Active model parameters are chosen to accommodate both “parametric” and “structural” uncertainties. Theoretical parameters (e.g. barrier heights) are included as active model parameters to account for parametric uncertainties in the theoretical treatment; experimental parameters (e.g. initial temperatures) are included to account for parametric uncertainties in the physical models of the experiments. RMG software is used to assess potential structural uncertainties due to missing reactions. Additionally, branching ratios among product channels are included as active model parameters to account for structural uncertainties related to difficulties in modeling sequences of multiple chemically activated steps. The approach is demonstrated here for interpreting time-resolved measurements of OH, HO2, n-propyl, i-propyl, propene, oxetane, and methyloxirane from photolysis-initiated low-temperature oxidation of propane at pressures from 4 to 60 Torr and temperatures from 300 to 700 K. In particular, the multi-scale informed

Effect of Temperature Profile on Reaction Violence in Heated and Self-Ignited PBX 9501

Science.gov (United States)

Asay, Blaine; Dickson, Peter; Henson, Bryan; Smilowitz, Laura; Tellier, Larry

2002-07-01

Historically, the location of ignition in heated explosives has been implicated in the violence of subsequent reactions. This is based on the observation that typically, when an explosive is heated quickly, ignition occurs at the surface, leading to premature failure of confinement, a precipitous drop in pressure, and failure of the reaction. During slow heating, reaction usually occurs near the center of the charge, and more violent reactions are observed. Many safety protocols use these global results in determining safety envelopes and procedures. We are conducting instrumented experiments with cylindrical symmetry and precise thermal boundary conditions which are beginning to show that the temperature profile in the explosive, along with the time spent at critical temperatures, and not the location of ignition, are responsible for the level of violence observed. Microwave interferometry was used to measure case expansion velocities which can be considered a measure of reaction violence. We are using the data in a companion study to develop better kinetic models for HMX and PBX 9501. Additionally, the spatially- and temporally-resolved temperature data are being made available for those who would like to use them.

Glass precursor approach to high-temperature superconductors

Science.gov (United States)

Bansal, Narottam P.

1992-01-01

The available studies on the synthesis of high T sub c superconductors (HTS) via the glass precursor approach were reviewed. Melts of the Bi-Sr-Ca-Cu-O system as well as those doped with oxides of some other elements (Pb, Al, V, Te, Nb, etc.) could be quenched into glasses which, on further heat treatments under appropriate conditions, crystallized into the superconducting phase(s). The nature of the HTS phase(s) formed depends on the annealing temperature, time, atmosphere, and the cooling rate and also on the glass composition. Long term annealing was needed to obtain a large fraction of the 110 K phase. The high T sub c phase did not crystallize out directly from the glass matrix, but was preceded by the precipitation of other phases. The 110 K HTS was produced at high temperatures by reaction between the phases formed at lower temperatures resulting in multiphase material. The presence of a glass former such as B2O3 was necessary for the Y-Ba-Cu-O melt to form a glass on fast cooling. A discontinuous YBa2Cu3O(7-delta) HTS phase crystallized out on heat treatment of this glass. Attempts to prepare Tl-Ba-Ca-Cu-O system in the glassy state were not successful.

An improved stochastic algorithm for temperature-dependent homogeneous gas phase reactions

CERN Document Server

Kraft, M

2003-01-01

We propose an improved stochastic algorithm for temperature-dependent homogeneous gas phase reactions. By combining forward and reverse reaction rates, a significant gain in computational efficiency is achieved. Two modifications of modelling the temperature dependence (with and without conservation of enthalpy) are introduced and studied quantitatively. The algorithm is tested for the combustion of n-heptane, which is a reference fuel component for internal combustion engines. The convergence of the algorithm is studied by a series of numerical experiments and the computational cost of the stochastic algorithm is compared with the DAE code DASSL. If less accuracy is needed the stochastic algorithm is faster on short simulation time intervals. The new stochastic algorithm is significantly faster than the original direct simulation algorithm in all cases considered.

Low-temperature (75 °C) solid-state reaction enhanced by less-crystallized nanoporous PbI2 films for efficient CH3NH3PbI3 perovskite solar cells

International Nuclear Information System (INIS)

Zheng, Huifeng; Liu, Yangqiao; Sun, Jing

2017-01-01

Highlights: • Efficient perovskite solar cells were prepared with solid-state reaction at 75 °C. • Ln-PbI 2 is superior to c-PbI 2 when applied in low-temperature solid-state reaction. • A higher champion PCE was obtained at 75 °C (13.8%) than that of 140 °C (11.8%). • Non-radiative defects increase significantly when annealed at high temperature. - Abstract: Organohalide perovskite films are usually prepared with the solid-state reaction at a high temperature ≥100 °C, which causes the increase of non-radiative defects and decomposition of perovskite films. Here, we demonstrate it’s feasible to prepare high-quality perovskite films with the solid-state reaction method even at a temperature of 75 °C, when enhanced by less-crystallized nanoporous PbI 2 (ln-PbI 2 ) films. The replacement of compact PbI 2 (c-PbI 2 ) by ln-PbI 2 , results in a significant improvement of crystallinity of perovskite films, besides the elimination of remnant PbI 2 . As a result, ln-PbI 2 based perovskite solar cells display much higher power conversion efficiency (PCE) and better stability. Moreover, annealing duration was found to be critical for high PCE and was optimized as 60 min. Finally, with the optimal process, the champion device displayed a PCE of 13.8% and the average PCE reached 10.1% with a satisfactory deviation. Furthermore, we found annealing at high temperature (140 °C) led to a lower PCE compared with that annealed at 75 °C, because non-radiative defects increased significantly during high-temperature annealing. This work may open up a promising avenue for preparing high-quality perovskite films with the low-temperature solid-state reaction method, which is desirable for real application.

Metallic Membranes for High Temperature Hydrogen Separation

DEFF Research Database (Denmark)

Ma, Y.H.; Catalano, Jacopo; Guazzone, Federico

2013-01-01

membrane fabrication methods have matured over the last decades, and the deposition of very thin films (1–5 µm) of Pd over porous ceramics or modified porous metal supports is quite common. The H2 permeances and the selectivities achieved at 400–500 °C were in the order of 50–100 Nm3/m/h/bar0.5 and greater......Composite palladium membranes have extensively been studied in laboratories and, more recently, in small pilot industrial applications for the high temperature separation of hydrogen from reactant mixtures such as water-gas shift (WGS) reaction or methane steam reforming (MSR). Composite Pd...... than 1000, respectively. This chapter describes in detail composite Pd-based membrane preparation methods, which consist of the grading of the support and the deposition of the dense metal layer, their performances, and their applications in catalytic membrane reactors (CMRs) at high temperatures (400...

Preparation of silver doped high temperature superconductors

International Nuclear Information System (INIS)

Stavek, Jiri; Zapletal, Vladimir

1989-01-01

High temperature superconductors were prepared by the controlled double-jet precipitation to manipulate the chemical composition, composition gradients, average grain size, grain size distribution, and other factors which contribute to the actual properties and performance of HTSC. The cations (Y-Ba-Cu or Bi-Pb-Ca-Sr-Cu) and oxalic anions solutions were simultaneously separately introduced to the crystallizer with a stirred solution of gelatin under conditions where the temperature, excess of oxalic anions in solution, pH, reactant addition rate, and other reaction conditions were tightly controlled to prepare the high sinterability powder. To increase the sinterability of submicron particles of produced precursor, the silver ions were introduced at the end of the controlled double-jet precipitation. This approach improves the electrical and mechanical properties of produced HTSC specimens. The controlled double jet precipitation provides a viable technique for preparation of oxide superconductors and the process is amenable for scaling up

Detonation cell size measurements in high-temperature hydrogen-air-steam mixtures at the BNL high-temperature combustion facility

International Nuclear Information System (INIS)

Ciccarelli, G.; Ginsberg, T.; Boccio, J.L.

1997-11-01

The High-Temperature Combustion Facility (HTCF) was designed and constructed with the objective of studying detonation phenomena in mixtures of hydrogen-air-steam at initially high temperatures. The central element of the HTCF is a 27-cm inner-diameter, 21.3-m long cylindrical test vessel capable of being heating to 700K ± 14K. A unique feature of the HTCF is the 'diaphragmless' acetylene-oxygen gas driver which is used to initiate the detonation in the test gas. Cell size measurements have shown that for any hydrogen-air-steam mixture, increasing the initial mixture temperature, in the range of 300K to 650K, while maintaining the initial pressure of 0.1 MPa, decreases the cell size and thus makes the mixture more detonable. The effect of steam dilution on cell size was tested in stoichiometric and off-stoichiometric (e.g., equivalence ratio of 0.5) hydrogen-air mixtures. Increasing the steam dilution in hydrogen-air mixtures at 0.1 MPa initial pressure increases the cell size, irrespective of initial temperature. It is also observed that the desensitizing effect of steam diminished with increased initial temperature. A 1-dimensional, steady-state Zel'dovich, von Neumann, Doring (ZND) model, with full chemical kinetics, has been used to predict cell size for hydrogen-air-steam mixtures at different initial conditions. Qualitatively the model predicts the overall trends observed in the measured cell size versus mixture composition and initial temperature and pressure. It was found that the proportionality constant used to predict detonation cell size from the calculated ZND model reaction zone varies between 10 and 100 depending on the mixture composition and initial temperature. 32 refs., 35 figs

A study on sodium-concrete reaction

Energy Technology Data Exchange (ETDEWEB)

Bae, Jae Heum; Min, Byong Hun [Suwon University, Suwon (Korea, Republic of)

1997-07-01

A small sodium-concrete reaction facility was designed, manufactured and installed. this facility has been operated under inert gas(N{sub 2}) with different experimental variables such as sodium injection temperature, injection amount of sodium, aging period of concrete, sodium reservoir temperature. As a result, it was found that sodium injection temperature and injected amount of sodium has little effect on sodium-concrete reaction. However, sodium reservoir temperature and aging period of concrete has relatively high impact on sodium-concrete reaction. Sodium-concrete reaction model has also been developed and compared with experimental results. (Author) 51 refs., 16 tabs., 64 figs.

Soluble and meltable hyperbranched polyborosilazanes toward high-temperature stable SiBCN ceramics.

Science.gov (United States)

Kong, Jie; Wang, Minjun; Zou, Jianhua; An, Linan

2015-04-01

High-temperature stable siliconborocarbonitride (SiBCN) ceramics produced from single-source preceramic polymers have received increased attention in the last two decades. In this contribution, soluble and meltable polyborosilazanes with hyperbranched topology (hb-PBSZ) were synthesized via a convenient solvent-free, catalyst-free and one-pot A2 + B6 strategy, an aminolysis reaction of the A2 monomer of dichloromethylsilane and the B6 monomer of tris(dichloromethylsilylethyl)borane in the presence of hexamethyldisilazane. The amine transition reaction between the intermediates of dichlorotetramethyldisilazane and tri(trimethylsilylmethylchlorosilylethyl)borane led to the formation of dendritic units of aminedialkylborons rather than trialkylborons. The cross-linked hb-PBSZ precursors exhibited a ceramic yield higher 80%. The resultant SiBCN ceramics with a boron atomic composition of 6.0-8.5% and a representative formula of Si1B(0.19)C(1.21)N(0.39)O(0.08) showed high-temperature stability and retained their amorphous structure up to 1600 °C. These hyperbranched polyborosilazanes with soluble and meltable characteristics provide a new perspective for the design of preceramic polymers possessing advantages for high-temperature stable polymer-derived ceramics with complex structures/shapes.

Thermal reaction norms and the scale of temperature variation: latitudinal vulnerability of intertidal nacellid limpets to climate change.

Science.gov (United States)

Morley, Simon A; Martin, Stephanie M; Day, Robert W; Ericson, Jess; Lai, Chien-Houng; Lamare, Miles; Tan, Koh-Siang; Thorne, Michael A S; Peck, Lloyd S

2012-01-01

The thermal reaction norms of 4 closely related intertidal Nacellid limpets, Antarctic (Nacella concinna), New Zealand (Cellana ornata), Australia (C. tramoserica) and Singapore (C. radiata), were compared across environments with different temperature magnitude, variability and predictability, to test their relative vulnerability to different scales of climate warming. Lethal limits were measured alongside a newly developed metric of "duration tenacity", which was tested at different temperatures to calculate the thermal reaction norm of limpet adductor muscle fatigue. Except in C. tramoserica which had a wide optimum range with two break points, duration tenacity did not follow a typical aerobic capacity curve but was best described by a single break point at an optimum temperature. Thermal reaction norms were shifted to warmer temperatures in warmer environments; the optimum temperature for tenacity (T(opt)) increased from 1.0°C (N. concinna) to 14.3°C (C. ornata) to 18.0°C (an average for the optimum range of C. tramoserica) to 27.6°C (C. radiata). The temperature limits for duration tenacity of the 4 species were most consistently correlated with both maximum sea surface temperature and summer maximum in situ habitat logger temperature. Tropical C. radiata, which lives in the least variable and most predictable environment, generally had the lowest warming tolerance and thermal safety margin (WT and TSM; respectively the thermal buffer of CT(max) and T(opt) over habitat temperature). However, the two temperate species, C. ornata and C. tramoserica, which live in a variable and seasonally unpredictable microhabitat, had the lowest TSM relative to in situ logger temperature. N. concinna which lives in the most variable, but seasonally predictable microhabitat, generally had the highest TSMs. Intertidal animals live at the highly variable interface between terrestrial and marine biomes and even small changes in the magnitude and predictability of their

Theoretical estimation of adiabatic temperature rise from the heat flow data obtained from a reaction calorimeter

International Nuclear Information System (INIS)

Das, Parichay K.

2012-01-01

Highlights: ► This method for estimating ΔT ad (t) against time in a semi-batch reactor is distinctively pioneer and novel. ► It has established uniquely a direct correspondence between the evolution of ΔT ad (t) in RC and C A (t) in a semi-batch reactor. ► Through a unique reaction scheme, the independent effects of heat of mixing and reaction on ΔT ad (t) has been demonstrated quantitatively. ► This work will help to build a thermally safe corridor of a thermally hazard reaction. ► This manuscript, the author believes will open a new vista for further research in Adiabatic Calorimetry. - Abstract: A novel method for estimating the transient profile of adiabatic rise in temperature has been developed from the heat flow data for exothermic chemical reactions that are conducted in reaction calorimeter (RC). It has also been mathematically demonstrated by the present design that there exists a direct qualitative equivalence between the temporal evolution of the adiabatic temperature rise and the concentration of the limiting reactant for an exothermic chemical reaction, carried out in semi batch mode. The proposed procedure shows that the adiabatic temperature rise will always be less than that of the reaction executed at batch mode thereby affording a thermally safe corridor. Moreover, a unique reaction scheme has been designed to establish the independent heat effect of dissolution and reaction quantitatively. It is hoped that the testimony of the transient adiabatic temperature rise that can be prepared by the proposed method, may provide ample scope for further research.

The Effect of Temperature on the Enzyme-Catalyzed Reaction: Insights from Thermodynamics

Science.gov (United States)

Aledo, Juan Carlos; Jimenez-Riveres, Susana; Tena, Manuel

2010-01-01

When teaching the effect of temperature on biochemical reactions, the problem is usually oversimplified by confining the thermal effect to the catalytic constant, which is identified with the rate constant of the elementary limiting step. Therefore, only positive values for activation energies and values greater than 1 for temperature coefficients…

OH+ Formation in the Low-temperature O+(4S) + H2 Reaction

Science.gov (United States)

Kovalenko, Artem; Dung Tran, Thuy; Rednyk, Serhiy; Roučka, Štěpán; Dohnal, Petr; Plašil, Radek; Gerlich, Dieter; Glosík, Juraj

2018-04-01

Formation of OH+ in collisions of ground-state O+(4S) ions with normal H2 has been studied using a variable temperature 22-pole RF ion trap. From 300 to 30 K the measured reaction rate coefficient is temperature-independent, with a small decrease toward 15 K. The recent wave packet calculation predicts a slightly steeper temperature dependence. The rate coefficients at 300 and 15 K are almost the same, (1.4 ± 0.3) × 10‑9 cm3 s‑1 and (1.3 ± 0.3) × 10‑9 cm3 s‑1, respectively. The influence of traces of the two metastable ions, O+(2D) and O+(2P), has been examined by monitoring the H+ products of their reactions with H2, as well as by chemically probing them with N2 reactant gas.

Gravitropic reaction of primary seminal roots of Zea mays L. influenced by temperature and soil water potential.

Science.gov (United States)

Nakamoto, T

1995-03-01

The growth of the primary seminal root of maize (Zea mays L.) is characterized by an initial negative gravitropic reaction and a later positive one that attains a plagiotropic liminal angle. The effects of temperature and water potential of the surrounding soil on these gravitropic reactions were studied. Temperatures of 32, 25, and 18C and soil water potentials of -5, -38, and -67 kPa were imposed and the direction of growth was measured for every 1 cm length of the root. The initial negative gravitropic reaction extended to a distance of about 10 cm from the grain. Higher temperatures reduced the initial negative gravitropic reaction. Lower soil water potential induced a downward growth at root emergence. A mathematical model, in which it was assumed that the rate of the directional change of root growth was a sum of a time-dependent negative gravitropic reaction and an establishment of the liminal angle, adequately fitted the distance-angle relations. It was suggested that higher temperatures and/or a lower water potential accelerated the diminution of the initial negative gravitropic reaction.

Ab initio molecular dynamics study of thermite reaction at Al and CuO nano-interfaces at different temperatures

Science.gov (United States)

Tang, Cui-Ming; Chen, Xiao-Xu; Cheng, Xin-Lu; Zhang, Chao-Yang; Lu, Zhi-Peng

2018-05-01

The thermite reaction at Al/CuO nano-interfaces is investigated with ab initio molecular dynamics calculations in canonical ensemble at 500 K, 800 K, 1200 K and 1500 K, respectively. The reaction process and reaction products are analyzed in terms of chemical bonds, average charge, time constants and total potential energy. The activity of the reactants enhances with increasing temperature, which induces a faster thermite reaction. The alloy reaction obviously expands outward at Cu-rich interface of Al/CuO system, and the reaction between Al and O atoms obviously expands outward at O-rich interface as temperature increases. Different reaction products are found at the outermost layer of different interfaces in the Al/CuO system. In generally, the average charge of the outer layer aluminum atoms (i.e., Al1, Al2, Al5 and Al6) increases with temperature. The potential energy of Al/CuO system decreases significantly, which indicates that drastic exothermic reaction occurs at the Al/CuO system. This research enhances fundamental understanding in temperature effect on the thermite reaction at atomic level, which can potentially open new possibilities for its industrial application.

High-Temperature Piezoelectric Sensing

Directory of Open Access Journals (Sweden)

Xiaoning Jiang

2013-12-01

Full Text Available Piezoelectric sensing is of increasing interest for high-temperature applications in aerospace, automotive, power plants and material processing due to its low cost, compact sensor size and simple signal conditioning, in comparison with other high-temperature sensing techniques. This paper presented an overview of high-temperature piezoelectric sensing techniques. Firstly, different types of high-temperature piezoelectric single crystals, electrode materials, and their pros and cons are discussed. Secondly, recent work on high-temperature piezoelectric sensors including accelerometer, surface acoustic wave sensor, ultrasound transducer, acoustic emission sensor, gas sensor, and pressure sensor for temperatures up to 1,250 °C were reviewed. Finally, discussions of existing challenges and future work for high-temperature piezoelectric sensing are presented.

High Temperature Corrosion of Nickel in NaVO3-V2O5 Melts

Directory of Open Access Journals (Sweden)

J. Porcayo-Calderon

2017-01-01

Full Text Available Many alloys used at high temperature in industrial processes are Ni-based and many others contain it in appreciable quantities, so it is of interest to evaluate the performance of pure nickel in order to determine the behavior of its alloys once the elements responsible for their protection have been depleted due to accelerated corrosion processes in the presence of vanadium-rich molten salts. Due to this, this work presents the study of Ni behavior in NaVO3-V2O5 mixtures at different temperatures. The behavior of pure nickel was determined by both electrochemical and mass loss measurements. The results show that the aggressiveness of the vanadium salts is increased by increasing both the V2O5 content and temperature. V2O5 addition considerably increases the current densities of the anodic and cathodic reactions. The corrosion process of Ni is modified due to the presence of its corrosion products, and its presence increases the activation energy by at least one order of magnitude. Although nickel shows a high reactivity in vanadium-rich salts, its reaction products are highly stable and protect it from the corrosive medium because the corrosion reactions trap the vanadium and block the migration of nickel ions.

Temperature dependence of electrocatalytic and photocatalytic oxygen evolution reaction rates using NiFe oxide

KAUST Repository

Nurlaela, Ela; Shinagawa, Tatsuya; Qureshi, Muhammad; Dhawale, Dattatray Sadashiv; Takanabe, Kazuhiro

2016-01-01

The present work compares oxygen evolution reaction (OER) in electrocatalysis and photocatalysis in aqueous solutions using nanostructured NiFeOx as catalysts. The impacts of pH and reaction temperature on the electrocatalytic and photocatalytic OER

Analysis of final products from the liquid alkanes radiolysis at low dose, low temperature and high dose rate

International Nuclear Information System (INIS)

Tilquin, B.; Doncker, J. de.

1991-01-01

Yields of final products (dimers) from the radiolysis of n-hexane and 2,3-dimethylbutane are studied by capillary chromatographic techniques for trace analysis. Reaction of intermediates with the products, the alkane molecules or impurities, is reduced by using low dose (1 kGy), low temperature (195 K) and high dose rate (LINAC). Temperature is the most important experiment variable; by reducing the temperature, reactions with significant activation energies do not compete with radical-radical termination reactions. Products from LINAC radiolysis provide information about active species (reactive fragment, allylic radical...) which deserve a more detailed examination by direct methods [fr

Initiation Temperature for Runaway Tri-n-Butyl Phosphate/Nitric Acid Reaction

Energy Technology Data Exchange (ETDEWEB)

Rudisill, T.S.

2000-11-28

During a review of the H-Canyon authorization basis, Defense Nuclear Facility Safety Board (DNFSB) staff members questioned the margin of safety associated with a postulated tri-n-butyl phosphate (TBP)/nitric acid runaway reaction due to the inadvertent heating of a canyon tank containing greater than 3000 lbs (1362 kg) of TBP. The margin of safety was partially based on experiments and calculations performed by the Actinide Technology Section (ATS) to support deletion of indication of tank agitation as a Safety Class System. In the technical basis for deletion of this system, ATS personnel conservatively calculated the equilibrium temperature distribution of a canyon tank containing TBP and nitric acid layers which were inadvertently heated by a steam jet left on following a transfer. The maximum calculated temperature (128 degrees C) was compared to the minimum initiation temperature for a runaway reaction (greater than 130 degrees C) documented by experimental work in the mid 195 0s. In this work, the initiation temperature as a function of nitric acid concentration was measured for 0 and 20 wt percent dissolved solids. The DNFSB staff members were concerned that data for 0 wt percent dissolved solids were not conservative given the facts that data for 20 wt percent dissolved solids show initiation temperatures at or below 130 degrees C and H-Canyon solutions normally contained a small amount of dissolved solids.

Rate Coefficients of the Reaction of OH with Allene and Propyne at High Temperatures

KAUST Repository

Es-sebbar, Et-touhami

2016-09-28

Allene (H2C═C═CH2; a-C3H4) and propyne (CH3C≡CH; p-C3H4) are important species in various chemical environments. In combustion processes, the reactions of hydroxyl radicals with a-C3H4 and p-C3H4 are critical in the overall fuel oxidation system. In this work, rate coefficients of OH radicals with allene (OH + H2C═C═CH2 → products) and propyne (OH + CH3C≡CH → products) were measured behind reflected shock waves over the temperature range of 843–1352 K and pressures near 1.5 atm. Hydroxyl radicals were generated by rapid thermal decomposition of tert-butyl hydroperoxide ((CH3)3–CO–OH), and monitored by narrow line width laser absorption of the well-characterized R1(5) electronic transition of the OH A–X (0,0) electronic system near 306.7 nm. Results show that allene reacts faster with OH radicals than propyne over the temperature range of this study. Measured rate coefficients can be expressed in Arrhenius form as follows: kallene+OH(T) = 8.51(±0.03) × 10–22T3.05 exp(2215(±3)/T), T = 843–1352 K; kpropyne+OH(T) = 1.30(±0.07) × 10–21T3.01 exp(1140(±6)/T), T = 846–1335 K.

Catalyst evaluation for oxygen reduction reaction in concentrated phosphoric acid at elevated temperatures

Science.gov (United States)

Hu, Yang; Jiang, Yiliang; Jensen, Jens Oluf; Cleemann, Lars N.; Li, Qingfeng

2018-01-01

Phosphoric acid is the common electrolyte for high-temperature polymer electrolyte fuel cells (HT-PEMFCs) that have advantages such as enhanced CO tolerance and simplified heat and water management. The currently used rotating disk electrode technique is limited to tests in dilute solutions at low temperatures and hence is not suitable for catalyst evaluation for HT-PEMFCs. In this study, we have designed and constructed a half-cell setup to measure the intrinsic activities of catalysts towards the oxygen reduction reaction (ORR) in conditions close to HT-PEMFC cathodes. By optimization of the hydrophobic characteristics of electrodes and the catalyst layer thickness, ORR activities of typical Pt/C catalysts are successfully measured in concentrated phosphoric acid at temperatures above 100 °C. In terms of mass-specific activities, the catalyst exhibits about two times higher activity in the half-cell electrode than that observed in fuel cells, indicating the feasibility of the technique as well as the potential for further improvement of fuel cell electrode performance.

Low-temperature conversion of high-moisture biomass: Topical report, January 1984--January 1988

Energy Technology Data Exchange (ETDEWEB)

Sealock, L.J. Jr.; Elliott, D.C.; Butner, R.S.; Neuenschwander, G.G.

1988-10-01

Pacific Northwest Laboratory (PNL) is developing a low-temperature, catalytic process that converts high-moisture biomass feedstocks and other wet organic substances to useful gaseous and liquid fuels. The advantage of this process is that it works without the need for drying or dewatering the feedstock. Conventional thermal gasification processes, which require temperatures above 750/degree/C and air or oxygen for combustion to supply reaction heat, generally cannot utilize feedstocks with moisture contents above 50 wt %, as the conversion efficiency is greatly reduced as a result of the drying step. For this reason, anaerobic digestion or other bioconversion processes traditionally have been used for gasification of high-moisture feedstocks. However, these processes suffer from slow reaction rates and incomplete carbon conversion. 50 refs., 21 figs., 22 tabs.

Cationic Pd(II-catalyzed C–H activation/cross-coupling reactions at room temperature: synthetic and mechanistic studies

Directory of Open Access Journals (Sweden)

Takashi Nishikata

2016-05-01

Full Text Available Cationic palladium(II complexes have been found to be highly reactive towards aromatic C–H activation of arylureas at room temperature. A commercially available catalyst [Pd(MeCN4](BF42 or a nitrile-free cationic palladium(II complex generated in situ from the reaction of Pd(OAc2 and HBF4, effectively catalyzes C–H activation/cross-coupling reactions between aryl iodides, arylboronic acids and acrylates under milder conditions than those previously reported. The nature of the directing group was found to be critical for achieving room temperature conditions, with the urea moiety the most effective in promoting facile coupling reactions at an ortho C–H position. This methodology has been utilized in a streamlined and efficient synthesis of boscalid, an agent produced on the kiloton scale annually and used to control a range of plant pathogens in broadacre and horticultural crops. Mechanistic investigations led to a proposed catalytic cycle involving three steps: (1 C–H activation to generate a cationic palladacycle; (2 reaction of the cationic palladacycle with an aryl iodide, arylboronic acid or acrylate, and (3 regeneration of the active cationic palladium catalyst. The reaction between a cationic palladium(II complex and arylurea allowed the formation and isolation of the corresponding palladacycle intermediate, characterized by X-ray analysis. Roles of various additives in the stepwise process have also been studied.

Highly efficient high temperature electrolysis

DEFF Research Database (Denmark)

Hauch, Anne; Ebbesen, Sune; Jensen, Søren Højgaard

2008-01-01

High temperature electrolysis of water and steam may provide an efficient, cost effective and environmentally friendly production of H-2 Using electricity produced from sustainable, non-fossil energy sources. To achieve cost competitive electrolysis cells that are both high performing i.e. minimum...... internal resistance of the cell, and long-term stable, it is critical to develop electrode materials that are optimal for steam electrolysis. In this article electrolysis cells for electrolysis of water or steam at temperatures above 200 degrees C for production of H-2 are reviewed. High temperature...... electrolysis is favourable from a thermodynamic point of view, because a part of the required energy can be supplied as thermal heat, and the activation barrier is lowered increasing the H-2 production rate. Only two types of cells operating at high temperature (above 200 degrees C) have been described...

Fundamental study on temperature estimation of steam generator tubes at sodium-water reaction

International Nuclear Information System (INIS)

Furukawa, Tomohiro; Yoshida, Eiichi

2008-11-01

In case of the tube failure in the steam generator of the sodium cooled fast breeder reactor, its adjoined tubes are rapidly heated up by the chemical reaction between sodium and water/steam. And it is known that the tubes have the damage called 'wastage' by the disclosure steam jet. This research is a fundamental study based on the metallography about temperature estimation of the damaged tubes at the sodium-water reaction for the establishment of mechanism analysis technique of the behavior. In the examination, the material which gave the rapid thermal history which imitated sodium-water reaction was produced. And it was investigated whether the thermal history (i.e. maximum temperature and the holding time) of the samples could be presumed from the metallurgical examination of the samples. The major results are as follows: (1) The microstructure of the sample which was given the rapid thermal heating has reserved the influence of the maximum temperature and the time, and the structure can explain by referring to the equilibrium diagram and the continuous cooling transformation diagram. (2) Results of the electrolytic extraction of the samples, the ratio of the remained volume to the electrolyzed volume degreased with the increase of the maximum temperature and the time. Furthermore, it was observed the correlation between the remained volume of each element (Cr, Mo, Fe, V and Nb) and the thermal history. (3) It was obtained that the thermal history of the tubes damaged by sodium-water reaction might be able to be estimated from the metallurgical examinations. (author)

Free radical reaction characteristics of coal low-temperature oxidation and its inhibition method.

Science.gov (United States)

Li, Zenghua; Kong, Biao; Wei, Aizhu; Yang, Yongliang; Zhou, Yinbo; Zhang, Lanzhun

2016-12-01

Study on the mechanism of coal spontaneous combustion is significant for controlling fire disasters due to coal spontaneous combustion. The free radical reactions can explain the chemical process of coal at low-temperature oxidation. Electron spin resonance (ESR) spectroscopy was used to measure the change rules of the different sorts and different granularity of coal directly; ESR spectroscopy chart of free radicals following the changes of temperatures was compared by the coal samples applying air and blowing nitrogen, original coal samples, dry coal samples, and demineralized coal samples. The fragmentation process was the key factor of producing and initiating free radical reactions. Oxygen, moisture, and mineral accelerated the free radical reactions. Combination of the free radical reaction mechanism, the mechanical fragmentation leaded to the elevated CO concentration, fracturing of coal pillar was more prone to spontaneous combustion, and spontaneous combustion in goaf accounted for a large proportion of the fire in the mine were explained. The method of added diphenylamine can inhibit the self-oxidation of coal effectively, the action mechanism of diphenylamine was analyzed by free radical chain reaction, and this research can offer new method for the development of new flame retardant.

Wide temperature range (T = 295 K and 770-1305 K) study of the kinetics of the reactions HCO + NO and HCO + NO2 using frequency modulation spectroscopy.

Science.gov (United States)

Dammeier, J; Colberg, M; Friedrichs, G

2007-08-21

The rate constants for , HCO + NO --> HNO + CO, and , HCO + NO(2)--> products, have been measured at temperatures between 770 K modulation (FM) absorption spectroscopy. Kinetic simulations based on a comprehensive reaction mechanism showed that the rate constants for the title reactions could be sensitively extracted from the measured HCO profiles. The determined high temperature rate constants are k(1)(769-1307 K) = (7.1 +/- 2.7) x 10(12) cm(3) mol(-1) s(-1) and k(2)(804-1186 K) = (3.3 +/- 1.8) x 10(13) cm(3) mol(-1) s(-1). The room temperature values were found to be in very good agreement with existing literature data and show that both reactions are essentially temperature independent. The weak temperature dependence of can be explained by the interplay of a dominating direct abstraction pathway and a complex-forming mechanism. Both pathways yield the products HNO + CO. In contrast to , no evidence for a significant contribution of a direct high temperature abstraction channel was found for . Here, the observed temperature independent overall rate constant can be described by a complex-forming mechanism with several product channels. Detailed information on the strongly temperature dependent channel branching ratios is provided. Moreover, the high temperature rate constant of , OH + (CHO)(2), has been determined to be k(7) approximately 1.1 x 10(13) cm(3) mol(-1) s(-1).

Characterization and reaction behavior of ferrocyanide simulants and Hanford Site high-level ferrocyanide waste

International Nuclear Information System (INIS)

Jeppson, D.W.; Simpson, B.C.

1994-02-01

Nonradioactive waste simulants and initial ferrocyanide tank waste samples were characterized to assess potential safety concerns associated with ferrocyanide high-level radioactive waste stored at the Hanford Site in underground single-shell tanks (SSTs). Chemical, physical, thermodynamic, and reaction properties of the waste simulants were determined and compared to properties of initial samples of actual ferrocyanide wastes presently in the tanks. The simulants were shown to not support propagating reactions when subjected to a strong ignition source. The simulant with the greatest ferrocyanide concentration was shown to not support a propagating reaction that would involve surrounding waste because of its high water content. Evaluation of dried simulants indicated a concentration limit of about 14 wt% disodium mononickel ferrocyanide, below which propagating reactions could not occur in the ambient temperature bulk tank waste. For postulated localized hot spots where dried waste is postulated to be at an initial temperature of 130 C, a concentration limit of about 13 wt% disodium mononickel ferrocyanide was determined, below which propagating reactions could not occur. Analyses of initial samples of the presently stored ferrocyanide waste indicate that the waste tank ferrocyanide concentrations are considerably lower than the limit for propagation for dry waste and that the water content is near that of the as-prepared simulants. If the initial trend continues, it will be possible to show that runaway ferrocyanide reactions are not possible under present tank conditions. The lower ferrocyanide concentrations in actual tank waste may be due to tank waste mixing and/or degradation from radiolysis and/or hydrolysis, which may have occurred over approximately 35 years of storage

Development of an ozone high sensitive sensor working at ambient temperature

International Nuclear Information System (INIS)

Berger, F; Ghaddab, B; Sanchez, J B; Mavon, C

2011-01-01

Hybrid SnO 2 /SWNTs thin layer were deposited by using sol-gel process. Such sensitive layers showed very high performances for O 3 flow detection at ambient temperature. Limit sensitivity, lower than 21,5 ppb of O 3 in air has been reached by using these hybrid layers. Compared to usefull metal oxide sensors, the main advantage of the use of such hybrid layers, is that these devices enable the detection of O 3 traces at room temperature. The influence of sensor's working temperature is discussed and finally a reactional mechanism for the detection of O 3 is proposed.

In Situ formation of pentafluorophosphate benzimidazole anion stabilizes high-temperature performance of lithium-ion batteries

International Nuclear Information System (INIS)

Pradanawati, Sylvia Ayu; Wang, Fu-Ming; Rick, John

2014-01-01

Highlights: • A new pentafluorophosphate benzimidazole anion was formed by Lewis acid-base reaction. • This pentafluorophosphate benzimidazole anion is fabricated with the benzimidazole anion and PF 5 . • This pentafluorophosphate benzimidazole anion avoids the ominous side reactions that PF 5 reacts SEI to form LiF and HF at high temperature. • The additional pentafluorophosphate benzimidazole anion formation well maintains the battery performance at 60 °C measurement compares to the electrolyte only with contains the salt, LiPF 6 . - Abstract: Lithium salts play a critical role in initiating electrochemical reactions in Li-ion batteries. Single Li ions dissociate from bulk-salt and associate with carbonates to form a solid electrolyte interface (SEI) during the first charge-discharge of the battery. SEI formation and the chemical stability of salt must both be controlled and optimized to minimize irreversible reactions in SEI formation and to suppress the decomposition of the salt at high temperatures. This study synthesizes a new benzimidazole-based anion in the electrolyte. This anion, pentafluorophosphate benzimidazole, results from a Lewis acid-base reaction between the benzimidazole anion and PF 5 . The new pentafluorophosphate benzimidazole anion inhibits the decomposition of LiPF 6 by inhibiting PF 5 side reactions, which degrade the SEI, and lead to the formation of LiF and HF at high temperatures. In addition, the use of the pentafluorophosphate benzimidazole anion results in the formation of a modified SEI that is able to modify the battery's performance. Cyclic voltammetry, scanning electron microscopy, differential scanning calorimetry, electrochemical impedance spectroscopy, as well as charge-discharge and X-ray photoelectron spectroscopy measurements have been used to characterize the materials in this study. The formation of the pentafluorophosphate benzimidazole anion in the electrolyte caused a 14% decrease in the activation energy

Assessing the High Temperature, High Pressure Subsurface for Anaerobic Methane Oxidation

Science.gov (United States)

Harris, R. L.; Bartlett, D.; Byrnes, A. W.; Walsh, K. M.; Lau, C. Y. M.; Onstott, T. C.

2017-12-01

The anaerobic oxidation of methane (AOM) is an important sink in the global methane (CH4) budget. ANMEs are known to oxidize CH4 either independently or in consortia with bacteria, coupling the reduction of electron acceptors such as, SO42-, NO2-, NO3-, Mn4+, or Fe3+. To further constrain the contribution of AOM to the global CH4 budget, it is important to assess unexplored environments where AOM is thermodynamically possible such as the high pressure, high temperature deep biosphere. Provided plausible electron acceptor availability, increased temperature and pCH4 yield favorable Gibbs free energies for AOM reactions and the production of ATP (Fig. 1). To date, only sulfate-dependent AOM metabolism has been documented under high temperature conditions (50-72˚C), and AOM has not been assessed above 10.1 MPa. Given that ANMEs share close phylogenetic and metabolic heritage with methanogens and that the most heat-tolerant microorganism known is a barophilic methanogen, there possibly exist thermophilic ANMEs. Here we describe preliminary results from high pressure, high temperature stable isotope tracer incubation experiments on deep biosphere samples. Deep sub-seafloor sediments collected by IODP 370 from the Nankai Trough (257 - 865 m below seafloor) and deep fracture fluid from South Africa (1339 m below land surface) were incubated anaerobically in hydrostatic pressure vessels at 40 MPa in simulated in situ temperatures (40˚ - 80˚C). Sediments and fracture fluid were incubated in sulfate-free artificial seawater, a 2:98 13CH4:N2 headspace, and treated with one of the potential electron acceptors listed above in addition to kill and endogenous activity (i.e. no added electron acceptor) controls. Stable isotope analysis of dissolved inorganic carbon (DIC) suggests that AOM occurred within 60 days of incubation for all investigated electron acceptors and temperatures except 50˚C. Sulfate-dependent AOM rates are consistent with those previously reported in the

Temperature dependence of electrocatalytic and photocatalytic oxygen evolution reaction rates using NiFe oxide

KAUST Repository

Nurlaela, Ela

2016-01-25

The present work compares oxygen evolution reaction (OER) in electrocatalysis and photocatalysis in aqueous solutions using nanostructured NiFeOx as catalysts. The impacts of pH and reaction temperature on the electrocatalytic and photocatalytic OER kinetics were investigated. For electrocatalysis, a NiFeOx catalyst was hydrothermally decorated on Ni foam. In 1 M KOH solution, the NiFeOx electrocatalyst achieved 10 mA cm-2 at an overpotential of 260 mV. The same catalyst was decorated on the surface of Ta3N5 photocatalyst powder. The reaction was conducted in the presence of 0.1 M Na2S2O8 as a strong electron scavenger, thus likely leading to the OER being kinetically relevant. When compared with the bare Ta3N5, NiFeOx/Ta3N5 demonstrated a 5-fold improvement in photocatalytic activity in the OER under visible light irradiation, achieving a quantum efficiency of 24 % at 480 nm. Under the conditions investigated, a strong correlation between the electrocatalytic and photocatalytic performances was identified: an improvement in electrocatalysis corresponded with an improvement in photocatalysis without altering the identity of the materials. The rate change at different pH was likely associated with electrocatalytic kinetics that accordingly influenced the photocatalytic rates. The sensitivity of the reaction rates with respective to the reaction temperature resulted in an apparent activation energy of 25 kJ mol-1 in electrocatalysis, whereas that in photocatalysis was 16 kJ mol-1. The origin of the difference in these activation energy values is likely attributed to the possible effects of temperature on the individual thermodynamic and kinetic parameters of the reaction process. The work described herein demonstrates a method of “transferring the knowledge of electrocatalysis to photocatalysis” as a strong tool to rationally and quantitatively understand the complex reaction schemes involved in photocatalytic reactions.

Hadron--hadron reactions, high multiplicity

International Nuclear Information System (INIS)

Diebold, R.

1978-09-01

A coverage of results on high energy and high multiplicity hadron reactions, charm searches and related topics, ultrahigh energy events and exotic phenomena (cosmic rays), and the nuclear effects in high energy collisions and related topics is discussed. 67 references

High temperature materials and mechanisms

CERN Document Server

2014-01-01

The use of high-temperature materials in current and future applications, including silicone materials for handling hot foods and metal alloys for developing high-speed aircraft and spacecraft systems, has generated a growing interest in high-temperature technologies. High Temperature Materials and Mechanisms explores a broad range of issues related to high-temperature materials and mechanisms that operate in harsh conditions. While some applications involve the use of materials at high temperatures, others require materials processed at high temperatures for use at room temperature. High-temperature materials must also be resistant to related causes of damage, such as oxidation and corrosion, which are accelerated with increased temperatures. This book examines high-temperature materials and mechanisms from many angles. It covers the topics of processes, materials characterization methods, and the nondestructive evaluation and health monitoring of high-temperature materials and structures. It describes the ...

The effect of irradiation temperature on the non-enzymatic browning reaction in cooked rice

Energy Technology Data Exchange (ETDEWEB)

Lee, Ju-Woon [Radiation Application Research Division, Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, PO Box 1266, Jeongeup, Jeonbuk 580-185 (Korea, Republic of); Oh, Sang-Hee [Radiation Application Research Division, Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, PO Box 1266, Jeongeup, Jeonbuk 580-185 (Korea, Republic of); Kim, Jae-Hun [Radiation Application Research Division, Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, PO Box 1266, Jeongeup, Jeonbuk 580-185 (Korea, Republic of); Byun, Eui-Hong [Radiation Application Research Division, Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, PO Box 1266, Jeongeup, Jeonbuk 580-185 (Korea, Republic of); Ree Kim, Mee [Department of Food and Nutrition, Chungnam National University, Gung-Dong 220, Yuseong, Daejeon 305-764 (Korea, Republic of); Baek, Min [Atomic Energy Policy Division, Ministry of Science and Technology, Government Complex-Gwacheon, Kyunggi 427-715 (Korea, Republic of); Byun, Myung-Woo [Radiation Application Research Division, Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, PO Box 1266, Jeongeup, Jeonbuk 580-185 (Korea, Republic of)]. E-mail: mwbyun@kaeri.re.kr

2007-05-15

The effect of irradiation temperature on the non-enzymatic browning reaction in a sugar-glycine solution and cooked rice generated by gamma irradiation was evaluated in the present study. When the sugar-glycine solution and cooked rice were irradiated at room temperature, the browning reaction was dramatically increased during the post-irradiation period. In the case of irradiation at below the freezing point, the browning by irradiation was retarded during not only irradiation but also a post-irradiation period. The changes of the sugar profile, such as a sugar loss or reducing power of the irradiated sugar-glycine solution and the electron spin resonance signal intensity of the irradiated cooked rice were also decreased with lower irradiation temperature. The present results may suggest that the production of free radicals and a radiolysis product is inhibited during gamma irradiation in the frozen state and it may prevent the browning reaction generated by gamma irradiation from occurring.

The effect of irradiation temperature on the non-enzymatic browning reaction in cooked rice

International Nuclear Information System (INIS)

Lee, Ju-Woon; Oh, Sang-Hee; Kim, Jae-Hun; Byun, Eui-Hong; Ree Kim, Mee; Baek, Min; Byun, Myung-Woo

2007-01-01

The effect of irradiation temperature on the non-enzymatic browning reaction in a sugar-glycine solution and cooked rice generated by gamma irradiation was evaluated in the present study. When the sugar-glycine solution and cooked rice were irradiated at room temperature, the browning reaction was dramatically increased during the post-irradiation period. In the case of irradiation at below the freezing point, the browning by irradiation was retarded during not only irradiation but also a post-irradiation period. The changes of the sugar profile, such as a sugar loss or reducing power of the irradiated sugar-glycine solution and the electron spin resonance signal intensity of the irradiated cooked rice were also decreased with lower irradiation temperature. The present results may suggest that the production of free radicals and a radiolysis product is inhibited during gamma irradiation in the frozen state and it may prevent the browning reaction generated by gamma irradiation from occurring

Method for local temperature measurement in a nanoreactor for in situ high-resolution electron microscopy.

Science.gov (United States)

Vendelbo, S B; Kooyman, P J; Creemer, J F; Morana, B; Mele, L; Dona, P; Nelissen, B J; Helveg, S

2013-10-01

In situ high-resolution transmission electron microscopy (TEM) of solids under reactive gas conditions can be facilitated by microelectromechanical system devices called nanoreactors. These nanoreactors are windowed cells containing nanoliter volumes of gas at ambient pressures and elevated temperatures. However, due to the high spatial confinement of the reaction environment, traditional methods for measuring process parameters, such as the local temperature, are difficult to apply. To address this issue, we devise an electron energy loss spectroscopy (EELS) method that probes the local temperature of the reaction volume under inspection by the electron beam. The local gas density, as measured using quantitative EELS, is combined with the inherent relation between gas density and temperature, as described by the ideal gas law, to obtain the local temperature. Using this method we determined the temperature gradient in a nanoreactor in situ, while the average, global temperature was monitored by a traditional measurement of the electrical resistivity of the heater. The local gas temperatures had a maximum of 56 °C deviation from the global heater values under the applied conditions. The local temperatures, obtained with the proposed method, are in good agreement with predictions from an analytical model. Copyright © 2013 Elsevier B.V. All rights reserved.

High temperature refrigerator

International Nuclear Information System (INIS)

Steyert, W.A. Jr.

1978-01-01

A high temperature magnetic refrigerator is described which uses a Stirling-like cycle in which rotating magnetic working material is heated in zero field and adiabatically magnetized, cooled in high field, then adiabatically demagnetized. During this cycle the working material is in heat exchange with a pumped fluid which absorbs heat from a low temperature heat source and deposits heat in a high temperature reservoir. The magnetic refrigeration cycle operates at an efficiency 70% of Carnot

Theoretical study of chemical reaction effects on vertical oscillating plate with variable temperature

Directory of Open Access Journals (Sweden)

Muthucumaraswamy R.

2006-01-01

Full Text Available An exact solution to the flow of a viscous incompressible unsteady flow past an infinite vertical oscillating plate with variable temperature and mass diffusion is presented here, taking into account of the homogeneous chemical reaction of first-order. Both the plate temperature and the concentration level near the plate are raised linearly with respect to time. The dimensionless governing equations has been obtained by the Laplace transform method, when the plate is oscillating harmonically in its own plane. The effects of velocity and concentration are studied for different parameters like phase angle, chemical reaction parameter, thermal Grashof number, mass Grashof number, Schmidt number and time are studied. The solutions are valid only for small values of time t. It is observed that the velocity increases with decreasing phase angle ωt or chemical reaction parameter. .

Tantalum high-temperature oxidation kinetics

International Nuclear Information System (INIS)

Grigor'ev, Yu.M.; Sarkisyan, A.A.; Merzhanov, A.G.

1981-01-01

Kinetics of heat release and scale growth during tantalum oxidation within 650-1300 deg C temperature range in oxygen-containing media is investigated. Kinetic equations and temperature and pressure dependences of constants are ound Applicability of the kinetic Lorie mechanism for the description of the tantalum oxidation kinetics applicably to rapid-passing processes is shown. It is stated that the process rate (reaction ability) is determined by adsorption desorption factors on the external surface of the ''protective'' oxide for the ''linear'' oxidation stage [ru

Heat pump cycle by hydrogen-absorbing alloys to assist high-temperature gas-cooled reactor in producing hydrogen

International Nuclear Information System (INIS)

Satoshi, Fukada; Nobutaka, Hayashi

2010-01-01

A chemical heat pump system using two hydrogen-absorbing alloys is proposed to utilise heat exhausted from a high-temperature source such as a high-temperature gas-cooled reactor (HTGR), more efficiently. The heat pump system is designed to produce H 2 based on the S-I cycle more efficiently. The overall system proposed here consists of HTGR, He gas turbines, chemical heat pumps and reaction vessels corresponding to the three-step decomposition reactions comprised in the S-I process. A fundamental research is experimentally performed on heat generation in a single bed packed with a hydrogen-absorbing alloy that may work at the H 2 production temperature. The hydrogen-absorbing alloy of Zr(V 1-x Fe x ) 2 is selected as a material that has a proper plateau pressure for the heat pump system operated between the input and output temperatures of HTGR and reaction vessels of the S-I cycle. Temperature jump due to heat generated when the alloy absorbs H 2 proves that the alloy-H 2 system can heat up the exhaust gas even at 600 deg. C without any external mechanical force. (authors)

Temperature uniformity mapping in a high pressure high temperature reactor using a temperature sensitive indicator

NARCIS (Netherlands)

Grauwet, T.; Plancken, van der I.; Vervoort, L.; Matser, A.M.; Hendrickx, M.; Loey, van A.

2011-01-01

Recently, the first prototype ovomucoid-based pressure–temperature–time indicator (pTTI) for high pressure high temperature (HPHT) processing was described. However, for temperature uniformity mapping of high pressure (HP) vessels under HPHT sterilization conditions, this prototype needs to be

Experimental and Theoretical Study of Thermodynamics of the Reaction of Titania and Water at High Temperatures

Science.gov (United States)

Nguyen, Quynhgiao N.; Myers, Dwight L.; Jacobson, Nathan S.; Opila, Elizabeth J.

2014-01-01

The transpiration method was used to determine the volatility of titanium dioxide (TiO2) in water vapor-containing environments at temperatures between 1473 and 1673 K. Water contents ranged from 0 to 76 mole % in oxygen or argon carrier gases for 20 to 250 hr exposure times. Results indicate that oxygen is not a key contributor to volatilization and the primary reaction for volatilization in this temperature range is: TiO2(s) + H2O(g) = TiO(OH)2(g). Data were analyzed with both the second and third law methods to extract an enthalpy and entropy of formation. The geometry and vibrational frequencies of TiO(OH)2(g) were computed using B3LYP density functional theory, and the enthalpy of formation was computed using the coupled-cluster singles and doubles method with a perturbative correction for connected triple substitutions [CCSD(T)]. Thermal functions are calculated using both a structure with bent and linear hydroxyl groups. Calculated second and third heats show closer agreement with the linear hydroxyl group, suggesting more experimental and computational spectroscopic and structural work is needed on this system.

Effect of reaction temperature on structure and fluorescence properties of nitrogen-doped carbon dots

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yi [Key Laboratory of Interface Science and Engineering in Advanced Materials (Taiyuan University of Technology), Ministry of Education, Taiyuan 030024 (China); College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024 (China); Department of Chemistry and Chemical Engineering, Lyuliang University, Lyuliang 033001 (China); Research Center on Advanced Materials Science and Technology, Taiyuan University of Technology, Taiyuan 030024 (China); Wang, Yaling [Key Laboratory of Interface Science and Engineering in Advanced Materials (Taiyuan University of Technology), Ministry of Education, Taiyuan 030024 (China); Research Center on Advanced Materials Science and Technology, Taiyuan University of Technology, Taiyuan 030024 (China); Feng, Xiaoting [Key Laboratory of Interface Science and Engineering in Advanced Materials (Taiyuan University of Technology), Ministry of Education, Taiyuan 030024 (China); College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024 (China); Zhang, Feng [Key Laboratory of Interface Science and Engineering in Advanced Materials (Taiyuan University of Technology), Ministry of Education, Taiyuan 030024 (China); Research Center on Advanced Materials Science and Technology, Taiyuan University of Technology, Taiyuan 030024 (China); Yang, Yongzhen, E-mail: yyztyut@126.com [Key Laboratory of Interface Science and Engineering in Advanced Materials (Taiyuan University of Technology), Ministry of Education, Taiyuan 030024 (China); Research Center on Advanced Materials Science and Technology, Taiyuan University of Technology, Taiyuan 030024 (China); Liu, Xuguang, E-mail: liuxuguang@tyut.edu.cn [Key Laboratory of Interface Science and Engineering in Advanced Materials (Taiyuan University of Technology), Ministry of Education, Taiyuan 030024 (China); College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024 (China)

2016-11-30

Highlights: • Nitrogen-doped carbon dots (NCDs) from ammonia solution and citric acid were synthesized at different temperatures. • Quantum yield (QY) of NCDs depends largely on the amount of fluorescent polymer chains (FPC), more FPC gives higher QY. • The law of QY of NCDs first increase and then decrease with the reaction temperature increased is found and explained. • Nitrogen doping plays significant role in getting increased UV–vis absorption and QY. - Abstract: To investigate the effect of reaction temperature and nitrogen doping on the structure and fluorescence properties of carbon dots (CDs), six kinds of nitrogen-doped CDs (NCDs) were synthesized at reaction temperatures of 120, 140, 160, 180, 200 and 220 °C, separately, by using citric acid as carbon source and ammonia solution as nitrogen source. Nitrogen-free CDs (N-free CDs-180) was also prepared at 180 °C by using citric acid as the only carbon source for comparison. Results show that reaction temperature has obvious effect on carbonization degree, quantum yield (QY), ultraviolet-visible (UV–vis) absorption and photoluminescence (PL) spectra but less effect on functional groups, nitrogen doping degree and fluorescence lifetime of NCDs. Compared with N-free CDs-180, NCDs-180 possesses enchanced QY and longer fluorescence lifetime. Doping nitrogen has obvious effect on UV–vis absorption and PL spectra but less effect on particles sizes and carbonization degree. The formation mechanism of NCDs is explored: QY of NCDs depends largely on the number of fluorescent polymer chains (FPC), the competition between FPC formation on the surface of NCDs and carbon core growth leads to the change in number of FPC, and consequently to the NCDs with highest QY at appropriate hydrothermal temperature.

The influence of high temperatures on milk proteins

Directory of Open Access Journals (Sweden)

Maćej Ognjen D.

2002-01-01

Full Text Available High temperatures Induce certain changes in milk constituents, but the degree of these changes depends on both the temperature and time of heat treatment. The most pronounced changes take place in milk proteins. The forewarming of milk causes an increase in acidity, the precipitation of soluble Ca-phosphate, whey protein denaturation and coagulation, as well as the interaction with casein micelles, the Maillard browning reaction, the dephosphorylation of casein, the hydrolysis of casein micelles, changes in whey proteins, an extension of the rennet coagulation time and an exchange of the rheological properties of the acid and rennet casein gels, changes in the zeta-potential and casein micelle hydration, the interaction between the milk proteins and proteins of milk fat globule membrane.

Pycnonuclear 12C+12C reaction at zero temperature

International Nuclear Information System (INIS)

Gasques, L R; Beard, M; Chamon, L C; Wiescher, M

2005-01-01

We present pycnonuclear reaction calculations for a one-component ionic crystal at zero temperature considering different theoretical approaches. The rates depend directly on the determination of the astrophysical S-factor at low energies, which has been obtained through the barrier penetration formalism. A totally parameter-free model for the real part of the nuclear interaction has been employed in the calculation of 12 C+ 12 C fusion cross sections

High Temperature Polymers for use in Fuel Cells

Science.gov (United States)

Peplowski, Katherine M.

2004-01-01

NASA Glenn Research Center (GRC) is currently working on polymers for fuel cell and lithium battery applications. The desire for more efficient, higher power density, and a lower environmental impact power sources has led to interest in proton exchanges membrane fuels cells (PEMFC) and lithium batteries. A PEMFC has many advantages as a power source. The fuel cell uses oxygen and hydrogen as reactants. The resulting products are electricity, heat, and water. The PEMFC consists of electrodes with a catalyst, and an electrolyte. The electrolyte is an ion-conducting polymer that transports protons from the anode to the cathode. Typically, a PEMFC is operated at a temperature of about 80 C. There is intense interest in developing a fuel cell membrane that can operate at higher temperatures in the range of 80 C- 120 C. Operating the he1 cell at higher temperatures increases the kinetics of the fuel cell reaction as well as decreasing the susceptibility of the catalyst to be poisoned by impurities. Currently, Nafion made by Dupont is the most widely used polymer membrane in PEMFC. Nafion does not function well above 80 C due to a significant decrease in the conductivity of the membrane from a loss of hydration. In addition to the loss of conductivity at high temperatures, the long term stability and relatively high cost of Nafion have stimulated many researches to find a substitute for Nafion. Lithium ion batteries are popular for use in portable electronic devices, such as laptop computers and mobile phones. The high power density of lithium batteries makes them ideal for the high power demand of today s advanced electronics. NASA is developing a solid polymer electrolyte that can be used for lithium batteries. Solid polymer electrolytes have many advantages over the current gel or liquid based systems that are used currently. Among these advantages are the potential for increased power density and design flexibility. Automobiles, computers, and cell phones require

Synthesis of nano-sized amorphous boron powders through active dilution self-propagating high-temperature synthesis method

Energy Technology Data Exchange (ETDEWEB)

Wang, Jilin [The State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070 (China); Gu, Yunle [School of Material Science and Engineering, Wuhan Institute of Technology, Wuhan 430073 (China); Li, Zili [The State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070 (China); Wang, Weimin, E-mail: wangwm@hotmail.com [The State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070 (China); Fu, Zhengyi [The State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070 (China)

2013-06-01

Graphical abstract: Nano-sized amorphous boron powders were synthesized by active dilution self-propagating high-temperature synthesis (SHS) method. The effects of endothermic reaction rate, the possible chemical reaction mechanism and active dilution model for synthesis of the product were also discussed. Highlights: ► Nano-sized amorphous boron powders were synthesized by active dilution self-propagating high-temperature synthesis method. ► The morphology, particle size and purity of the samples could be effectively controlled via changing the endothermic rate. ► The diluter KBH{sub 4} played an important role in active dilution synthesis of amorphous nano-sized boron powders. ► The active dilution method could be further popularized and become a common approach to prepare various inorganic materials. - Abstract: Nano-sized amorphous boron powders were synthesized by active dilution self-propagating high-temperature synthesis (SHS) method at temperatures ranging from 700 °C to 850 °C in a SHS furnace using Mg, B{sub 2}O{sub 3} and KBH{sub 4} as raw materials. Samples were characterized by X-ray powder diffraction (XRD), Laser particle size analyzer, Fourier transform infrared spectra (FTIR), X-ray energy dispersive spectroscopy (EDX), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high-resolution transmission TEM (HRTEM). The boron powders demonstrated an average particle size of 50 nm with a purity of 95.64 wt.%. The diluter KBH{sub 4} played an important role in the active dilution synthesis of amorphous nano-sized boron powders. The effects of endothermic reaction rate, the possible chemical reaction mechanism and active dilution model for synthesis of the product were also discussed.

Synthesis of nano-sized amorphous boron powders through active dilution self-propagating high-temperature synthesis method

International Nuclear Information System (INIS)

Wang, Jilin; Gu, Yunle; Li, Zili; Wang, Weimin; Fu, Zhengyi

2013-01-01

Graphical abstract: Nano-sized amorphous boron powders were synthesized by active dilution self-propagating high-temperature synthesis (SHS) method. The effects of endothermic reaction rate, the possible chemical reaction mechanism and active dilution model for synthesis of the product were also discussed. Highlights: ► Nano-sized amorphous boron powders were synthesized by active dilution self-propagating high-temperature synthesis method. ► The morphology, particle size and purity of the samples could be effectively controlled via changing the endothermic rate. ► The diluter KBH 4 played an important role in active dilution synthesis of amorphous nano-sized boron powders. ► The active dilution method could be further popularized and become a common approach to prepare various inorganic materials. - Abstract: Nano-sized amorphous boron powders were synthesized by active dilution self-propagating high-temperature synthesis (SHS) method at temperatures ranging from 700 °C to 850 °C in a SHS furnace using Mg, B 2 O 3 and KBH 4 as raw materials. Samples were characterized by X-ray powder diffraction (XRD), Laser particle size analyzer, Fourier transform infrared spectra (FTIR), X-ray energy dispersive spectroscopy (EDX), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high-resolution transmission TEM (HRTEM). The boron powders demonstrated an average particle size of 50 nm with a purity of 95.64 wt.%. The diluter KBH 4 played an important role in the active dilution synthesis of amorphous nano-sized boron powders. The effects of endothermic reaction rate, the possible chemical reaction mechanism and active dilution model for synthesis of the product were also discussed

Fast screening of analytes for chemical reactions by reactive low-temperature plasma ionization mass spectrometry.

Science.gov (United States)

Zhang, Wei; Huang, Guangming

2015-11-15

Approaches for analyte screening have been used to aid in the fine-tuning of chemical reactions. Herein, we present a simple and straightforward analyte screening method for chemical reactions via reactive low-temperature plasma ionization mass spectrometry (reactive LTP-MS). Solution-phase reagents deposited on sample substrates were desorbed into the vapor phase by action of the LTP and by thermal desorption. Treated with LTP, both reagents reacted through a vapor phase ion/molecule reaction to generate the product. Finally, protonated reagents and products were identified by LTP-MS. Reaction products from imine formation reaction, Eschweiler-Clarke methylation and the Eberlin reaction were detected via reactive LTP-MS. Products from the imine formation reaction with reagents substituted with different functional groups (26 out of 28 trials) were successfully screened in a time of 30 s each. Besides, two short-lived reactive intermediates of Eschweiler-Clarke methylation were also detected. LTP in this study serves both as an ambient ionization source for analyte identification (including reagents, intermediates and products) and as a means to produce reagent ions to assist gas-phase ion/molecule reactions. The present reactive LTP-MS method enables fast screening for several analytes from several chemical reactions, which possesses good reagent compatibility and the potential to perform high-throughput analyte screening. In addition, with the detection of various reactive intermediates (intermediates I and II of Eschweiler-Clarke methylation), the present method would also contribute to revealing and elucidating reaction mechanisms. Copyright © 2015 John Wiley & Sons, Ltd.

Thermochemical heat storage for high temperature applications. A review

Energy Technology Data Exchange (ETDEWEB)

Felderhoff, Michael [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany); Urbanczyk, Robert; Peil, Stefan [Institut fuer Energie- und Umwelttechnik e.V. (IUTA), Duisburg (Germany)

2013-07-01

Heat storage for high temperature applications can be performed by several heat storage techniques. Very promising heat storage methods are based on thermochemical gas solid reactions. Most known systems are metal oxide/steam (metal hydroxides), carbon dioxide (metal carbonates), and metal/hydrogen (metal hydrides) systems. These heat storage materials posses high gravimetric and volumetric heat storage densities and because of separation of the reaction products and their storage in different locations heat losses can be avoided. The reported volumetric heat storage densities are 615, 1340 and 1513 [ kWh m{sup -3}] for calcium hydroxide Ca(OH){sub 2}, calcium carbonate CaCO{sub 3} and magnesium iron hydride Mg{sub 2}FeH{sub 6} respectively. Additional demands for gas storage decrease the heat storage density, but metal hydride systems can use available hydrogen storage possibilities for example caverns, pipelines and chemical plants. (orig.)

Thermal reaction norms and the scale of temperature variation: latitudinal vulnerability of intertidal nacellid limpets to climate change.

Directory of Open Access Journals (Sweden)

Simon A Morley

Full Text Available The thermal reaction norms of 4 closely related intertidal Nacellid limpets, Antarctic (Nacella concinna, New Zealand (Cellana ornata, Australia (C. tramoserica and Singapore (C. radiata, were compared across environments with different temperature magnitude, variability and predictability, to test their relative vulnerability to different scales of climate warming. Lethal limits were measured alongside a newly developed metric of "duration tenacity", which was tested at different temperatures to calculate the thermal reaction norm of limpet adductor muscle fatigue. Except in C. tramoserica which had a wide optimum range with two break points, duration tenacity did not follow a typical aerobic capacity curve but was best described by a single break point at an optimum temperature. Thermal reaction norms were shifted to warmer temperatures in warmer environments; the optimum temperature for tenacity (T(opt increased from 1.0°C (N. concinna to 14.3°C (C. ornata to 18.0°C (an average for the optimum range of C. tramoserica to 27.6°C (C. radiata. The temperature limits for duration tenacity of the 4 species were most consistently correlated with both maximum sea surface temperature and summer maximum in situ habitat logger temperature. Tropical C. radiata, which lives in the least variable and most predictable environment, generally had the lowest warming tolerance and thermal safety margin (WT and TSM; respectively the thermal buffer of CT(max and T(opt over habitat temperature. However, the two temperate species, C. ornata and C. tramoserica, which live in a variable and seasonally unpredictable microhabitat, had the lowest TSM relative to in situ logger temperature. N. concinna which lives in the most variable, but seasonally predictable microhabitat, generally had the highest TSMs. Intertidal animals live at the highly variable interface between terrestrial and marine biomes and even small changes in the magnitude and predictability of their

A green synthesis of a layered titanate, potassium lithium titanate; lower temperature solid-state reaction and improved materials performance

International Nuclear Information System (INIS)

Ogawa, Makoto; Morita, Masashi; Igarashi, Shota; Sato, Soh

2013-01-01

A layered titanate, potassium lithium titanate, with the size range from 0.1 to 30 µm was prepared to show the effects of the particle size on the materials performance. The potassium lithium titanate was prepared by solid-state reaction as reported previously, where the reaction temperature was varied. The reported temperature for the titanate preparation was higher than 800 °C, though 600 °C is good enough to obtain single-phase potassium lithium titanate. The lower temperature synthesis is cost effective and the product exhibit better performance as photocatalysts due to surface reactivity. - Graphical abstract: Finite particle of a layered titanate, potassium lithium titanate, was prepared by solid-state reaction at lower temperature to show modified materials performance. Display Omitted - Highlights: • Potassium lithium titanate was prepared by solid-state reaction. • Lower temperature reaction resulted in smaller sized particles of titanate. • 600 °C was good enough to obtain single phased potassium lithium titanate. • The product exhibited better performance as photocatalyst

Sugarcane bagasse gasification: Global reaction mechanism of syngas evolution

International Nuclear Information System (INIS)

Ahmed, I.I.; Gupta, A.K.

2012-01-01

Highlights: ► Gasification of sugarcane bagasse has been investigated using a semi batch reactor. ► Global reaction mechanism combining pyrolysis and gasification reactions is presented. ► High flow rates of syngas supported fragmentation and secondary reactions. ► CO flow rate increased at higher heating rates at the expense of CO 2 production. ► At high temperatures merger between pyrolysis and char gasification occurs. -- Abstract: Steam gasification of sugarcane bagasse has been investigated. A semi batch reactor with a fixed amount of sugarcane bagasse sample placed in steady flow of high temperature steam at atmospheric pressure has been used. The gasification of bagasse was examined at reactor and steam temperatures of 800, 900 and 1000 °C. The evolution of syngas flow rate and chemical composition has been monitored. The evolution of chemical composition and total flow rate of the syngas has been used to formulate a global reaction mechanism. The mechanism combines pyrolysis reaction mechanisms from the literature and steam gasification/reforming reactions. Steam gasification steps include steam–hydrocarbons reforming, char gasification and water gas shift reactions. Evidence of fragmentation, secondary ring opening reactions and tertiary reactions resulting in formation of gaseous hydrocarbons is supported by higher flow rates of syngas and hydrogen at high heating rates and high reactor temperatures. Increase in carbon monoxide flow rate at the expense of carbon dioxide flow rate with the increase in reactor temperature has been observed. This increase in the ratio of CO/CO 2 flow rate confirms the production of CO and CO 2 from the competing reaction routes. At 1000 °C gasification a total merging between the pyrolysis step and the char gasification step has been observed. This is attributed to acceleration of char gasification reactions and acceleration of steam–hydrocarbons reforming reactions. These hydrocarbons are the precursors to

Development of a high density fuel based on uranium-molybdenum alloys with high compatibility in high temperatures

International Nuclear Information System (INIS)

Oliveira, Fabio Branco Vaz de

2008-01-01

This work has as its objective the development of a high density and low enriched nuclear fuel based on the gamma-UMo alloys, for utilization where it is necessary satisfactory behavior in high temperatures, considering its utilization as dispersion. For its accomplishment, it was started from the analysis of the RERTR ('Reduced Enrichment for Research and Test Reactors') results and some theoretical works involving the fabrication of gamma-uranium metastable alloys. A ternary addition is proposed, supported by the properties of binary and ternary uranium alloys studied, having the objectives of the gamma stability enhancement and an ease to its powder fabrication. Alloys of uranium-molybdenum were prepared with 5 to 10% Mo addition, and 1 and 3% of ternary, over a gamma U7Mo binary base alloy. In all the steps of its preparation, the alloys were characterized with the traditional techniques, to the determination of its mechanical and structural properties. To provide a process for the alloys powder obtention, its behavior under hydrogen atmosphere were studied, in thermo analyser-thermo gravimeter equipment. Temperatures varied from the ambient up to 1000 deg C, and times from 15 minutes to 16 hours. The results validation were made in a semi-pilot scale, where 10 to 50 g of powders of some of the alloys studied were prepared, under static hydrogen atmosphere. Compatibility studies were conducted by the exposure of the alloys under oxygen and aluminum, to the verification of possible reactions by means of differential thermal analysis. The alloys were exposed to a constant heat up to 1000 deg C, and their performances were evaluated in terms of their reaction resistance. On the basis of the results, it was observed that ternary additions increases the temperatures of the reaction with aluminum and oxidation, in comparison with the gamma UMo binaries. A set of conditions to the hydration of the alloys were defined, more restrictive in terms of temperature, time and

Efficient dual layer interconnect coating for high temperature electrochemical devices

DEFF Research Database (Denmark)

Palcut, Marián; Mikkelsen, Lars; Neufeld, Kai

2012-01-01

Effects of novel dual layer coatings Co3O4/La0.85Sr0.15MnO3−δ on high temperature oxidation behaviour of candidate steels for interconnects are studied at 1123 K in flowing simulated ambient air (air + 1% H2O) and oxygen. Four alloys are investigated: Crofer 22 APU, Crofer 22 H, E-Brite and AL 29...... that the oxidation reaction is limited by outward Cr3+ diffusion in the chromia scale. The coating effectively reduces the oxidation rate. Reactions and cation inter-diffusion between the coating and the oxide scale are observed. Long term effects of these interactions are discussed and practical implications...

Patented Techniques for Acrylamide Mitigation in High-Temperature Processed Foods

DEFF Research Database (Denmark)

Mariotti, Salome; Pedreschi, Franco; Antonio Carrasco, José

2011-01-01

Heating foods has many advantages since it adds taste, color, texture and minimizes harmful germs, among others. Flavor and aroma compounds are produced via the Maillard reaction, where various hazardous com-pounds may form as well, such as acrylamide. Maillard reaction is believed to be the main...... for acrylamide reduction in foods processed at high temperatures are mentioned and briefly analyzed in order to develop new mitigation techniques for acrylamide in different food matrixes.......Heating foods has many advantages since it adds taste, color, texture and minimizes harmful germs, among others. Flavor and aroma compounds are produced via the Maillard reaction, where various hazardous com-pounds may form as well, such as acrylamide. Maillard reaction is believed to be the main...... route for acrylamide for-mation between reducing sugars (glucose and fructose), sucrose, and the amino acid asparagine, and, consequently, a variety of technologies have been developed to reduce acrylamide concentration in thermally processed foods based ei-ther on: (i) Changing process parameters (e...

A kinetic study of gaseous potassium capture by coal minerals in a high temperature fixed-bed reactor

DEFF Research Database (Denmark)

Zheng, Yuanjing; Jensen, Peter Arendt; Jensen, Anker Degn

2008-01-01

The reactions between gaseous potassium chloride and coal minerals were investigated in a lab-scale high temperature fixed-bed reactor using single sorbent pellets. The applied coal minerals included kaolin, mullite, silica, alumina, bituminous coal ash, and lignite coal ash that were formed...... into long cylindrical pellets. Kaolin and bituminous coal ash that both have significant amounts of Si and Al show superior potassium capture characteristics. Experimental results show that capture of potassium by kaolin is independent of the gas oxygen content. Kaolin releases water and forms metakaolin...... when heated at temperatures above 450°C. The amounts of potassium captured by metakaolin pellet decreases with increasing reaction temperature in the range of 900-1300°C and increases again with further increasing the temperature up to 1500°C. There is no reaction of pre-made mullite with KCl...

Hydrogen production from water gas shift reaction in a high gravity (Higee) environment using a rotating packed bed

Energy Technology Data Exchange (ETDEWEB)

Chen, Wei-Hsin; Syu, Yu-Jhih [Department of Greenergy, National University of Tainan, Tainan 700 (China)

2010-10-15

Hydrogen production via the water gas shift reaction (WGSR) was investigated in a high gravity environment. A rotating packed bed (RPB) reactor containing a Cu-Zn catalyst and spinning in the range of 0-1800 rpm was used to create high centrifugal force. The reaction temperature and the steam/CO ratio ranged from 250 to 350 C and 2 to 8, respectively. A dimensionless parameter, the G number, was derived to account for the effect of centrifugal force on the enhancement of the WGSR. With the rotor speed of 1800 rpm, the induced centrifugal force acting on the reactants was as high as 234 g on average in the RPB. As a result, the CO conversion from the WGSR was increased up to 70% compared to that without rotation. This clearly revealed that the centrifugal force was conducive to hydrogen production, resulting from intensifying mass transfer and elongating the path of the reactants in the catalyst bed. From Le Chatelier's principle, a higher reaction temperature or a lower steam/CO ratio disfavors CO conversion; however, under such a situation the enhancement of the centrifugal force on hydrogen production from the WGSR tended to become more significant. Accordingly, a correlation between the enhancement of CO conversion and the G number was established. As a whole, the higher the reaction temperature and the lower the steam/CO ratio, the higher the exponent of the G number function and the better the centrifugal force on the WGSR. (author)

The effect of addition of primary positive salts, complex salt, on the ionic strength and rate constant at various temperatures by reaction kinetics

Science.gov (United States)

Kurade, S. S.; Ramteke, A. A.

2018-05-01

In this work, we have investigated the rate of reaction by using ionic strength at different temperatures. The main goal of this experiment is to determine the relation between ionic strength with reaction rate, reaction time and rate constant with temperature. It is observed that the addition of positive salt indicate the increasing ionic strength with increase in run time at various temperatures. Thus the temperature affects the speed of reaction and mechanism by which chemical reaction occurs and time variable plays vital role in the progress of reaction at different temperatures.

Defect reactions on the phosphorus sublattice in low-temperature electron-irradiated InP

International Nuclear Information System (INIS)

Sibille, A.; Suski, J.

1985-01-01

This Rapid Communication describes several thermally or electronically stimulated defect reactions involving the dominant deep centers in low-temperature (25--300 K) electron-irradiated InP. Some of these reactions result in an increased concentration of the centers, thereby revealing the existence of a secondary production mechanism of the related defects. Low-energy irradiations allows one to select the type of the ejected atom (P) and gives direct evidence that only a phosphorus species, interstitial or vacancy, is involved in the creation-reaction-annealing events

Self-propagating high-temperature synthesis of TiC-WC composite materials

International Nuclear Information System (INIS)

Mas-Guindal, M.J.; Contreras, L.; Turrillas, X.; Vaughan, G.B.M.; Kvick, A.; Rodriguez, M.A.

2006-01-01

TiC-WC composites have been obtained in situ by self-propagating high-temperature synthesis (SHS) from a mixture of compacted powders of elemental titanium, tungsten and graphite. The Rietveld method has proved to be a useful tool to quantify the different phases in the reaction and calculate the cell parameters of the solid solution found in the products. The reaction has also been followed in real time by X-ray diffraction at the European Synchrotron Radiation Facility (ESRF ID-11 Materials Science Beamline). The mechanism of the reaction is discussed in terms of the diffusion of liquid titanium to yield titanium carbide with a solid solution of tungsten. The microstructures of the materials obtained by this method are presented

Room Temperature, Hybrid Sodium-Based Flow Batteries with Multi-Electron Transfer Redox Reactions

Science.gov (United States)

Shamie, Jack S.; Liu, Caihong; Shaw, Leon L.; Sprenkle, Vincent L.

2015-01-01

We introduce a new concept of hybrid Na-based flow batteries (HNFBs) with a molten Na alloy anode in conjunction with a flowing catholyte separated by a solid Na-ion exchange membrane for grid-scale energy storage. Such HNFBs can operate at ambient temperature, allow catholytes to have multiple electron transfer redox reactions per active ion, offer wide selection of catholyte chemistries with multiple active ions to couple with the highly negative Na alloy anode, and enable the use of both aqueous and non-aqueous catholytes. Further, the molten Na alloy anode permits the decoupled design of power and energy since a large volume of the molten Na alloy can be used with a limited ion-exchange membrane size. In this proof-of-concept study, the feasibility of multi-electron transfer redox reactions per active ion and multiple active ions for catholytes has been demonstrated. The critical barriers to mature this new HNFBs have also been explored. PMID:26063629

High temperature in operando and in situ spectroscopy on electrified surfaces and interfaces

DEFF Research Database (Denmark)

Chatzichristodoulou, Christodoulos; Hansen, Karin Vels; Holtappels, Peter

electrodes without contaminants have demanded a better insight into the electrode surface reactions and chemistries. Spectroscopic techniques can be applied to these cells but are still experimentally challenging due to the high temperature operation conditions. DTU Energy has in the recent years invested...

High temperature attack of ores by a liquor containing essentially a soluble bicarbonate

International Nuclear Information System (INIS)

Maurel, Pierre; Nicolas, Francois; Bosca, Bernard.

1978-01-01

New process for high temperature oxidizing digestion of ores containing at least one metal in the uranium, vanadium and molybdenum group, by an aqueous liquor containing sodium bicarbonate and sodium carbonate in the presence of free oxygen insufflated into the reaction medium [fr

The contact-temperature ignition (CTI) criteria for propagating chemical reactions including the effect of moisture and application to Hanford waste

International Nuclear Information System (INIS)

Cash, R.J.

1995-01-01

To assure the continued absence of uncontrolled condensed-phase chemical reactions in connection with the Hanford waste materials, efforts have been underway including both theoretical and experimental investigations to clarify the requirements for such reactions. This document defines the differences and requirements for homogeneous runaway and propagating chemical reactions incuding a discussion of general contact-temperature ignition (CTI) condition for propagating reactions that include the effect of moisture. The CTI condition implies that the contact temperature or interface temperature between reacted and unreacted materials must exceed the ignition temperature and is compared to experimental data including both synthetic ferrocyanide and surrogate organic materials. In all cases, the occurrences of ignition accompanied by self-propagating reactions are consistent with the theoretical anticipations of the CTI condition

Pyrolyzed feather fibers for adsorbent and high temperature applications

Science.gov (United States)

Senoz, Erman

Chicken feather fibers (CFF) are problematic and costly for the poultry industry in terms of managing maintenance and disposal. Considering their great availability, low cost, and unique protein structure, CFF can be an environmentally friendly and bio-renewable candidate to replace petroleum products. CFF's low degradation and melting temperature render them useless at high temperatures. Pyrolysis methods were developed for CFF by using two temperature steps to convert them into high temperature resistant and adsorbent fibers while retaining their original physical appearance and affine dimensions. An intermolecular crosslinking mechanism in the first step of pyrolysis at 215 ºC for 24 h provided an intact fibrous structure with no subsequent melting. The evidence obtained from the thermal, bulk, and surface analysis techniques was indication of the simultaneous side chain degradation, polypeptide backbone scission, disulfide bond cleavage, and isopeptide crosslinking. The variation in the reaction kinetics of disulfide bond cleavage and isopeptide crosslinking played an important role in the melting transition. Consequently, long-lasting heat treatments below the melting point provided sufficient crosslinks in the protein matrix to keep the fibrous structure intact. Water-insoluble and crosslinked CFF reinforced the triglyceride-fatty acid based composites by providing a 15 fold increase in storage and tensile modulus at room temperature. These thermally stable fibers can be used instead of CFF in composites which may require high temperature compounding and molding processes. The second step of pyrolysis at 400--450 ºC for 1 h resulted in microporous fibers with a micropore volume of ˜0.18 cm3/g STP and with a narrower pore size distribution than commercial activated carbons through thermal degradation. Nearly all accessible pores in the microporous pyrolyzed chicken feather fibers (PCFF) had diameters less than 1 nm and therefore, showed a potential to be

A Rechargeable High-Temperature Molten Salt Iron-Oxygen Battery.

Science.gov (United States)

Peng, Cheng; Guan, Chengzhi; Lin, Jun; Zhang, Shiyu; Bao, Hongliang; Wang, Yu; Xiao, Guoping; Chen, George Zheng; Wang, Jian-Qiang

2018-06-11

The energy and power density of conventional batteries are far lower than their theoretical expectations, primarily because of slow reaction kinetics that are often observed under ambient conditions. Here we describe a low-cost and high-temperature rechargeable iron-oxygen battery containing a bi-phase electrolyte of molten carbonate and solid oxide. This new design merges the merits of a solid-oxide fuel cell and molten metal-air battery, offering significantly improved battery reaction kinetics and power capability without compromising the energy capacity. The as-fabricated battery prototype can be charged at high current density, and exhibits excellent stability and security in the highly charged state. It typically exhibits specific energy, specific power, energy density, and power density of 129.1 Wh kg -1 , 2.8 kW kg -1 , 388.1 Wh L -1 , and 21.0 kW L -1 , respectively, based on the mass and volume of the molten salt. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Room temperature ferromagnetism in Eu-doped ZnO nanoparticulate powders prepared by combustion reaction method

International Nuclear Information System (INIS)

Franco, A.; Pessoni, H.V.S.; Soares, M.P.

2014-01-01

Nanoparticulate powders of Eu-doped ZnO with 1.0, 1.5, 2.0 and 3.0 at% Eu were synthesized by combustion reaction method using zinc nitrate, europium nitrate and urea as fuel without subsequent heat treatments. X-ray diffraction patterns (XRD) of all samples showed broad peaks consistent with the ZnO wurtzite structure. The absence of extra reflections in the diffraction patterns ensures the phase purity, except for x=0.03 that exhibits small reflection corresponding to Eu 2 O 3 phase. The average crystallite size determined from the most prominent (1 0 1) peak of the diffraction using Scherrer's equation was in good agreement with those determined by transmission electron microscopy (TEM); being ∼26 nm. The magnetic properties measurements were performed using a vibrating sample magnetometer (VSM) in magnetic fields up to 2.0 kOe at room temperature. The hysteresis loops, typical of magnetic behaviors, indicating that the presence of an ordered magnetic structure can exist in the Eu-doped ZnO wurtzite structure at room temperature. The room temperature ferromagnetism behavior increases with the Eu 3+ doping concentration. All samples exhibited the same Curie temperature (T C ) around ∼726 K, except for x=0.01; T C ∼643 K. High resolution transmission electron microscopy (HRTEM) images revealed defects/strain in the lattice and grain boundaries of Eu-doped ZnO nanoparticulate powders. The origin of room temperature ferromagnetism in Eu-doped ZnO nanoparticulate powders was discussed in terms of these defects, which increase with the Eu 3+ doping concentration. - Highlights: • Room-temperature ferromagnetism. • Structural and magnetic properties of nanoparticulate powders of Zn 1−x Eu x O. • Combustion reaction method

Effect of degree of polymerization and of temperature on the reactivity of poly(vinyl alcohol) by applying T-for-H exchange reaction

International Nuclear Information System (INIS)

Imaizumi, Hiroshi; Imai, Kazunari

1999-01-01

In order to reveal the effect of the degree of polymerization and of temperature on the reactivity of functional polymers, the hydrogen-isotope exchange reaction between poly(vinyl alcohol) (PVA) having each degree of polymerization and tritiated water vapor (HTO vapor) was dynamically observed at 35-80 deg C in a gas-solid system. The reason of the observation at 35 deg C is to clarify the possibility of the T-for-H exchange reaction at a temperature near the environment. The degree of polymerization of PVA used in this work was 500, 1000, 2000, 2800, or 3500. Applying the A''-McKay plot method to the data obtained in each observation, the rate constant (k) for each PVA in the reaction was calculated. Moreover, the Arrhenius plot for each PVA was made by using the k values. Comparing the k values and the results obtained previously, the following six matters have been clarified. In the temperature range of 35-80 deg C, the T-for-H exchange reaction between HTO vapor and each PVA occurred, and in this case, the atoms participating in the reaction are the H atoms in the OH groups in PVA and T atoms in HTO vapor. The reactivity of each PVA increases with rising temperature, and decreases with increasing the degree of polymerization. The rate of the decreasing of k with increasing the degree of polymerization changes at near the degree of polymerization of 1000, and the rate is fairly large under the degree of 1000. Under the degree of polymerization of 1000, the reactivity of PVA is more affected by the effect of the degree of polymerization than by the effect of temperature, and the reactivity is large when the degree of polymerization is small. Over the degree of polymerization of 1000, the reactivity of PVA is affected by both the degree of polymerization and temperature, and the reactivity is large when temperature is high. For the T-for-H exchange reaction in a gas-solid system, the reaction form is unchanged in the range of 35-80 deg C, and the reactivity at 35

Effect of temperature towards lipid oxidation and non-enzymatic browning reactions in krill oil upon storage

DEFF Research Database (Denmark)

Lu, Henna Fung Sieng; Bruheim, I.; Haugsgjerd, B.O.

2014-01-01

was assessed by peroxide value and anisidine value, measurement of lipid derived volatiles, lipid classes and antioxidants. The non-enzymatic browning reactions were assessed through the measurement of pyrroles, free amino acids content and Strecker-derived volatiles. The increase of incubation temperature......The main objective of this study was to investigate the effect of temperature towards lipid oxidation and non-enzymatic browning reactions in krill oil upon storage. Krill oil was incubated at two different temperatures (20 and 40°C) for 28 or 42 days. The oxidative stability of krill oil...

Nano-Scale Au Supported on Carbon Materials for the Low Temperature Water Gas Shift (WGS Reaction

Directory of Open Access Journals (Sweden)

Paula Sánchez

2011-12-01

Full Text Available Au-based catalysts supported on carbon materials with different structures such as graphite (G and fishbone type carbon nanofibers (CNF-F were prepared using two different methods (impregnation and gold-sol to be tested in the water gas shift (WGS reaction. Atomic absorption spectrometry, transmission electron microscopy (TEM, temperature-programmed oxidation (TPO, X-ray diffraction (XRD, Raman spectroscopy, elemental analyses (CNH, N2 adsorption-desorption analysis, temperature-programmed reduction (TPR and temperature-programmed decomposition were employed to characterize both the supports and catalysts. Both the crystalline nature of the carbon supports and the method of gold incorporation had a strong influence on the way in which Au particles were deposited on the carbon surface. The higher crystallinity and the smaller and well dispersed Au particle size were, the higher activity of the catalysts in the WGS reaction was noted. Finally, catalytic activity showed an important dependence on the reaction temperature and steam-to-CO molar ratio.

Reaction OH + OH studied over the 298-834 K temperature and 1-100 bar pressure ranges.

Science.gov (United States)

Sangwan, Manuvesh; Chesnokov, Evgeni N; Krasnoperov, Lev N

2012-06-21

Self-reaction of hydroxyl radicals, OH + OH → H(2)O + O (1a) and OH + OH → H(2)O(2) (1b), was studied using pulsed laser photolysis coupled to transient UV-vis absorption spectroscopy over the 298-834 K temperature and 1-100 bar pressure ranges (bath gas He). A heatable high-pressure flow reactor was employed. Hydroxyl radicals were prepared using reaction of electronically excited oxygen atoms, O((1)D), produced in photolysis of N(2)O at 193 nm, with H(2)O. The temporal behavior of OH radicals was monitored via transient absorption of light from a dc discharge in H(2)O/Ar low-pressure resonance lamp at ca. 308 nm. The absolute intensity of the photolysis light was determined by accurate in situ actinometry based on the ozone formation in the presence of molecular oxygen. The results of this study combined with the literature data indicate that the rate constant of reaction 1a, associated with the pressure independent component, decreases with temperature within the temperature range 298-414 K and increases above 555 K. The pressure dependent rate constant for (1b) was parametrized using the Troe expression as k(1b,inf) = (2.4 ± 0.6) × 10(-11)(T/300)(-0.5) cm(3) molecule(-1) s(-1), k(1b,0) = [He] (9.0 ± 2.2) × 10(-31)(T/300)(-3.5±0.5) cm(3) molecule(-1) s(-1), F(c) = 0.37.

Effect of reaction temperature on the PM10 features during coal combustion

International Nuclear Information System (INIS)

Sui, J.C.; Du, Y.G.; Liu, Q.C.

2008-01-01

Coal-fired power plants produce fine fly ash consisting of particulate matter (PM). Particulate matter less than 10 micrometers in aerodynamic diameter (PM 1 0) is of significant concern because of its adverse environmental and health impacts. This paper studied the effect of reaction temperature on particulate matter (PM 1 0) emission and its chemical composition. The emission characteristics and elemental partition of PM 1 0 from coal combustion were investigated in a drop tube furnace. The paper discussed the experimental apparatus and conditions as well as the coal properties and sample analysis. Liupanshui (LPS) bituminous coal from China was used for the study. The fuel composition of LPS coal and the composition of low temperature ash of Chinese LPS coal were described. The paper also presented the results of the study with reference to particle size distribution and emission characteristic of PM 1 0; elemental partition within PM 1 0; and effect of the reaction temperature on elemental partition within PM 1 0. The PM mass size distribution was found to be bimodal. 14 refs., 2 tabs., 6 figs

Temperature influence on the reaction kinetics of V(IV)/V(V) in methanesulfonic acid for all-vanadium redox flow battery

International Nuclear Information System (INIS)

Wang, Qiuhong; Daoud, Walid A.

2016-01-01

Highlights: • Diffusion coefficients and standard rate constants of V(IV) and V(V) in MSA at different temperatures are studied. • Carbon-based and metal electrodes are investigated under the same experimental condition at high temperature. • The influence of temperature on reaction kinetics is more significant on carbon-based electrode than metal electrode. • Gold electrode shows inefficient performance in MSA solution. - Abstract: In this study, methanesulfonic acid has been investigated as the supporting electrolyte for vanadium solutions due to the improvement of mass transfer rate and reaction kinetics. Here, we applied different temperatures (0–55 °C) for electrochemical experiments of 0.1 M vanadium ions in 1.0 M MSA electrolyte on gold, platinum and glassy carbon electrodes separately to study the temperature-related kinetics. Considering that electron transfer is the control path for the whole reduction potential window, the rotating disc electrode approach was utilized for the oxidation of V(IV) ions, while the reduction of V(V) ions was studied by cyclic voltammetry. The influence of temperature on charge-transfer resistance and mass transport for both V(IV) and V(V) solutions was studied by electrochemical impedance spectroscopy on glassy carbon electrode. The results showed that the diffusion coefficients in both redox reactions on all electrodes increased with temperature, and most were in the order of 10 −6 cm 2 s −1 . The positive influence of temperature was also observed on the standard rate constants for all conditions in this study, most significantly on the glassy carbon electrode. Comparison between glassy carbon electrode and metal electrodes indicates a promising potential of carbon-based material as electrode for redox flow battery.

Aseismic study of high temperature gas-cooled reactor core with block-type fuel, 3

International Nuclear Information System (INIS)

Ikushima, Takeshi; Honma, Toshiaki.

1985-01-01

A two-dimensional horizontal seismic experiment with single axis and simultaneous two-axes excitations was performed to obtain the core seismic design data on the block-type high temperature gas-cooled reactor. Effects of excitation directions and core side support stiffness on characteristics of core displacements and reaction forces of support were revealed. The values of the side reaction forces are the largest in the excitation of flat-to-flat of hexagonal block. Preload from the core periphery to the core center are effective to decrease core displacements and side reaction forces. (author)

Direct measurements of rate constants for the reactions of CH3 radicals with C2H6, C2H4, and C2H2 at high temperatures.

Science.gov (United States)

Peukert, S L; Labbe, N J; Sivaramakrishnan, R; Michael, J V

2013-10-10

The shock tube technique has been used to study the reactions CH3 + C2H6 → C2H4 + CH4 + H (1), CH3 + C2H4 → Products + H (2), and CH3 + C2H2 → Products + H (3). Biacetyl, (CH3CO)2, was used as a clean high temperature thermal source for CH3-radicals for all the three reactions studied in this work. For reaction 1, the experiments span a T-range of 1153 K ≤ T ≤ 1297 K, at P ~ 0.4 bar. The experiments on reaction 2 cover a T-range of 1176 K ≤ T ≤ 1366 K, at P ~ 1.0 bar, and those on reaction 3 a T-range of 1127 K ≤ T ≤ 1346 K, at P ~ 1.0 bar. Reflected shock tube experiments performed on reactions 1-3, monitored the formation of H-atoms with H-atom Atomic Resonance Absorption Spectrometric (ARAS). Fits to the H-atom temporal profiles using an assembled kinetics model were used to make determinations for k1, k2, and k3. In the case of C2H6, the measurements of [H]-atoms were used to derive direct high-temperature rate constants, k1, that can be represented by the Arrhenius equation k1(T) = 5.41 × 10(-12) exp(-6043 K/T) cm(3) molecules(-1) s(-1) (1153 K ≤ T ≤ 1297 K) for the only bimolecular process that occurs, H-atom abstraction. TST calculations based on ab initio properties calculated at the CCSD(T)/CBS//M06-2X/cc-pVTZ level of theory show excellent agreement, within ±20%, of the measured rate constants. For the reaction of CH3 with C2H4, the present rate constant results, k2', refer to the sum of rate constants, k(2b) + k(2c), from two competing processes, addition-elimination, and the direct abstraction CH3 + C2H4 → C3H6 + H (2b) and CH3 + C2H4 → C2H2 + H + CH4 (2c). Experimental rate constants for k2' can be represented by the Arrhenius equation k2'(T) = 2.18 × 10(-10) exp(-11830 K/T) cm(3) molecules(-1) s(-1) (1176 K ≤ T ≤ 1366 K). The present results are in excellent agreement with recent theoretical predictions. The present study provides the only direct measurement for the high-temperature rate constants for these channels

The [sup 26]Al(p,[gamma])[sup 27]Si reaction at low stellar temperature

Energy Technology Data Exchange (ETDEWEB)

Champagne, A E [North Carolina Univ., Chapel Hill, NC (United States). Dept. of Physics and Astronomy Duke Univ., Durham, NC (United States). Triangle Universities Nuclear Lab.; Brown, B A [Michigan State Univ., East Lansing, MI (United States). Dept. of Physics and Astronomy Michigan State Univ., East Lansing, MI (United States). National Superconducting Cyclotron Lab.; Sherr, R [Princeton Univ., NJ (United States). Dept. of Physics

1993-05-03

Shell-model calculations have been used to predict the locations of states in [sup 27]Si which are analogous to well-studied states in [sup 27]Al. From this, we have determined the resonance properties of the known states in [sup 27]Si near the [sup 26]Al+p threshold. The resulting thermonuclear reaction rate is uncertain by about a factor of ten at low temperatures, but it appears that the [sup 26]Al(p, [gamma])[sup 27]Si reaction is too slow to destroy a significant amount of [sup 26]Al at these temperatures. (orig.)

Low-temperature (75 °C) solid-state reaction enhanced by less-crystallized nanoporous PbI{sub 2} films for efficient CH{sub 3}NH{sub 3}PbI{sub 3} perovskite solar cells

Energy Technology Data Exchange (ETDEWEB)

Zheng, Huifeng [State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050 (China); University of Chinese Academy of Sciences, 19 Yuquan Road, Beijing 100049 (China); Liu, Yangqiao, E-mail: yqliu@mail.sic.ac.cn [State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050 (China); Suzhou Institute of SICCAS (Shanghai Institute of Ceramics, Chinese Academy of Sciences), 238 North Changchun Road, Taicang 215499, Jiangsu Province (China); Sun, Jing, E-mail: jingsun@mail.sic.ac.cn [State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050 (China)

2017-05-31

Highlights: • Efficient perovskite solar cells were prepared with solid-state reaction at 75 °C. • Ln-PbI{sub 2} is superior to c-PbI{sub 2} when applied in low-temperature solid-state reaction. • A higher champion PCE was obtained at 75 °C (13.8%) than that of 140 °C (11.8%). • Non-radiative defects increase significantly when annealed at high temperature. - Abstract: Organohalide perovskite films are usually prepared with the solid-state reaction at a high temperature ≥100 °C, which causes the increase of non-radiative defects and decomposition of perovskite films. Here, we demonstrate it’s feasible to prepare high-quality perovskite films with the solid-state reaction method even at a temperature of 75 °C, when enhanced by less-crystallized nanoporous PbI{sub 2} (ln-PbI{sub 2}) films. The replacement of compact PbI{sub 2} (c-PbI{sub 2}) by ln-PbI{sub 2}, results in a significant improvement of crystallinity of perovskite films, besides the elimination of remnant PbI{sub 2}. As a result, ln-PbI{sub 2} based perovskite solar cells display much higher power conversion efficiency (PCE) and better stability. Moreover, annealing duration was found to be critical for high PCE and was optimized as 60 min. Finally, with the optimal process, the champion device displayed a PCE of 13.8% and the average PCE reached 10.1% with a satisfactory deviation. Furthermore, we found annealing at high temperature (140 °C) led to a lower PCE compared with that annealed at 75 °C, because non-radiative defects increased significantly during high-temperature annealing. This work may open up a promising avenue for preparing high-quality perovskite films with the low-temperature solid-state reaction method, which is desirable for real application.

Room-temperature and temperature-dependent QSRR modelling for predicting the nitrate radical reaction rate constants of organic chemicals using ensemble learning methods.

Science.gov (United States)

Gupta, S; Basant, N; Mohan, D; Singh, K P

2016-07-01

Experimental determinations of the rate constants of the reaction of NO3 with a large number of organic chemicals are tedious, and time and resource intensive; and the development of computational methods has widely been advocated. In this study, we have developed room-temperature (298 K) and temperature-dependent quantitative structure-reactivity relationship (QSRR) models based on the ensemble learning approaches (decision tree forest (DTF) and decision treeboost (DTB)) for predicting the rate constant of the reaction of NO3 radicals with diverse organic chemicals, under OECD guidelines. Predictive powers of the developed models were established in terms of statistical coefficients. In the test phase, the QSRR models yielded a correlation (r(2)) of >0.94 between experimental and predicted rate constants. The applicability domains of the constructed models were determined. An attempt has been made to provide the mechanistic interpretation of the selected features for QSRR development. The proposed QSRR models outperformed the previous reports, and the temperature-dependent models offered a much wider applicability domain. This is the first report presenting a temperature-dependent QSRR model for predicting the nitrate radical reaction rate constant at different temperatures. The proposed models can be useful tools in predicting the reactivities of chemicals towards NO3 radicals in the atmosphere, hence, their persistence and exposure risk assessment.

Reaction F + C2H4: Rate Constant and Yields of the Reaction Products as a Function of Temperature over 298-950 K.

Science.gov (United States)

Bedjanian, Yuri

2018-03-29

The kinetics and products of the reaction of F + C 2 H 4 have been studied in a discharge flow reactor combined with an electron impact ionization mass spectrometer at nearly 2 Torr total pressure of helium in the temperature range 298-950 K. The total rate constant of the reaction, k 1 = (1.78 ± 0.30) × 10 -10 cm 3 molecule -1 s -1 , determined under pseudo-first-order conditions, monitoring the kinetics of F atom consumption in excess of C 2 H 4 , was found to be temperature independent in the temperature range used. H, C 2 H 3 F, and HF were identified as the reaction products. Absolute measurements of the yields of these species allowed to determine the branching ratios, k 1b / k 1 = (0.73 ± 0.07) exp(-(425 ± 45)/ T) and k 1a / k 1 = 1 - (0.73 ± 0.07) exp(-(425 ± 45)/ T) and partial rate constants for addition-elimination (H + C 2 H 3 F) and H atom abstraction (HF + C 2 H 3 ) pathways of the title reaction: k 1a = (0.80 ± 0.07) × 10 -10 exp(189 ± 37/ T) and k 1b = (1.26 ± 0.13) × 10 -10 exp(-414 ± 45/ T) cm 3 molecule -1 s -1 , respectively, at T = 298-950 K and with 2σ quoted uncertainties. The overall reaction rate constant can be adequately described by both the temperature independent value and as a sum of k 1a and k 1b . The kinetic and mechanistic data from the present study are discussed in comparison with previous absolute and relative measurements and theoretical calculations.

Generation of Hydrogen and Methane during Experimental Low-Temperature Reaction of Ultramafic Rocks with Water

Science.gov (United States)

McCollom, Thomas M.; Donaldson, Christopher

2016-06-01

Serpentinization of ultramafic rocks is widely recognized as a source of molecular hydrogen (H2) and methane (CH4) to support microbial activity, but the extent and rates of formation of these compounds in low-temperature, near-surface environments are poorly understood. Laboratory experiments were conducted to examine the production of H2 and CH4 during low-temperature reaction of water with ultramafic rocks and minerals. Experiments were performed by heating olivine or harzburgite with aqueous solutions at 90°C for up to 213 days in glass bottles sealed with butyl rubber stoppers. Although H2 and CH4 increased steadily throughout the experiments, the levels were very similar to those found in mineral-free controls, indicating that the rubber stoppers were the predominant source of these compounds. Levels of H2 above background were observed only during the first few days of reaction of harzburgite when CO2 was added to the headspace, with no detectable production of H2 or CH4 above background during further heating of the harzburgite or in experiments with other mineral reactants. Consequently, our results indicate that production of H2 and CH4 during low-temperature alteration of ultramafic rocks may be much more limited than some recent experimental studies have suggested. We also found no evidence to support a recent report suggesting that spinels in ultramafic rocks may stimulate H2 production. While secondary silicates were observed to precipitate during the experiments, formation of these deposits was dominated by Si released by dissolution of the glass bottles, and reaction of the primary silicate minerals appeared to be very limited. While use of glass bottles and rubber stoppers has become commonplace in experiments intended to study processes that occur during serpentinization of ultramafic rocks at low temperatures, the high levels of H2, CH4, and SiO2 released during heating indicate that these reactor materials are unsuitable for this purpose.

Low-Cost Temperature Logger for a Polymerase Chain Reaction Thermal Cycler

Directory of Open Access Journals (Sweden)

Chan-Young Park

2016-10-01

Full Text Available Polymerase chain reaction (PCR is a method of amplifying DNA which is normally carried out with a thermal cycler. To obtain more accurate and reliable PCR results, the temperature change within the chamber of the thermal cycler needs to be verified and calibrated regularly. Commercially available temperature loggers commonly used for temperature verification tests usually require a graphical user interface (GUI attached to the logger for convenience and straightforward understanding of the device. In this study, a host-local architecture for the temperature logger that significantly reduces the development time and cost is proposed. Employing standard computing devices as the host gives better development environment and user-friendly GUI. This paper presents the hardware and software design of the host-local temperature logger, and demonstrates the use of the local temperature logger connected to a personal computer with a Windows operating system. The probe design, thermistor resistance measurement, temperature filtering, and temperature calibration is described in detail. The thermistor self-heating problem was investigated in particular to determine the reference resistor that was serially connected to the thermistor. The temperature accuracy and temporal precision of the proposed system was 0.1 K.

Alternate applications of fusion power: development of a high-temperature blanket for synthetic-fuel production

International Nuclear Information System (INIS)

Howard, P.A.; Mattas, R.F.; Krajcinovic, D.; DePaz, J.; Gohar, Y.

1981-11-01

This study has shown that utilization of the unique features of a fusion reactor can result in a novel and potentially economical method of decomposing steam into hydrogen and oxygen. Most of the power of fusion reactors is in the form of energetic neutrons. If this power could be used to produce high temperature uncontaminated steam, a large fraction of the energy needed to decomposee the steam could be supplied as thermal energy by the fusion reaction. Proposed high temperature electrolysis processes require steam temperature in excess of 1000 0 C for high efficiency. The design put forth in this study details a system that can accomplish that end

Reaction of tellurium with Zircaloy-4

International Nuclear Information System (INIS)

Boer, R. de; Cordfunke, E.H.P.

1994-09-01

Interaction of tellurium vapour with Zircaloy during the initial stage of an accident will lead to retention of tellurium in the core. For reliable estimation of the release behaviour of tellurium, it is necessary to know which zirconium tellurides are formed during this interaction. In this work the reaction of tellurium with Zircaloy-4 has been studied, using various reaction temperatures and tellurium vapour pressures. The compound ZrTe 2-x is formed on the surface of the Zircaloy in a broad range of reaction temperatures and vapour pressures. It is found that the formation of the more zirconium-rich compound Zr 5 Te 4 is favoured at high reaction temperatures is combination with low tellurium vapour pressures. (orig.)

The high temperature oxidation behaviour of austenitic stainless steels

International Nuclear Information System (INIS)

Hales, R.

1977-04-01

High temperature annealing in a dynamic vacuum has been utilised to induce the growth of duplex oxide over the whole surface of stainless steel specimens. It is found that duplex oxide grows at a rate which does not obey a simple power law. The oxidation kinetics and oxide morphology have also been studied for a series of ternary austenitic alloys which cover a range of composition between 5 and 20% chromium. A model has been developed to describe the formation of duplex oxide and the subsequent formation of a 'healing layer' which virtually causes the oxidation process to stop. This phase tends to form at grain boundaries and a relationship has been derived for the reaction kinetics which relates the reaction rate with grain size of the substrate. (author)

Phosphoric acid doped AB-PBI membranes and its applications in high temperature PEMFC

DEFF Research Database (Denmark)

He, Ronghuan; Qingfeng, Li; Bjerrum, Niels

2005-01-01

Poly(2,5-benzimidazole) (ab-PBI) was prepared from 3，4-diaminobenzoic acid via a polymerisation reaction. The obtained polymer exhibits excellent thermal stability in a temperature range ….. The membrane of ab-PBI when doped with phosphoric acid at room temperaturepresents high proton conductivity...

A novel rate of the reaction between NaOH with CO2 at low temperature in spray dryer

Directory of Open Access Journals (Sweden)

Yadollah Tavan

2017-03-01

Full Text Available Carbon dioxide (CO2 is an influential greenhouse gas that has a significant impact on global warming partly. Nowadays, many techniques are available to control and remove CO2 in different chemical processes. Since the spray dryer has high removal efficiency rate, a laboratory-scale spray dryer is used to absorb carbon dioxide from air in aqueous solution of NaOH. In the present study, the impact of NaOH concentration, operating temperature and nozzle diameter on removal efficiency of CO2 is explored through experimental study. Moreover, the reaction kinetic of NaOH with CO2 is studied over the temperature range of 50–100 °C in a laboratory-scale spray dryer absorber. In the present contribution, a simple reaction rate equation is proposed that shows the lowest deviation from the experimental data with error less than 2%.

High energy gamma-ray production in nuclear reactions

International Nuclear Information System (INIS)

Pinston, J.A.; Nifenecker, H.; Nifenecker, H.

1989-01-01

Experimental techniques used to study high energy gamma-ray production in nuclear reactions are reviewed. High energy photon production in nucleus-nucleus collisions is discussed. Semi-classical descriptions of the nucleus-nucleus gamma reactions are introduced. Nucleon-nucleon gamma cross sections are considered, including theoretical aspects and experimental data. High energy gamma ray production in proton-nucleus reactions is explained. Theoretical explanations of photon emission in nucleus-nucleus collisions are treated. The contribution of charged pion currents to photon production is mentioned

A high-throughput platform for low-volume high-temperature/pressure sealed vessel solvent extractions

Energy Technology Data Exchange (ETDEWEB)

Damm, Markus [Christian Doppler Laboratory for Microwave Chemistry (CDLMC) and Institute of Chemistry, Karl-Franzens-University Graz, Heinrichstrasse 28, A-8010 Graz (Austria); Kappe, C. Oliver, E-mail: oliver.kappe@uni-graz.at [Christian Doppler Laboratory for Microwave Chemistry (CDLMC) and Institute of Chemistry, Karl-Franzens-University Graz, Heinrichstrasse 28, A-8010 Graz (Austria)

2011-11-30

Highlights: Black-Right-Pointing-Pointer Parallel low-volume coffee extractions in sealed-vessel HPLC/GC vials. Black-Right-Pointing-Pointer Extractions are performed at high temperatures and pressures (200 Degree-Sign C/20 bar). Black-Right-Pointing-Pointer Rapid caffeine determination from the liquid phase. Black-Right-Pointing-Pointer Headspace analysis of volatiles using solid-phase microextraction (SPME). - Abstract: A high-throughput platform for performing parallel solvent extractions in sealed HPLC/GC vials inside a microwave reactor is described. The system consist of a strongly microwave-absorbing silicon carbide plate with 20 cylindrical wells of appropriate dimensions to be fitted with standard HPLC/GC autosampler vials serving as extraction vessels. Due to the possibility of heating up to four heating platforms simultaneously (80 vials), efficient parallel analytical-scale solvent extractions can be performed using volumes of 0.5-1.5 mL at a maximum temperature/pressure limit of 200 Degree-Sign C/20 bar. Since the extraction and subsequent analysis by either gas chromatography or liquid chromatography coupled with mass detection (GC-MS or LC-MS) is performed directly from the autosampler vial, errors caused by sample transfer can be minimized. The platform was evaluated for the extraction and quantification of caffeine from commercial coffee powders assessing different solvent types, extraction temperatures and times. For example, 141 {+-} 11 {mu}g caffeine (5 mg coffee powder) were extracted during a single extraction cycle using methanol as extraction solvent, whereas only 90 {+-} 11 were obtained performing the extraction in methylene chloride, applying the same reaction conditions (90 Degree-Sign C, 10 min). In multiple extraction experiments a total of {approx}150 {mu}g caffeine was extracted from 5 mg commercial coffee powder. In addition to the quantitative caffeine determination, a comparative qualitative analysis of the liquid phase coffee

A high-throughput platform for low-volume high-temperature/pressure sealed vessel solvent extractions

International Nuclear Information System (INIS)

Damm, Markus; Kappe, C. Oliver

2011-01-01

Highlights: ► Parallel low-volume coffee extractions in sealed-vessel HPLC/GC vials. ► Extractions are performed at high temperatures and pressures (200 °C/20 bar). ► Rapid caffeine determination from the liquid phase. ► Headspace analysis of volatiles using solid-phase microextraction (SPME). - Abstract: A high-throughput platform for performing parallel solvent extractions in sealed HPLC/GC vials inside a microwave reactor is described. The system consist of a strongly microwave-absorbing silicon carbide plate with 20 cylindrical wells of appropriate dimensions to be fitted with standard HPLC/GC autosampler vials serving as extraction vessels. Due to the possibility of heating up to four heating platforms simultaneously (80 vials), efficient parallel analytical-scale solvent extractions can be performed using volumes of 0.5–1.5 mL at a maximum temperature/pressure limit of 200 °C/20 bar. Since the extraction and subsequent analysis by either gas chromatography or liquid chromatography coupled with mass detection (GC–MS or LC–MS) is performed directly from the autosampler vial, errors caused by sample transfer can be minimized. The platform was evaluated for the extraction and quantification of caffeine from commercial coffee powders assessing different solvent types, extraction temperatures and times. For example, 141 ± 11 μg caffeine (5 mg coffee powder) were extracted during a single extraction cycle using methanol as extraction solvent, whereas only 90 ± 11 were obtained performing the extraction in methylene chloride, applying the same reaction conditions (90 °C, 10 min). In multiple extraction experiments a total of ∼150 μg caffeine was extracted from 5 mg commercial coffee powder. In addition to the quantitative caffeine determination, a comparative qualitative analysis of the liquid phase coffee extracts and the headspace volatiles was performed, placing special emphasis on headspace analysis using solid-phase microextraction (SPME

In situ high temperature MAS NMR study of the mechanisms of catalysis. Ethane aromatization on Zn-modified zeolite BEA.

Science.gov (United States)

Arzumanov, Sergei S; Gabrienko, Anton A; Freude, Dieter; Stepanov, Alexander G

2009-04-01

Ethane conversion into aromatic hydrocarbons over Zn-modified zeolite BEA has been analyzed by high-temperature MAS NMR spectroscopy. Information about intermediates (Zn-ethyl species) and reaction products (mainly toluene and methane), which were formed under the conditions of a batch reactor, was obtained by (13)C MAS NMR. Kinetics of the reaction, which was monitored by (1)H MAS NMR in situ at the temperature of 573K, provided information about the reaction mechanism. Simulation of the experimental kinetics within the frames of the possible kinetic schemes of the reaction demonstrates that a large amount of methane evolved under ethane aromatization arises from the stage of direct ethane hydrogenolysis.

On the high-temperature unimolecular decomposition of ethyl levulinate

KAUST Repository

Alabbad, Mohammed; Giri, Binod; Szőri, Milá n; Farooq, Aamir

2016-01-01

The pyrolysis of ethyl levulinate (EL) was studied behind reflected shock waves over the temperature range of 1015-1325K and pressures of 750-1650Torr. The reaction progress was followed by measuring ethylene mole fraction using CO2 gas laser absorption near 10.532 μm. The rate coefficients for the unimolecular dissociation of EL were extracted from the initial slope method and further ascertained by using a complete kinetic model. Our data exhibited no discernible pressure dependence under the current experimental conditions. To rationalize our results further, high-level quantum chemical and master equation calculations were employed to calculate the pressure- and temperature-dependence of the reaction. Our calculations revealed that unimolecular dissociation of EL involves simultaneous 1,5-hydrogen shift of the β-hydrogen to the carbonyl group, rupture of the O-C ester bond and formation of the π-bond (C α -C β ). Our results present evidences that the C2H4 elimination from EL occurs in a concerted manner. To our knowledge, this work represents the first experimental and theoretical study of the thermal unimolecular dissociation of ethyl levulinate. © 2016 The Combustion Institute.

On the high-temperature unimolecular decomposition of ethyl levulinate

KAUST Repository

Alabbad, Mohammed

2016-09-20

The pyrolysis of ethyl levulinate (EL) was studied behind reflected shock waves over the temperature range of 1015-1325K and pressures of 750-1650Torr. The reaction progress was followed by measuring ethylene mole fraction using CO2 gas laser absorption near 10.532 μm. The rate coefficients for the unimolecular dissociation of EL were extracted from the initial slope method and further ascertained by using a complete kinetic model. Our data exhibited no discernible pressure dependence under the current experimental conditions. To rationalize our results further, high-level quantum chemical and master equation calculations were employed to calculate the pressure- and temperature-dependence of the reaction. Our calculations revealed that unimolecular dissociation of EL involves simultaneous 1,5-hydrogen shift of the β-hydrogen to the carbonyl group, rupture of the O-C ester bond and formation of the π-bond (C α -C β ). Our results present evidences that the C2H4 elimination from EL occurs in a concerted manner. To our knowledge, this work represents the first experimental and theoretical study of the thermal unimolecular dissociation of ethyl levulinate. © 2016 The Combustion Institute.

Thermal Stability of Hexamethyldisiloxane (MM for High-Temperature Organic Rankine Cycle (ORC

Directory of Open Access Journals (Sweden)

Markus Preißinger

2016-03-01

Full Text Available The design of efficient Organic Rankine Cycle (ORC units for the usage of industrial waste heat at high temperatures requires direct contact evaporators without intermediate thermal oil circuits. Therefore, the thermal stability of high-temperature working fluids gains importance. In this study, the thermal degradation of hexamethyldisiloxane (MM is investigated in an electrically heated tube. Qualitative results concerning remarks on degradation products as well as quantitative results like the annual degradation rate are presented. It is shown that MM is stable up to a temperature of 300 °C with annual degradation rates of less than 3.5%. Furthermore, the break of a silicon–carbon bond can be a main chemical reaction that influences the thermal degradation. Finally, it is discussed how the results may impact the future design of ORC units.

Reaction of chlorine nitrate with hydrogen chloride and water at Antarctic stratospheric temperatures

Science.gov (United States)

Tolbert, Margaret A.; Rossi, Michel J.; Malhotra, Ripudaman; Golden, David M.

1987-01-01

Laboratory studies of heterogeneous reactions important for ozone depletion over Antarctica are reported. The reaction of chlorine nitrate (ClONO2) with H2O and HCl on surfacers that simulate polar stratospheric clouds are studied at temperatures relevant to the Antarctic stratosphere. The gaseous products of the resulting reactions, HOCl, Cl2O, and Cl2, could readily photolyze in the Antarctic spring to produce active chlorine for ozone depletion. Furthermore, the additional formation of condensed-phase HNO3 could serve as a sink for odd nitrogen species that would otherwise scavenge the active chlorine.

Advances in high temperature chemistry

CERN Document Server

Eyring, Leroy

1969-01-01

Advances in High Temperature Chemistry, Volume 2 covers the advances in the knowledge of the high temperature behavior of materials and the complex and unfamiliar characteristics of matter at high temperature. The book discusses the dissociation energies and free energy functions of gaseous monoxides; the matrix-isolation technique applied to high temperature molecules; and the main features, the techniques for the production, detection, and diagnosis, and the applications of molecular beams in high temperatures. The text also describes the chemical research in streaming thermal plasmas, as w

Monazite behaviours during high-temperature metamorphism: a case study from Dinggye region, Tibetan Himalaya

Science.gov (United States)

Wang, Jia-Min; Wu, Fu-Yuan; Rubatto, Daniela; Liu, Shi-Ran; Zhang, Jin-Jiang

2017-04-01

Monazite is a key accessory mineral for metamorphic geochronology, but its growth mechanisms during melt-bearing high-temperature metamorphism is not well understood. Therefore, the petrology, pressure-temperature and timing of metamorphism have been investigated in pelitic and psammitic granulites from the Greater Himalayan Crystalline Complex (GHC) in Dinggye, southern Tibet. These rocks underwent an isothermal decompression process from pressure conditions of >10 kbar to armour effect of matrix crystals (biotite and quartz). Most monazite grains formed at the M3-stage (21-19 Ma) through either dissolution-reprecipitation or recrystallization that was related to biotite dehydration melting reaction. These monazite grains record HREE and Y signatures in local equilibrium with different reactions involving either garnet breakdown or peritectic garnet growth. Another peak of monazite growth occurs during melt crystallization ( 15 Ma), and these monazites are unzoned and have homogeneous compositions. Our results documented the widespread recrystallization to account for monazite growth during high-temperature metamorphism and related melting reactions that trigger monazite recrystallization. In a regional sense, our P-T-t data along with published data indicate that the pre-M1 eclogite-facies metamorphism occurred at 39-30 Ma in the Dinggye Himalaya. Our results are in favour of a steady exhumation of the GHC rocks since Oligocene that was contributed by partial melting. Key words: U-Th-Pb geochronology, Monazite, Recrystallization, Pelitic granulite, Himalaya

High-temperature rate constant measurements for OH+xylenes

KAUST Repository

Elwardani, Ahmed Elsaid

2015-06-01

The overall rate constants for the reactions of hydroxyl (OH) radicals with o-xylene (k 1), m-xylene (k 2), and p-xylene (k 3) were measured behind reflected shock waves over 890-1406K at pressures of 1.3-1.8atm using OH laser absorption near 306.7nm. Measurements were performed under pseudo-first-order conditions. The measured rate constants, inferred using a mechanism-fitting approach, can be expressed in Arrhenius form as:k1=2.93×1013exp(-1350.3/T)cm3mol-1s-1(890-1406K)k2=3.49×1013exp(-1449.3/T)cm3mol-1s-1(906-1391K)k3=3.5×1013exp(-1407.5/T)cm3mol-1s-1(908-1383K)This paper presents, to our knowledge, first high-temperature measurements of the rate constants of the reactions of xylene isomers with OH radicals. Low-temperature rate-constant measurements by Nicovich et al. (1981) were combined with the measurements in this study to obtain the following Arrhenius expressions, which are applicable over a wider temperature range:k1=2.64×1013exp(-1181.5/T)cm3mol-1s-1(508-1406K)k2=3.05×109exp(-400/T)cm3mol-1s-1(508-1391K)k3=3.0×109exp(-440/T)cm3mol-1s-1(526-1383K) © 2015 The Combustion Institute.

Oxidation Study of an Ultra High Temperature Ceramic Coatings Based on HfSiCN

Science.gov (United States)

Sacksteder, Dagny; Waters, Deborah L.; Zhu, Dongming

2018-01-01

High temperature fiber-reinforced ceramic matrix composites (CMCs) are important for aerospace applications because of their low density, high strength, and significantly higher-temperature capabilities compared to conventional metallic systems. The use of the SiCf/SiC and Cf/SiC CMCs allows the design of lighter-weight, more fuel efficient aircraft engines and also more advanced spacecraft airframe thermal protection systems. However, CMCs have to be protected with advanced environmental barrier coatings when they are incorporated into components for the harsh environments such as in aircraft engine or spacecraft applications. In this study, high temperature oxidation kinetics of an advanced HfSiCN coating on Cf/SiC CMC substrates were investigated at 1300 C, 1400 C, and 1500 C by using thermogravimetric analysis (TGA). The coating oxidation reaction parabolic rate constant and activation energy were estimated from the experimental results. The oxidation reaction studies showed that the coatings formed the most stable, predominant HfSiO4-HfO2 scales at 1400 C. A peroxidation test at 1400 C then followed by subsequent oxidation tests at various temperatures also showed more adherent scales and slower scale growth because of reduced the initial transient oxidation stage and increased HfSiO4-HfO2 content in the scales formed on the HfSiCN coatings.

Preliminary estimations on the heat recovery method for hydrogen production by the high temperature steam electrolysis

International Nuclear Information System (INIS)

Koh, Jae Hwa; Yoon, Duck Joo

2009-01-01

As a part of the project 'development of hydrogen production technologies by high temperature electrolysis using very high temperature reactor', we have developed an electrolyzer model for high temperature steam electrolysis (HTSE) system and carried out some preliminary estimations on the effects of heat recovery on the HTSE hydrogen production system. To produce massive hydrogen by using nuclear energy, the HTSE process is one of the promising technologies with sulfur-iodine and hybrid sulfur process. The HTSE produces hydrogen through electrochemical reaction within the solid oxide electrolysis cell (SOEC), which is a reverse reaction of solid oxide fuel cell (SOFC). The HTSE system generally operates in the temperature range of 700∼900 .deg. C. Advantages of HTSE hydrogen production are (a) clean hydrogen production from water without carbon oxide emission, (b) synergy effect due to using the current SOFC technology and (c) higher thermal efficiency of system when it is coupled nuclear reactor. Since the HTSE system operates over 700 .deg. C, the use of heat recovery is an important consideration for higher efficiency. In this paper, four different heat recovery configurations for the HTSE system have been investigated and estimated

High temperature oxidation of β-NbTi alloys

International Nuclear Information System (INIS)

Parida, S.C.; Gupta, N.K.; Rama Rao, G.A.; Sen, B.K.; Krishnan, K.

2008-01-01

The isothermal oxidation kinetics of pure Ti metal and two different β-NbTi alloys with compositions of 85 and 75 at.% Ti were studied using thermogravimetric technique in the temperature range of 1073-1323 K at an interval of 50 K. The value of the power exponent n of the rate equation was found to be close to one suggesting that each reaction follows first order kinetic rate law. X-ray diffraction analysis of oxidation products at each temperature revealed the simultaneous formation of TiO 2 and TiNb 2 O 7 . The rate constants and the activation energies of oxidation reactions for each alloy compositions were evaluated. (author)

WO{sub 3} nanorods prepared by low-temperature seeded growth hydrothermal reaction

Energy Technology Data Exchange (ETDEWEB)

Ng, Chai Yan [School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang (Malaysia); Abdul Razak, Khairunisak, E-mail: khairunisak@eng.usm.my [School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang (Malaysia); NanoBiotechnology Research and Innovation (NanoBRI), Institute for Research in Molecular Medicine (INFORMM), Universiti Sains Malaysia, 11800 USM, Penang (Malaysia); Lockman, Zainovia, E-mail: zainovia@eng.usm.my [School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang (Malaysia)

2014-03-05

Highlights: • WO{sub 3} nanorods with 5–10 nm diameter were grown directly on seeded tungsten foil. • WO{sub 3} nanorods were successfully grown at low temperature of 80 °C. • WO{sub 3} nanorods were grown on the entire surface of the seed layer after 24 h. • Annealed nanorods showed better electrochromic properties than as-made nanorods. -- Abstract: This work describes the first tungsten oxide (WO{sub 3}) nanorods hydrothermally grown on W foil. WO{sub 3} nanorods were successfully grown at low hydrothermal temperature of 80 °C by seeded growth hydrothermal reaction. The seed layer was prepared by thermally oxidized the W foil at 400 °C for 0.5 h. This work discusses the effect of hydrothermal reaction and annealing period on the morphological, structural, and electrochromic properties of WO{sub 3} nanorods. Various hydrothermal reaction periods (8–24 h) were studied. Monoclinic WO{sub 3} nanorods with 5–10 nm diameter were obtained after hydrothermal reaction for 24 h. These 24 h WO{sub 3} nanorods were also annealed at 400 °C with varying dwelling periods (0.5–4 h). Electrochromic properties of WO{sub 3} nanorods in an acidic electrolyte were analyzed using cyclic voltammetry and UV–vis spectrophotometry. WO{sub 3} nanorods annealed at 400 °C for 1 h showed the highest charge capacity and the largest optical contrast among the 24 h WO{sub 3} films. The sample also showed good cycling stability without significant degradation. Based on the results, the reaction mechanism of WO{sub 3} nanorod formation on W foil was proposed.

Solid gas reaction phase diagram under high gas pressure

International Nuclear Information System (INIS)

Ishizaki, K.

1992-01-01

This paper reports that to evaluate which are the stable phases under high gas pressure conditions, a solid-gas reaction phase diagram under high gas pressure (HIP phase diagram) has been proposed by the author. The variables of the diagram are temperature, reactant gas partial pressure and total gas pressure. Up to the present time the diagrams have been constructed using isobaric conditions. In this work, the stable phases for a real HIP process were evaluated assuming an isochoric condition. To understand the effect of the total gas pressure on stability is of primary importance. Two possibilities were considered and evaluated, those are: the total gas pressure acts as an independent variable, or it only affects the fugacity values. The results of this work indicate that the total gas pressure acts as an independent variable, and in turn also affects the fugacity values

Red soil as a regenerable sorbent for high temperature removal of hydrogen sulfide from coal gas

International Nuclear Information System (INIS)

Ko, T.-H.; Chu Hsin; Lin, H.-P.; Peng, C.-Y.

2006-01-01

In this study, hydrogen sulfide (H 2 S) was removed from coal gas by red soil under high temperature in a fixed-bed reactor. Red soil powders were collected from the northern, center and southern of Taiwan. They were characterized by XRPD, porosity analysis and DCB chemical analysis. Results show that the greater sulfur content of LP red soils is attributed to the higher free iron oxides and suitable sulfidation temperature is around 773 K. High temperature has a negative effect for use red soil as a desulfurization sorbent due to thermodynamic limitation in a reduction atmosphere. During 10 cycles of regeneration, after the first cycle the red soil remained stable with a breakthrough time between 31 and 36 min. Hydrogen adversely affects sulfidation reaction, whereas CO exhibits a positive effect due to a water-shift reaction. COS was formed during the sulfidation stage and this was attributed to the reaction of H 2 S and CO. Results of XRPD indicated that, hematite is the dominant active species in fresh red soil and iron sulfide (FeS) is a product of the reaction between hematite and hydrogen sulfide in red soils. The spinel phase FeAl 2 O 4 was found during regeneration, moreover, the amount of free iron oxides decreased after regeneration indicating the some of the free iron oxide formed a spinel phase, further reducting the overall desulfurization efficiency

THE BEHAVIOR OF SOLUBLE METALS ELUTED FROM Ni/Fe-BASED ALLOY REACTORS AFTER HIGH-TEMPERATURE AND HIGH-PRESSURE WATER PROCESS

Directory of Open Access Journals (Sweden)

M. Faisal

2012-05-01

Full Text Available The behavior of heavy metals eluted from the wall of Ni/Fe-based alloy reactors after high-temperature and high-pressure water reaction were studied at temperatures ranging from 250 to 400oC. For this purpose, water and cysteic acid were heated in two reactor materials which are SUS 316 and Inconel 625. Under the tested conditions, the erratic behaviors of soluble metals eluted from the wall of Ni/Fe-based alloy in high temperature water were observed. Results showed that metals could be eluted even at a short contact time. The presence of air also promotes elution at sub-critical conditions. At sub-critical conditions, a significant amount of Cr was extracted from SUS 316, while only traces of Ni, Fe, Mo and Mn were eluted. In contrast, Ni was removed in significant amounts compared to Cr when Inconel 625 was tested. It was observed that eluted metals tend to increased under acidic conditions and most of those metals were over the limit of WHO guideline for drinking water. The results are significant both on the viewpoint of environmental regulation on disposal of wastes containing heavy metals, toxicity of resulting product and catalytic effect on a particular reaction.

Biogenic Methane Generation Potential in the Eastern Nankai Trough, Japan: Effect of Reaction Temperature and Total Organic Carbon

Science.gov (United States)

Aung, T. T.; Fujii, T.; Amo, M.; Suzuki, K.

2017-12-01

Understanding potential of methane flux from the Pleistocene fore-arc basin filled turbiditic sedimentary formation along the eastern Nankai Trough is important in the quantitative assessment of gas hydrate resources. We considered generated methane could exist in sedimentary basin in the forms of three major components, and those are methane in methane hydrate, free gas and methane dissolved in water. Generation of biomethane strongly depends on microbe activity and microbes in turn survive in diverse range of temperature, salinity and pH. This study aims to understand effect of reaction temperature and total organic carbon on generation of biomethane and its components. Biomarker analysis and cultural experiment results of the core samples from the eastern Nankai Trough reveal that methane generation rate gets peak at various temperature ranging12.5°to 35°. Simulation study of biomethane generation was made using commercial basin scale simulator, PetroMod, with different reaction temperature and total organic carbon to predict how these effect on generation of biomethane. Reaction model is set by Gaussian distribution with constant hydrogen index and standard deviation of 1. Series of simulation cases with peak reaction temperature ranging 12.5°to 35° and total organic carbon of 0.6% to 3% were conducted and analyzed. Simulation results show that linear decrease in generation potential while increasing reaction temperature. But decreasing amount becomes larger in the model with higher total organic carbon. At higher reaction temperatures, >30°, extremely low generation potential was found. This is due to the fact that the source formation modeled is less than 1 km in thickness and most of formation do not reach temperature more than 30°. In terms of the components, methane in methane hydrate and free methane increase with increasing TOC. Drastic increase in free methane was observed in the model with 3% of TOC. Methane amount dissolved in water shows almost

High-temperature oxidation of Zircaloy-2 and Zircaloy-4 in steam

International Nuclear Information System (INIS)

Urbanic, V.F.; Heidrick, T.R.

1978-01-01

At temperatures above the (α + β)/β transformation temperature for zirconium alloys, steam reacts with β-Zr to form a superficial layer of zirconium oxide (ZrO 2 ) and an intermediate layer of oxygen-stabilized α-Zr. Reaction kinetics and the rate of growth of the combined (ZrO 2 + α-Zr) layer for Zircaloy-2 and Zircaloy-4 oxidation in steam were measured over the temperature range 1050-1850 o C. The reaction rates for both alloys were similar, obeyed parabolic kinetics and were not limited by gas phase diffusion. The parabolic rate constants were consistently less than those given by the Baker and Just correlation for zirconium oxidation in steam. A discontinuity was found in the temperature dependence of both the reaction rate and the rate of growth of the combined (ZrO 2 + α-Zr) layer. The discontinuity is attributed to a change in the oxide microstructure at the discontinuity temperature, an observation which is consistent with the zirconium-oxygen phase diagram. (author)

High-temperature superconductivity

International Nuclear Information System (INIS)

Lynn, J.W.

1990-01-01

This book discusses development in oxide materials with high superconducting transition temperature. Systems with Tc well above liquid nitrogen temperature are already a reality and higher Tc's are anticipated. The author discusses how the idea of a room-temperature superconductor appears to be a distinctly possible outcome of materials research

ELOCA: fuel element behaviour during high temperature transients

International Nuclear Information System (INIS)

Sills, H.E.

1979-03-01

The ELOCA computer code was developed to simulate the uniform thermal-mechanical behaviour of a fuel element during high-temperature transients such as a loss-of-coolant accident (LOCA). Primary emphasis is on the diametral expansion of the fuel sheath. The model assumed is a single UO2/zircaloy-clad element with axisymmetric properties. Physical effects considered by the code are fuel expansion, cracking and melting; variation, during the transient, of internal gas pressure; changing fuel/sheath heat transfer; thermal, elastic and plastic sheath deformation (anisotropic); Zr/H 2 O chemical reaction effects; and beryllium-assisted crack penetration of the sheath. (author)

Low-temperature synthesis of actinide tetraborides by solid-state metathesis reactions

Science.gov (United States)

Lupinetti, Anthony J [Los Alamos, NM; Garcia, Eduardo [Los Alamos, NM; Abney, Kent D [Los Alamos, NM

2004-12-14

The synthesis of actinide tetraborides including uranium tetraboride (UB.sub.4), plutonium tetraboride (PuB.sub.4) and thorium tetraboride (ThB.sub.4) by a solid-state metathesis reaction are demonstrated. The present method significantly lowers the temperature required to .ltoreq.850.degree. C. As an example, when UCl.sub.4 is reacted with an excess of MgB.sub.2, at 850.degree. C., crystalline UB.sub.4 is formed. Powder X-ray diffraction and ICP-AES data support the reduction of UCl.sub.3 as the initial step in the reaction. The UB.sub.4 product is purified by washing water and drying.

Determining Annealing Temperatures for Polymerase Chain Reaction

Science.gov (United States)

Porta, Angela R.; Enners, Edward

2012-01-01

The polymerase chain reaction (PCR) is a common technique used in high school and undergraduate science teaching. Students often do not fully comprehend the underlying principles of the technique and how optimization of the protocol affects the outcome and analysis. In this molecular biology laboratory, students learn the steps of PCR with an…

Alcohol synthesis in a high-temperature slurry reactor

Energy Technology Data Exchange (ETDEWEB)

Roberts, G.W.; Marquez, M.A.; McCutchen, M.S. [North Carolina State Univ., Raleigh, NC (United States)

1995-12-31

The overall objective of this contract is to develop improved process and catalyst technology for producing higher alcohols from synthesis gas or its derivatives. Recent research has been focused on developing a slurry reactor that can operate at temperatures up to about 400{degrees}C and on evaluating the so-called {open_quotes}high pressure{close_quotes} methanol synthesis catalyst using this reactor. A laboratory stirred autoclave reactor has been developed that is capable of operating at temperatures up to 400{degrees}C and pressures of at least 170 atm. The overhead system on the reactor is designed so that the temperature of the gas leaving the system can be closely controlled. An external liquid-level detector is installed on the gas/liquid separator and a pump is used to return condensed slurry liquid from the separator to the reactor. In order to ensure that gas/liquid mass transfer does not influence the observed reaction rate, it was necessary to feed the synthesis gas below the level of the agitator. The performance of a commercial {open_quotes}high pressure {close_quotes} methanol synthesis catalyst, the so-called {open_quotes}zinc chromite{close_quotes} catalyst, has been characterized over a range of temperature from 275 to 400{degrees}C, a range of pressure from 70 to 170 atm., a range of H{sub 2}/CO ratios from 0.5 to 2.0 and a range of space velocities from 2500 to 10,000 sL/kg.(catalyst),hr. Towards the lower end of the temperature range, methanol was the only significant product.

High PT electronuclear reactions and spin observables

International Nuclear Information System (INIS)

Laget, J.M.

1990-01-01

The main arguments of the following topics are reviewed: the high transverse momentum exclusive reactions, the determination of various spin observables and the production of different flavours in reactions induced by real and virtual photons

Effect of Reaction Temperature on Structure, Appearance and Bonding Type of Functionalized Graphene Oxide Modified P-Phenylene Diamine

Directory of Open Access Journals (Sweden)

Hong-Juan Sun

2018-04-01

Full Text Available In this study, graphene oxides with different functionalization degrees were prepared by a facile one-step hydrothermal reflux method at various reaction temperatures using graphene oxide (GO as starting material and p-phenylenediamine (PPD as the modifier. The effects of reaction temperature on structure, appearance and bonding type of the obtained materials were investigated by X-ray diffraction (XRD, Fourier transform infrared spectroscopy (FT-IR, X-ray photoelectron spectroscopy (XPS, and scanning electron microscopy (SEM. The results showed that when the reaction temperature was 10–70 °C, the GO reacted with PPD through non-covalent ionic bonds (–COO−H3+N–R and hydrogen bonds (C–OH…H2N–X. When the reaction temperature reached 90 °C, the GO was functionalized with PPD through covalent bonds of C–N. The crystal structure of products became more ordered and regular, and the interlayer spacing (d value and surface roughness increased as the temperature increased. Furthermore, the results suggested that PPD was grafted on the surface of GO through covalent bonding by first attacking the carboxyl groups and then the epoxy groups of GO.

Development and evaluation of high temperature materials for power plant

International Nuclear Information System (INIS)

Nickel, H.; Schubert, F.

1992-01-01

The development of high temperature materials requires the evaluation of the interaction of microstructure and mechanical properties, the implementation of the microstructural aspects in the constitutive equations for the analysis of loads in a high temperature component and verification of the materials reactions. In this way the full potential of materials properties can be better used. This fundamental method is the basis for the formulation of the structural design code KTA 3221 'Metallic HTR Components'. The method of 'design by analysis' is also activated for large internally cooled turbine blades for stationary gas turbines in combined cycle power plants. This kind of exploratory analysis during the dimensioning procedure are discussed with two examples: He/He-heat exchanger produced of NiCr23Co12Mo (Alloy 617) and turbine blades made of superalloys (e.g. IN 738 LC). (author)

High-temperature compatibility between liquid metal as PWR fuel gap filler and stainless steel and high-density concrete

Science.gov (United States)

Wongsawaeng, Doonyapong; Jumpee, Chayanit; Jitpukdee, Manit

2014-08-01

In conventional nuclear fuel rods for light-water reactors, a helium-filled as-fabricated gap between the fuel and the cladding inner surface accommodates fuel swelling and cladding creep down. Because helium exhibits a very low thermal conductivity, it results in a large temperature rise in the gap. Liquid metal (LM; 1/3 weight portion each of lead, tin, and bismuth) has been proposed to be a gap filler because of its high thermal conductivity (∼100 times that of He), low melting point (∼100 °C), and lack of chemical reactivity with UO2 and water. With the presence of LM, the temperature drop across the gap is virtually eliminated and the fuel is operated at a lower temperature at the same power output, resulting in safer fuel, delayed fission gas release and prevention of massive secondary hydriding. During normal reactor operation, should an LM-bonded fuel rod failure occurs resulting in a discharge of liquid metal into the bottom of the reactor pressure vessel, it should not corrode stainless steel. An experiment was conducted to confirm that at 315 °C, LM in contact with 304 stainless steel in the PWR water chemistry environment for up to 30 days resulted in no observable corrosion. Moreover, during a hypothetical core-melt accident assuming that the liquid metal with elevated temperature between 1000 and 1600 °C is spread on a high-density concrete basement of the power plant, a small-scale experiment was performed to demonstrate that the LM-concrete interaction at 1000 °C for as long as 12 h resulted in no penetration. At 1200 °C for 5 h, the LM penetrated a distance of ∼1.3 cm, but the penetration appeared to stop. At 1400 °C the penetration rate was ∼0.7 cm/h. At 1600 °C, the penetration rate was ∼17 cm/h. No corrosion based on chemical reactions with high-density concrete occurred, and, hence, the only physical interaction between high-temperature LM and high-density concrete was from tiny cracks generated from thermal stress. Moreover

Third O2 addition reactions promote the low-temperature auto-ignition of n-alkanes

KAUST Repository

Wang, Zhandong

2016-01-20

Comprehensive low-temperature oxidation mechanisms are needed to accurately predict fuel auto-ignition properties. This paper studies the effects of a previously unconsidered third O2 addition reaction scheme on the simulated auto-ignition of n-alkanes. We demonstrate that this extended low-temperature oxidation scheme has a minor effect on the simulation of n-pentane ignition; however, its addition significantly improves the prediction of n-hexane auto-ignition under low-temperature rapid compression machine conditions. Additional simulations of n-hexane in a homogeneous charge compression ignition engine show that engine-operating parameters (e.g., intake temperature and combustion phasing) are significantly altered when the third O2 addition kinetic mechanism is considered. The advanced combustion phasing is initiated by the formation and destruction of additional radical chain-branching intermediates produced in the third O2 addition process, e.g. keto-dihydroperoxides and/or keto-hydroperoxy cyclic ethers. Our results indicate that third O2 addition reactions accelerate low-temperature radical chain branching at conditions of relevance to advance engine technologies, and therefore these chemical pathways should also be considered for n-alkanes with 6 or more carbon atoms. © 2015 The Combustion Institute.

Temperature dependence of carbon kinetic isotope effect for the oxidation reaction of ethane by OH radicals under atmospherically relevant conditions

Science.gov (United States)

Piansawan, Tammarat; Saccon, Marina; Laumer, Werner; Gensch, Iulia; Kiendler-Scharr, Astrid

2015-04-01

Modeling of the global distribution of atmospheric ethane sources and sinks by using the 13C isotopic composition requires accurate knowledge of the carbon kinetic isotope effect (KIE) of its atmospheric removal reactions. The quantum mechanical prediction implies the necessity to elucidate the temperature dependence of KIE within atmospherically relevant temperature range by experiment. In this study, the KIE and its temperature dependence for ethane oxidation by OH radicals was investigated at ambient pressure in a temperature range of 243 K to 303 K. The chemical reactions were carried out in a 15 L PFE reaction chamber, suspended in a thermally controlled oven. The isotope ratios of the gas phase components during the course of the reactions were measured by Thermal Desorption -- Gas Chromatography -- Isotope Ratio Mass Spectrometry (TD-GC-IRMS). For each temperature, the KIE was derived from the temporal evolution of the concentration and stable carbon isotope ratio (δ13C) of ethane using a method adapted from the relative reaction rate concept. The room temperature KIE of the ethane reaction with OH radicals was found to be 6.85 ± 0.32 ‰. This value is in agreement with the previously reported value of 8.57 ± 1.95 ‰ [Anderson et al. 2004] but has a substantially lower uncertainty. The experimental results will be discussed with the KIE temperature dependence predicted by quantum mechanical calculations. Reference: Rebecca S. Anderson, Lin Huang, Richard Iannone, Alexandra E. Thompson, and Jochen Rudolph (2004), Carbon Kinetic Isotope Effects in the Gas Phase Reactions of Light Alkanes and Ethene with the OH Radical at 296 ± 4 K, J. Phys. Chem. A, 108, 11537--11544

Influence of rolling direction and carbide precipitation on IGSCC susceptibility in hydrogenated high temperature water

International Nuclear Information System (INIS)

Arioka, Koji; Yamada, Takuyo; Terachi, Takumi; Chiba, Goro

2005-01-01

IGSCC growth behaviors of austenitic stainless steels in hydrogenated high temperature water were studied using compact type specimens (0.5T for cold worked materials). The effect of cold rolling direction, alloy composition and carbide precipitation on crack growth behaviors was studied in hydrogenated high temperature water. Then, to examine the effect of cold work and carbide precipitation on IGSCC behaviors, the role of grain boundary sliding studied in high temperature air using CT specimens. The similar dependences of carbide precipitation and cold work on IGSCC and creep behaviors suggest that grain boundary sliding might play an important role by itself or in conjunction with other reactions such as crack tip dissolution etc. (author)

Synthesis of high saturation magnetic iron oxide nanomaterials via low temperature hydrothermal method

Energy Technology Data Exchange (ETDEWEB)

Bhavani, P.; Rajababu, C.H. [Department of Materials Science & Nanotechnology, Yogivemana University, Vemanapuram 516003, Kadapa (India); Arif, M.D. [Environmental Magnetism Laboratory, Indian Institute of Geomagnetism (IIG), Navi Mumbai 410218, Mumbai (India); Reddy, I. Venkata Subba [Department of Physics, Gitam University, Hyderabad Campus, Rudraram, Medak 502329 (India); Reddy, N. Ramamanohar, E-mail: manoharphd@gmail.com [Department of Materials Science & Nanotechnology, Yogivemana University, Vemanapuram 516003, Kadapa (India)

2017-03-15

Iron oxide nanoparticles (IONPs) were synthesized through a simple low temperature hydrothermal approach to obtain with high saturation magnetization properties. Two series of iron precursors (sulfates and chlorides) were used in synthesis process by varying the reaction temperature at a constant pH. The X-ray diffraction pattern indicates the inverse spinel structure of the synthesized IONPs. The Field emission scanning electron microscopy and high resolution transmission electron microscopy studies revealed that the particles prepared using iron sulfate were consisting a mixer of spherical (16–40 nm) and rod (diameter ~20–25 nm, length <100 nm) morphologies that synthesized at 130 °C, while the IONPs synthesized by iron chlorides are found to be well distributed spherical shapes with size range 5–20 nm. On other hand, the IONPs synthesized at reaction temperature of 190 °C has spherical (16–46 nm) morphology in both series. The band gap values of IONPs were calculated from the obtained optical absorption spectra of the samples. The IONPs synthesized using iron sulfate at temperature of 130 °C exhibited high saturation magnetization (M{sub S}) of 103.017 emu/g and low remanant magnetization (M{sub r}) of 0.22 emu/g with coercivity (H{sub c}) of 70.9 Oe{sub ,} which may be attributed to the smaller magnetic domains (d{sub m}) and dead magnetic layer thickness (t). - Highlights: • Comparison of iron oxide materials prepared with Fe{sup +2}/Fe{sup +3} sulfates and chlorides at different temperatures. • We prepared super-paramagnetic and soft ferromagnetic magnetite nanoparticles. • We report higher saturation magnetization with lower coercivity.

A feasibility study for high-temperature titanium reduction from TiCl4 using a magnesiothermic process

Science.gov (United States)

Ivanov, S. L.; Zablotsky, D.

2018-05-01

The current industrial practice for titanium extraction is a complex procedure, which produces a porous reaction mass of sintered titanium particulates fused to a steel retort wall with magnesium and MgCl2 trapped in the interstices. The reactor temperature is limited to approx. 900 °C due to the formation of fusible TiFe eutectic, which corrodes the retort and degrades the quality of titanium sponge. Here we examine the theoretical foundations and technological possibilities to design a shielded retort of niobium-zirconium alloy NbZr(1%), which is resistant to corrosion by titanium at high temperature. We consider the reactor at a temperature of approx. 1150 °C. Supplying stoichiometric quantities of reagents enables the reaction in the gas phase, whereas the exothermic process sustains the combustion of the reaction zone. When the pathway to the condenser is open, vacuum separation and evacuation of vaporized magnesium dichloride and excess magnesium into the water-cooled condenser take place. As both the reaction and the evacuation occur within seconds, the yield of the extraction is improved. We anticipate new possibilities for designing a device combining the retort function to conduct the reduction in the gas phase with fast vacuum separation of the reaction products and distillation of magnesium dichloride.

A novel fabrication technology of in situ TiB2/6063Al composites: High energy ball milling and melt in situ reaction

International Nuclear Information System (INIS)

Zhang, S.-L.; Yang, J.; Zhang, B.-R.; Zhao, Y.-T.; Chen, G.; Shi, X.-X.; Liang, Z.-P.

2015-01-01

Highlights: • This paper presents a novel technology to fabricate the TiB 2 /6063Al composites. • The novel technology decreases in situ reaction temperature and shortens the time. • The reaction mechanism of in situ reaction at the low temperature is discussed. • Effect of ball milling time and in situ reaction time on the composites is studied. - Abstract: TiB 2 /6063Al matrix composites are fabricated from Al–TiO 2 –B 2 O 3 system by the technology combining high energy ball milling with melt in situ reaction. The microstructure and tensile properties of the composites are investigated by XRD, SEM, EDS, TEM and electronic tensile testing. The results indicate that high energy ball milling technology decreases the in situ reaction temperature and shortens the reaction time for Al–TiO 2 –B 2 O 3 system in contrast with the conventional melt in situ synthesis. The morphology of in situ TiB 2 particles is exhibited in irregular shape or nearly circular shape, and the average size of the particles is less than 700 nm, thereinto the minimum size is approximately 200 nm. In addition, the morphology and size of the reinforced particles are affected by the time of ball milling and in situ reaction. TEM images indicate that the interface between 6063Al matrix and TiB 2 particles is clear and no interfacial outgrowth is observed. Tensile testing results show that the as-cast TiB 2 /6063Al composites exhibit a much higher strength, reaching 191 MPa, which is 1.23 times as high as the as-cast 6063Al matrix. Besides, the tensile fracture surface of the composites displays the dimple-fracture character

Modeling of helium effects in metals: High temperature embrittlement

International Nuclear Information System (INIS)

Trinkaus, H.

1985-01-01

The effects of helium on swelling, creep rupture and fatigue properties of fusion reactor materials subjected to (n,α)-reactions and/or direct α-injection, are controlled by bubble formation. The understanding of such effects requires therefore the modeling of (1) diffusional reactions of He atoms with other defects; (2) nucleation and growth of He bubbles; (3) transformation of such bubbles into cavities under continuous He generation and irradiation or creep stress. The present paper is focussed on the modeling of the (coupled) high temperature bubble nucleation and growth processes within and on grain boundaries. Two limiting cases are considered: di-atomic nucleation described by the simplest possible sets of rate equations, and multi-atomic nucleation described by classical nucleation theory. Scaling laws are derived which characterize the dependence of the bubble densities upon time (He-dose), He generation rate and temperature. Comparison with experimental data of AISI 316 SS α-implanted at temperatures around 1000 K indicates bubble nucleation of the multi-atomic type. The nucleation and growth models are applied to creep tests performed during α-implantation suggesting that in these cases gas driven bubble growth is the life time controlling mechanism. The narrow (creep stress/He generation rate) range of this mechanism in a mechanism map constructed from these tests indicates that in many reactor situations the time to rupture is probably controlled by stress driven cavity growth rather than by gas driven bubble growth. (orig.)

Computational and Experimental Study of Thermodynamics of the Reaction of Titania and Water at High Temperatures.

Science.gov (United States)

Nguyen, Q N; Bauschlicher, C W; Myers, D L; Jacobson, N S; Opila, E J

2017-12-14

Gaseous titanium hydroxide and oxyhydroxide species were studied with quantum chemical methods. The results are used in conjunction with an experimental transpiration study of titanium dioxide (TiO 2 ) in water vapor-containing environments at elevated temperatures to provide a thermodynamic description of the Ti(OH) 4 (g) and TiO(OH) 2 (g) species. The geometry and harmonic vibrational frequencies of these species were computed using the coupled-cluster singles and doubles method with a perturbative correction for connected triple substitutions [CCSD(T)]. For the OH bending and rotation, the B3LYP density functional theory was used to compute corrections to the harmonic approximations. These results were combined to determine the enthalpy of formation. Experimentally, the transpiration method was used with water contents from 0 to 76 mol % in oxygen or argon carrier gases for 20-250 h exposure times at 1473-1673 K. Results indicate that oxygen is not a key contributor to volatilization, and the primary reaction for volatilization in this temperature range is TiO 2 (s) + H 2 O(g) = TiO(OH) 2 (g). Data were analyzed with both the second and third law methods using the thermal functions derived from the theoretical calculations. The third law enthalpy of formation at 298.15 K for TiO(OH) 2 (g) at 298 K was -838.9 ± 6.5 kJ/mol, which compares favorably to the theoretical calculation of -838.7 ± 25 kJ/mol. We recommend the experimentally derived third law enthalpy of formation at 298.15 K for TiO(OH) 2 , the computed entropy of 320.67 J/mol·K, and the computed heat capacity [149.192 + (-0.02539)T + (8.28697 × 10 -6 )T 2 + (-15614.05)/T + (-5.2182 × 10 -11 )/T 2 ] J/mol-K, where T is the temperature in K.

Investigation of Na-CO2 Reaction with Initial Reaction in Various Reacting Surface

International Nuclear Information System (INIS)

Kim, Hyun Su; Park, Gunyeop; Kim, Soo Jae; Park, Hyun Sun; Kim, Moo Hwan; Wi, Myung-Hwan

2015-01-01

The reaction products that cause oxidation and erosion are threaten the heat transfer tubes so that it is necessary to investigate Na-CO 2 reaction according to various experimental parameter. Unlike SWR, Na-CO 2 reaction is more complex to deal with reaction kinetics. Since a comprehensive understanding of Na-CO 2 reaction mechanism is crucial for the safety analysis, the reaction phenomenon under the various conditions was investigated. The current issue is to make a database for developing computational code for CO 2 gas leak situation because it is experimentally difficult to analyze the actual accident situation. Most studies on Na-CO 2 interaction reports that chemical reaction is getting vigorous as temperature increased and reactivity is sensitive as temperature change between 400 .deg. C and 600 .deg. C. Therefore, temperature range is determined based on the operating condition (450 - 500 .deg. C) of KALIMER-600 employed as supercritical CO 2 brayton cycle energy conversion system for Na-CO 2 heat exchanger. And next parameter is sodium surface area which contact between sodium and CO 2 when CO 2 is injected into sodium pool in the accident situation. So, the fundamental surface reaction is experimentally studied in the range of 8 - 12cm 2 . Additionally, it has been reported in recent years that CO 2 Flow rate affects reactivity less significantly and CO 2 flow rate is assumed that 5 SLPM (standard liter per minute) is suitable as a basis for a small leakage. The finally selected control parameters is sodium temperature and reacting surface area with constant CO 2 flow rate. Na-CO 2 reaction test is performed for investigating risk of potential accident which contacts with liquid sodium and CO 2 . Amount of reaction is saturated as time passed because of kept a balance between production of solid phase reaction products and amount of diffusivity. These results contribute to make a database for the SFR safety analysis and additional experiments are needed

High-lying neutron hole strengths observed in pick-up reactions

International Nuclear Information System (INIS)

Gales, S.

1980-01-01

Neutron-hole states in orbits well below the Fermi surface have been observed in a number of medium-heavy nuclei from A=90 to 209 using one nucleon pick-up reactions. The excitation energies, angular distributions of such broad and enhanced structures will be discussed. The fragmentation of the neutron-hole strengths as well as the spreading of such simple mode of excitations into more complex states are compared to recent calculations within the quasiparticle-phonon or the single particle-vibration coupling nuclear models. We report on recent measurements of J for inner-hole states in 89 Zr and 115 Sn 119 Sn using the analyzing power of the (p,d) and (d,t) reactions. Large enhancement of cross-sections are observed at high excitation energy in the study of the (p,t) reactions on Zr, Cd, Sn, Te and Sm isotopes. The systematic features of such high-lying excitation are related to the ones observed in one neutron pick-up experiments. The origin of such concentration of two neutron-hole strengths in Cd and Sn isotopes will be discussed. Preliminary results obtained in the study of the (α, 6 He) reaction at 218 MeV incident energy on 90 Zr, 118 Sn and 208 Pb targets are presented and compared to the (p,t) results. Finally the properties of hole-analog states populated in neutron pick-up reactions (from 90 Zr to 208 Pb) will be presented

High temperature ductility of austenitic alloys exposed to thermal neutrons

International Nuclear Information System (INIS)

Watanabe, K.; Kondo, T.; Ogawa, Y.

1982-01-01

Loss of high temperature ductility due to thermal neutron irradiation was examined by slow strain rate test in vacuum up to 1000 0 C. The results on two heats of Hastelloy alloy X with different boron contents were analyzed with respect to the influence of the temperatures of irradiation and tensile tests, neutron fluence and the associated helium production due to nuclear transmutation reaction. The loss of ductility was enhanced by increasing either temperature or neutron fluence. Simple extrapolations yielded the estimated threshold fluence and the end-of-life ductility values at 900 and 1000 0 C in case where the materials were used in near-core regions of VHTR. The observed relationship between Ni content and the ductility loss has suggested a potential utilization of Fe-based alloys for seathing of the neutron absorber materials

Dehydration Kinetics of Chlorite at High Temperatures and Geophysical Implications

Science.gov (United States)

Shen, K.; Wang, D.; Liu, T.

2017-12-01

A significant amount of water is released from hydrous phases in subduction zones and the brought into the earth's interior. The resulting flux may trigger earthquakes and arc magmatism. Chlorite is one of the most important hydrous minerals with a high water content of 13.0 wt.% in the deep subduction zones, and the dehydration of chlorites are thought to be associated with many anomalies geophysical observations. To understand the nature of the geology and geophysical phenomenon, further research on the dehydration of chlorite should be carried out. Here we report the new results on dehydration kinetics of chlorite at high temperatures. We investigated the dehydration kinetics of chlorite using thermogravimetric analyses (TGA) and X-ray diffraction. The dehydration experiments were conducted with heating rates of 15, 20, 25 K/min up to 1466K. The fitted TGA data results indicate that the probable dehydroxylation mechanism of chlorite is a three-dimensional diffusion reaction with the Fick's second law. The results reveal that the dehydroxylation reaction can be divided into two stages corresponding to the hydroxyls in the two different layers: the first stage between 853 K and 973 K is related to the dehydroxylation of the interlayer hydroxide with the activation energy (Ea) of 159 kJ/ mol and pre-exponential factor (D0) value of 1.53x10-5 m2/s; the second stage between 973 K and 1093 K with an Ea value of 189 kJ/mol and D0 of 2.1x10-5 m2/s is due to the dehydroxylation of the `talc' layer. The mineral reactions and products were observed by high-temperature X-ray diffraction. There are metastable phases during reactions and product phases exhibited a topotactic relationship. The dehydroxylation reaction of chlorite is controlled by an inhomogeneous mechanism. We determine that the fluid production rates of chlorite are 2.7x10-4s-1, 4.5x10-4s-1, 7.3x10-4s-1, 1.2x10-3s-1, 1.7x10-4s-1, at 863 K, 883 K, 903 K, 923 K, 943 K for isothermal dehydration reaction. Our

Kinetics of reactions of oxidation of carbon by carbon dioxide and water steam at high temperatures and low pressures

International Nuclear Information System (INIS)

Boulangier, Francois

1956-01-01

The first objective of this research thesis was to obtain new and reliable experimental results about the reaction kinetics of the oxidation of carbon by carbon dioxide and water steam, and to avoid some disturbing phenomena, for example and more particularly the appearance of electric discharges beyond 1900 K initiated by the filament thermoelectric emission. The author tried to identify the mechanism of the accelerating effect. It appears that previous experiments had been performed only in these disturbed conditions. At the lowest temperatures, the author highlighted the existence of a surface contamination by the desorption products from the apparatus [fr

Effect of Reaction Temperature on Carbon Yield and Morphology of CNTs on Copper Loaded Nickel Nanoparticles

Directory of Open Access Journals (Sweden)

Hu Ming

2016-01-01

Full Text Available This investigation was attempted to introduce carbon nanotubes (CNTs onto surface of copper powders in order to improve heat transfer performance of copper matrix for engineering application of electrical packaging materials. The Ni/MgO catalyst was formed on the copper powders surface by means of codeposition method. CVD technique was executed to fabricate uniform CNTs on copper powders and effect of reaction temperature on the morphology of CNTs was surveyed. The results showed that CNTs products on the copper powder surface were distributed uniformly even if reaction temperature was different. The diameter dimension of CNTs was within the scope of 30~60 nm. Growth behaviors of CNTs by CVD method were considered to be “tip-growth” mechanism. Raman spectra of CNTs proved that intensity ratio of D-band to G-band (ID/IG increased as deposition reaction temperature increased, which implied that order degree of graphitic structure in synthesized CNTs improved.

Synthesis of high-temperature viscosity stabilizer used in drilling fluid

Science.gov (United States)

Zhang, Yanna; Luo, Huaidong; Shi, Libao; Huang, Hongjun

2018-02-01

Abstract For a well performance drilling fluid, when it operates in deep wells under high temperature, the most important property required is the thermal stability. The drilling fluid properties under high temperature can be controlled by proper selection of viscosity stabilizer, which can capture oxygen to protect polymer agent in the drilling fluid. In this paper a viscosity stabilizer PB-854 is described, which was synthesized by 4-phenoxybutyl bromide, paraformaldehyde, and phloroglucinol using etherification method and condensation reaction. We studied the effect of catalyst dosage, temperature, time, and stirring rate on the synthetic yield. Under this condition: molar ratio of 2-tert-Butylphenol, paraformaldehyde and phloroglucinol of 2:1:2.5, reacting temperature of 100 °C, stirring rate of 100 r min-1, and mass content of catalyst of 15 %, char yield of 5-bromine-3-tert-butyl salicylaldehyde reached 86 %. Under this condition: molar ratio of 5-bromine-3-tert-butyl salicylaldehyde and phloroglucinol of 4, reacting temperature of 60 °C, reacting time of 30 min, volume content of sulphuric acid of 80 %, char yield of the target product viscosity stabilizer PB-854 is 86%. Finally, in this paper, infrared spectroscopy is adopted to analyse the structure of the synthetic product PB-854.The improvement in the stability of drilling fluid was further shown after adding the viscosity stabilizer in the common polymer drilling fluid under high temperature conditions of 120 °C ˜ 180 °C. The results show significant change in terms of fluid stability in the presence of this new stabilizer as it provides better stability.

Kinetic mechanism of molecular energy transfer and chemical reactions in low-temperature air-fuel plasmas.

Science.gov (United States)

Adamovich, Igor V; Li, Ting; Lempert, Walter R

2015-08-13

This work describes the kinetic mechanism of coupled molecular energy transfer and chemical reactions in low-temperature air, H2-air and hydrocarbon-air plasmas sustained by nanosecond pulse discharges (single-pulse or repetitive pulse burst). The model incorporates electron impact processes, state-specific N(2) vibrational energy transfer, reactions of excited electronic species of N(2), O(2), N and O, and 'conventional' chemical reactions (Konnov mechanism). Effects of diffusion and conduction heat transfer, energy coupled to the cathode layer and gasdynamic compression/expansion are incorporated as quasi-zero-dimensional corrections. The model is exercised using a combination of freeware (Bolsig+) and commercial software (ChemKin-Pro). The model predictions are validated using time-resolved measurements of temperature and N(2) vibrational level populations in nanosecond pulse discharges in air in plane-to-plane and sphere-to-sphere geometry; temperature and OH number density after nanosecond pulse burst discharges in lean H(2)-air, CH(4)-air and C(2)H(4)-air mixtures; and temperature after the nanosecond pulse discharge burst during plasma-assisted ignition of lean H2-mixtures, showing good agreement with the data. The model predictions for OH number density in lean C(3)H(8)-air mixtures differ from the experimental results, over-predicting its absolute value and failing to predict transient OH rise and decay after the discharge burst. The agreement with the data for C(3)H(8)-air is improved considerably if a different conventional hydrocarbon chemistry reaction set (LLNL methane-n-butane flame mechanism) is used. The results of mechanism validation demonstrate its applicability for analysis of plasma chemical oxidation and ignition of low-temperature H(2)-air, CH(4)-air and C(2)H(4)-air mixtures using nanosecond pulse discharges. Kinetic modelling of low-temperature plasma excited propane-air mixtures demonstrates the need for development of a more accurate

A Novel Low Temperature PCR Assured High-Fidelity DNA Amplification

Directory of Open Access Journals (Sweden)

Shaoxia Zhou

2013-06-01

Full Text Available As previously reported, a novel low temperature (LoTemp polymerase chain reaction (PCR catalyzed by a moderately heat-resistant (MHR DNA polymerase with a chemical-assisted denaturation temperature set at 85 °C instead of the conventional 94–96 °C can achieve high-fidelity DNA amplification of a target DNA, even after up to 120 PCR thermal cycles. Furthermore, such accurate amplification is not achievable with conventional PCR. Now, using a well-recognized L1 gene segment of the human papillomavirus (HPV type 52 (HPV-52 as the template for experiments, we demonstrate that the LoTemp high-fidelity DNA amplification is attributed to an unusually high processivity and stability of the MHR DNA polymerase whose high fidelity in template-directed DNA synthesis is independent of non-existent 3'–5' exonuclease activity. Further studies and understanding of the characteristics of the LoTemp PCR technology may facilitate implementation of DNA sequencing-based diagnostics at the point of care in community hospital laboratories.

Laser thermal effect on silicon nitride ceramic based on thermo-chemical reaction with temperature-dependent thermo-physical parameters

International Nuclear Information System (INIS)

Pan, A.F.; Wang, W.J.; Mei, X.S.; Wang, K.D.; Zhao, W.Q.; Li, T.Q.

2016-01-01

Highlights: • A two-dimensional thermo-chemical reaction model is creatively built. • Thermal conductivity and heat capacity of β-Si_3N_4 are computed accurately. • The appropriate thermo-chemical reaction rate is fitted and reaction element length is set to assure the constringency. • The deepest ablated position was not the center of the ablated area due to plasma absorption. • The simulation results demonstrate the thermo-chemical process cant be simplified to be physical phase transition. - Abstract: In this study, a two-dimensional thermo-chemical reaction model with temperature-dependent thermo-physical parameters on Si_3N_4 with 10 ns laser was developed to investigate the ablated size, volume and surface morphology after single pulse. For model parameters, thermal conductivity and heat capacity of β-Si_3N_4 were obtained from first-principles calculations. Thermal-chemical reaction rate was fitted by collision theory, and then, reaction element length was deduced using the relationship between reaction rate and temperature distribution. Furthermore, plasma absorption related to energy loss was approximated as a function of electron concentration in Si_3N_4. It turned out that theoretical ablated volume and radius increased and then remained constant with increasing laser energy, and the maximum ablated depth was not in the center of the ablated zone. Moreover, the surface maximum temperature of Si_3N_4 was verified to be above 3000 K within pulse duration, and it was much higher than its thermal decomposition temperature of 1800 K, which indicated that Si_3N_4 was not ablated directly above the thermal decomposition temperature. Meanwhile, the single pulse ablation of Si_3N_4 was performed at different powers using a TEM_0_0 10 ns pulse Nd:YAG laser to validate the model. The model showed a satisfactory consistence between the experimental data and numerical predictions, presenting a new modeling technology that may significantly increase the

Modeling the pH and temperature dependence of aqueousphase hydroxyl radical reaction rate constants of organic micropollutants using QSPR approach.

Science.gov (United States)

Gupta, Shikha; Basant, Nikita

2017-11-01

Designing of advanced oxidation process (AOP) requires knowledge of the aqueous phase hydroxyl radical ( ● OH) reactions rate constants (k OH ), which are strictly dependent upon the pH and temperature of the medium. In this study, pH- and temperature-dependent quantitative structure-property relationship (QSPR) models based on the decision tree boost (DTB) approach were developed for the prediction of k OH of diverse organic contaminants following the OECD guidelines. Experimental datasets (n = 958) pertaining to the k OH values of aqueous phase reactions at different pH (n = 470; 1.4 × 10 6 to 3.8 × 10 10  M -1  s -1 ) and temperature (n = 171; 1.0 × 10 7 to 2.6 × 10 10  M -1  s -1 ) were considered and molecular descriptors of the compounds were derived. The Sanderson scale electronegativity, topological polar surface area, number of double bonds, and halogen atoms in the molecule, in addition to the pH and temperature, were found to be the relevant predictors. The models were validated and their external predictivity was evaluated in terms of most stringent criteria parameters derived on the test data. High values of the coefficient of determination (R 2 ) and small root mean squared error (RMSE) in respective training (> 0.972, ≤ 0.12) and test (≥ 0.936, ≤ 0.16) sets indicated high generalization and predictivity of the developed QSPR model. Other statistical parameters derived from the training and test data also supported the robustness of the models and their suitability for screening new chemicals within the defined chemical space. The developed QSPR models provide a valuable tool for predicting the ● OH reaction rate constants of emerging new water contaminants for their susceptibility to AOPs.

1,3,5-Triethylbenzene Transformation Reactions Compared to Its Transalkylation Reaction with Ethylbenzene

KAUST Repository

Akhtar, M. Naseem; Sulaiman, Al Khattaf

2009-01-01

The transalkylation of 1,3,5-triethylbenzene (1,3,5-TEB) with ethylbenzene (EB) has been studied over USYtype catalysts using a riser simulator that mimics the operation of a fluidized-bed reactor. The reaction mixture EB and 1,3,5-TEB was used at a molar ratio of 1:1, which is equivalent to 40:60 wt % of EB/1,3,5-TEB, respectively. The reaction temperature was varied from 350 to 500 °C with a time on stream ranging from 3-15 s. The effect of reaction conditions on 1,3,5-TEB conversion, DEB selectivity, and isomerization of 1,3,5-TEB is reported. The transalkylation of 1,3,5-TEB with EB has been compared to the transformation reaction of pure 1,3,5-TEB and EB. The experimental results have revealed that reactivity of 1,3,5-TEB and selectivity of DEB is increased during the transalkylation reaction (EB + 1,3,5-TEB) as compared to the transformation reaction of pure EB or 1,3,5-TEB. The 1,3,5-TEB undergoes isomerization and a cracking reaction to produce DEB and EB but does not undergo any appreciable disproportionation reaction. The isomerization of 1,3,5-TEB is more active at low temperatures, while cracking is more active at high temperatures. © 2009 American Chemical Society.

1,3,5-Triethylbenzene Transformation Reactions Compared to Its Transalkylation Reaction with Ethylbenzene

KAUST Repository

Akhtar, M. Naseem

2009-08-20

The transalkylation of 1,3,5-triethylbenzene (1,3,5-TEB) with ethylbenzene (EB) has been studied over USYtype catalysts using a riser simulator that mimics the operation of a fluidized-bed reactor. The reaction mixture EB and 1,3,5-TEB was used at a molar ratio of 1:1, which is equivalent to 40:60 wt % of EB/1,3,5-TEB, respectively. The reaction temperature was varied from 350 to 500 °C with a time on stream ranging from 3-15 s. The effect of reaction conditions on 1,3,5-TEB conversion, DEB selectivity, and isomerization of 1,3,5-TEB is reported. The transalkylation of 1,3,5-TEB with EB has been compared to the transformation reaction of pure 1,3,5-TEB and EB. The experimental results have revealed that reactivity of 1,3,5-TEB and selectivity of DEB is increased during the transalkylation reaction (EB + 1,3,5-TEB) as compared to the transformation reaction of pure EB or 1,3,5-TEB. The 1,3,5-TEB undergoes isomerization and a cracking reaction to produce DEB and EB but does not undergo any appreciable disproportionation reaction. The isomerization of 1,3,5-TEB is more active at low temperatures, while cracking is more active at high temperatures. © 2009 American Chemical Society.

FEM Modeling of the Relationship between the High-Temperature Hardness and High-Temperature, Quasi-Static Compression Experiment.

Science.gov (United States)

Zhang, Tao; Jiang, Feng; Yan, Lan; Xu, Xipeng

2017-12-26

The high-temperature hardness test has a wide range of applications, but lacks test standards. The purpose of this study is to develop a finite element method (FEM) model of the relationship between the high-temperature hardness and high-temperature, quasi-static compression experiment, which is a mature test technology with test standards. A high-temperature, quasi-static compression test and a high-temperature hardness test were carried out. The relationship between the high-temperature, quasi-static compression test results and the high-temperature hardness test results was built by the development of a high-temperature indentation finite element (FE) simulation. The simulated and experimental results of high-temperature hardness have been compared, verifying the accuracy of the high-temperature indentation FE simulation.The simulated results show that the high temperature hardness basically does not change with the change of load when the pile-up of material during indentation is ignored. The simulated and experimental results show that the decrease in hardness and thermal softening are consistent. The strain and stress of indentation were analyzed from the simulated contour. It was found that the strain increases with the increase of the test temperature, and the stress decreases with the increase of the test temperature.

FEM Modeling of the Relationship between the High-Temperature Hardness and High-Temperature, Quasi-Static Compression Experiment

Directory of Open Access Journals (Sweden)

Tao Zhang

2017-12-01

Full Text Available The high-temperature hardness test has a wide range of applications, but lacks test standards. The purpose of this study is to develop a finite element method (FEM model of the relationship between the high-temperature hardness and high-temperature, quasi-static compression experiment, which is a mature test technology with test standards. A high-temperature, quasi-static compression test and a high-temperature hardness test were carried out. The relationship between the high-temperature, quasi-static compression test results and the high-temperature hardness test results was built by the development of a high-temperature indentation finite element (FE simulation. The simulated and experimental results of high-temperature hardness have been compared, verifying the accuracy of the high-temperature indentation FE simulation.The simulated results show that the high temperature hardness basically does not change with the change of load when the pile-up of material during indentation is ignored. The simulated and experimental results show that the decrease in hardness and thermal softening are consistent. The strain and stress of indentation were analyzed from the simulated contour. It was found that the strain increases with the increase of the test temperature, and the stress decreases with the increase of the test temperature.

Analyses for experiment on sodium-water reaction temperature by the CHAMPAGNE code

International Nuclear Information System (INIS)

Yoshioka, Naoki; Kishida, Masako; Yamada, Yumi

2000-03-01

In this work, analyses on sodium-water reaction temperature in the new SWAT-1(SWAT-1R) test were completed by the CHAMPAGNE code in order to understand void and velocity distribution in sodium system, which was difficult to be measured in experiments. The application method of the RELAP5/Mod2 code was investigated to LMFBR steam generator (SG) blow down analysis, too. The following results were obtained. (1) Analyses on sodium-water reaction temperature in the SWAT-1R test. 1) Analyses were carried out for the SWAT-1R test under the condition water leak rate 600 g/s by treating the pressure loss coefficient, the interface friction coefficient and the coefficient related to reaction rate as parameters. The effect and mechanism of each parameter on the shape of reaction zone were well understood by these analyses. 2) The void and velocity distribution in sodium system were estimated by use of the most suitable parameters. These analytical results are expected to be useful for planning of the SWAT-1R test and evaluation of test result. (2) Investigation of the RELAP5/Mod2 code. 1) The items to be improved in the RELAP5/Mod2 code were clarified to apply this code to the FBR SG blow down analysis. 2) One of these items was an addition of the shell-side (sodium-side) model. A sodium-side model was designed and added to the RELAP5/Mod2 code. Test calculations were carried out by this improved code and the basic function of this code was confirmed. (author)

Development of coating technology for nuclear fuel by self-propagating high temperature synthesis

International Nuclear Information System (INIS)

Choi, Y.; Kim, Bong G.; Lee, Y. W.

1997-01-01

This paper presents experimental results of the preparation of silicon carbide and graphite layers on a nuclear fuel from silane and propane gases by a conventional chemical vapor deposition and combustion synthesis technologies. The direct reaction between silicon and pyrolytic carbon in a high temperature releases sufficient amount of energy to make a synthesis self-sustaining under the preheating of about 1200 deg C. During this high temperature process, lamellar structure with isotropic carbon synthesis. A full characterization of phase composition and final morphology of the coated layers by X-ray diffraction, SEM and AES is presented. (author). 6 refs., 1 tab., 11 figs

High stereoselective cyclopropanation reaction of 3-acylcoumarins ...

Indian Academy of Sciences (India)

Wintec

bromoketones at room temperature ..... Qin Zhao et al. 394. Table 2. Scope of reaction.a. Entry. R1. R2. Product. Time/h. Yieldb/%. 1. OC2H5. H. 3a. 2. 68. 2. OCH3. H. 3b. 2. 64. 3. CH3. H. 3c. 2. 40. 4. Ph. H. 3d. 3. 25c. 5. OC2H5. CH3. 3e. 2. 50. 6.

Temperature dependence of the rate constant for reactions of hydrated electrons with H, OH and H2O2

DEFF Research Database (Denmark)

Christensen, H.; Sehested, K.; Løgager, T.

1994-01-01

The temperature dependence of the rate constants, for the reactions of hydrated electrons with H atoms, OH radicals and H2O2 has been determined. The reaction with H atoms, studied in the temperature range 20-250-degrees-C gives k(20-degrees-C) = 2.4 x 10(10) M-1 s-1 and the activation energy E......-1 and E(A) = 15.6 kJ mol-1 (3.7 kcal mol-1) measured from 5-150-degrees-C. Thus, the activation energy for all three fast reactions is close to that expected for diffusion controlled reactions. As phosphates were used as buffer system, the rate constant and activation energy for the reaction......(A) = 14.0 kJ mol-1 (3.3 kcal mol-1). For reaction with OH radicals the corresponding values are, k(20-degrees-C) = 3.1 x 10(10) M-1 s-1 and E(A) = 14.7 kJ mol-1 (3.5 kcal mol-1) determined in the temperature range 5-175-degrees-C. For reaction with H2O2 the values are, k(20-degrees-C) = 1.2 x 10(10) M-1 s...

Supersymmetry at high temperatures

International Nuclear Information System (INIS)

Das, A.; Kaku, M.

1978-01-01

We investigate the properties of Green's functions in a spontaneously broken supersymmetric model at high temperatures. We show that, even at high temperatures, we do not get restoration of supersymmetry, at least in the one-loop approximation

High temperature high vacuum creep testing facilities

International Nuclear Information System (INIS)

Matta, M.K.

1985-01-01

Creep is the term used to describe time-dependent plastic flow of metals under conditions of constant load or stress at constant high temperature. Creep has an important considerations for materials operating under stresses at high temperatures for long time such as cladding materials, pressure vessels, steam turbines, boilers,...etc. These two creep machines measures the creep of materials and alloys at high temperature under high vacuum at constant stress. By the two chart recorders attached to the system one could register time and temperature versus strain during the test . This report consists of three chapters, chapter I is the introduction, chapter II is the technical description of the creep machines while chapter III discuss some experimental data on the creep behaviour. Of helium implanted stainless steel. 13 fig., 3 tab

ZrC Ceramics Prepared by Self-propagating High-temperature Synthesis/Single Action Pressing

Directory of Open Access Journals (Sweden)

CHENG Yong

2017-01-01

Full Text Available ZrC ceramics were prepared by mechanical axial compression of self-propagating high-temperature synthesis/single action pressing (SHS/SAP.The effects of pressure on microstructure and densification of the products,as well as the relationship between displacement/variation of the load curve and SHS reaction,were studied.The structure and properties of the products were investigated by XRD and SEM.In addition,the density was measured by the drain away liquid method.Meanwhile,universal testing machine was used to record the displacement and load curve alternations.The results indicate that products are mainly composed of ZrC phase,the process of exhaust are accelerated as the increasing of pressure as well,leading to the smaller size of porosity and crystal particles.Density manifested as an increasing pattern by the elevated pressure with no longer change at 80MPa.Due to the strong attenuation of pressure at the peak of temperature,the density of the production is only 65.7% in 120MPa.The end point of the SHS reaction and the plastic time of the products can be monitored by displacement and load curve.The results provide evidence for the application of self-propagating high-temperature synthesis/pseudo-hot isostatic pressing to further improve the density of ceramics.

Exploiting Synergistic Effects in Organozinc Chemistry for Direct Stereoselective C-Glycosylation Reactions at Room Temperature.

Science.gov (United States)

Hernan-Gomez, Alberto; Orr, Samantha; Uzelac, Marina; Kennedy, Alan; Barroso, Santiago; Jusseau, Xavier; Lemaire, Sebastien; Farina, Vittorio; Hevia, Eva

2018-06-01

Pairing a range of bis(aryl) zinc reagents ZnAr2 with the stronger Lewis acidic [(ZnArF2)] (ArF = C6F5), enables highly stereoselective cross-coupling between glycosyl bromides and ZnAr2 without the use of a transition metal. Reactions occur at room temperature with excellent levels of stereoselectivity, where ZnArF2 acts as a non-coupling partner although its presence is crucial for the execution of the C(sp2)-C(sp3) bond formation process. Mechanistic studies have uncovered a unique synergistic partnership between the two zinc reagents, which circumvents the need for transition-metal catalysis or forcing reaction conditions. Key to the success of the coupling is the avoidance of solvents that act as Lewis bases vs. diarylzinc compounds (e.g. THF. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermo chemical calculations applied to the study of ceramic corrosion at high temperature - Steel-making applications; Apport de la thermodynamique a l'etude de la corrosion des ceramiques a haute temperature - Applications siderurgiques

Energy Technology Data Exchange (ETDEWEB)

Poirier, J. [Orleans Univ., Polytechnique, 45 (France); Centre National de la Recherche Scientifique (CNRS/CEMHTI), 45 - Orleans-la-Source (France)

2008-05-15

At high temperature, corrosion by gas, slag or metal is recognized in many cases as the essential degradation mode of ceramics. The reaction between the ceramic and the corrosive agent should be described taking into account both the kinetic aspects (rates and mechanisms of the reactions) and the thermodynamic aspects (equilibrium conditions). After a short description of the thermodynamic tools, we will show how some thermo chemical calculations, involving complex multi-component systems at high temperature, can be applied to explain some practical situations. Different examples, from steel making, will be considered: effects of composition changes upon the stability of the refractories and reactions of corrosion between the refractories, the gas and the liquid oxides. (author)

High Temperature Analysis of Aluminum-Lithium 2195 Alloy to Aid in the Design of Improved Welding Techniques

Science.gov (United States)

Talia, George E.; Widener, Christian

1996-01-01

Aluminum-lithium alloys have extraordinary properties. The addition of lithium to an aluminum alloy decreases its density, while making large increases in its strength and hardness. The down side is that they are unstable at higher temperatures, and are subsequently difficult to weld or even manufacture. Martin Marietta, though, developed an aluminum-lithium alloy 2195 that was reported to have exceptional properties and good weldability. Thus, it was chosen as the alloy for the space shuttles super light external tank. Unfortunately, welding 2195 has turned out to be much more of a challenge than anticipated. Thus, research has been undergone in order to understand the mechanisms that are causing the welding problems. Gas reactions have been observed to be detrimental to weld strength. Water vapor has often been identified as having a significant role in these reactions. Nitrogen, however, has also been shown to have a direct correlation to porosity. These reactions were suspected as being complex and responsible for the two main problems of welding 2195. One, the initial welds of 2195 are much weaker than the parent metal. Second, each subsequent welding pass increases the size and number of cracks and porosity, yielding significant reductions in strength. Consequently, the objective of this research was to characterize the high-temperature reactions of 2195 in order to understand the mechanisms for crack growth and the formation of porosity in welds. In order to accomplish that goal, an optical hot-stage microscope, HSM, was used to observe those reactions as they occurred. Surface reactions of 2195 were observed in a variety of environments, such as air, vacuum, nitrogen and helium. For comparison, some samples of Al-2219 were also observed. Some of the reacted surfaces were then analyzed on a scanning electron microscope, SEM. Additionally, a gas chromatograph was used to analyze the gaseous products of the high temperature reactions.

High temperature shock tube experiments and kinetic modeling study of diisopropyl ketone ignition and pyrolysis

KAUST Repository

Barari, Ghazal; Pryor, Owen; Koroglu, Batikan; Sarathy, Mani; Masunov, Artë m E.; Vasu, Subith S.

2017-01-01

Diisopropyl ketone (DIPK) is a promising biofuel candidate, which is produced using endophytic fungal conversion. In this work, a high temperature detailed combustion kinetic model for DIPK was developed using the reaction class approach. DIPK ignition and pyrolysis experiments were performed using the UCF shock tube. The shock tube oxidation experiments were conducted between 1093K and 1630K for different reactant compositions, equivalence ratios (φ=0.5–2.0), and pressures (1–6atm). In addition, methane concentration time-histories were measured during 2% DIPK pyrolysis in argon using cw laser absorption near 3400nm at temperatures between 1300 and 1400K near 1atm. To the best of our knowledge, current ignition delay times (above 1050K) and methane time histories are the first such experiments performed in DIPK at high temperatures. Present data were used as validation targets for the new kinetic model and simulation results showed fair agreement compared to the experiments. The reaction rates corresponding to the main consumption pathways of DIPK were found to have high sensitivity in controlling the reactivity, so these were adjusted to attain better agreement between the simulation and experimental data. A correlation was developed based on the experimental data to predict the ignition delay times using the temperature, pressure, fuel concentration and oxygen concentration.

High temperature shock tube experiments and kinetic modeling study of diisopropyl ketone ignition and pyrolysis

KAUST Repository

Barari, Ghazal

2017-03-10

Diisopropyl ketone (DIPK) is a promising biofuel candidate, which is produced using endophytic fungal conversion. In this work, a high temperature detailed combustion kinetic model for DIPK was developed using the reaction class approach. DIPK ignition and pyrolysis experiments were performed using the UCF shock tube. The shock tube oxidation experiments were conducted between 1093K and 1630K for different reactant compositions, equivalence ratios (φ=0.5–2.0), and pressures (1–6atm). In addition, methane concentration time-histories were measured during 2% DIPK pyrolysis in argon using cw laser absorption near 3400nm at temperatures between 1300 and 1400K near 1atm. To the best of our knowledge, current ignition delay times (above 1050K) and methane time histories are the first such experiments performed in DIPK at high temperatures. Present data were used as validation targets for the new kinetic model and simulation results showed fair agreement compared to the experiments. The reaction rates corresponding to the main consumption pathways of DIPK were found to have high sensitivity in controlling the reactivity, so these were adjusted to attain better agreement between the simulation and experimental data. A correlation was developed based on the experimental data to predict the ignition delay times using the temperature, pressure, fuel concentration and oxygen concentration.

Ultra-high temperature direct propulsion

International Nuclear Information System (INIS)

Araj, K.J.; Slovik, G.; Powell, J.R.; Ludewig, H.

1987-01-01

Potential advantages of ultra-high exhaust temperature (3000 K - 4000 K) direct propulsion nuclear rockets are explored. Modifications to the Particle Bed Reactor (PBR) to achieve these temperatures are described. Benefits of ultra-high temperature propulsion are discussed for two missions - orbit transfer (ΔV = 5546 m/s) and interplanetary exploration (ΔV = 20000 m/s). For such missions ultra-high temperatures appear to be worth the additional complexity. Thrust levels are reduced substantially for a given power level, due to the higher enthalpy caused by partial disassociation of the hydrogen propellant. Though technically challenging, it appears potentially feasible to achieve such ultra high temperatures using the PBR

Verification of the high temperature phase by the electron pair measurement at RHIC

International Nuclear Information System (INIS)

Akiba, Yasuyuki

2013-01-01

At the high energy nuclear collisions of the RHIC accelerator, the high density parton materials are created. If the matter is the quark gluon plasma (QGP) in the high temperature phase of the QCD, thermal photons are expected to be to be radiated there. The direct photon production from the gold + gold collision reactions at RHIC has been measured by using the 'virtual photon method'. In the gold + gold collisions, very many photons are produced compared with the p + p collisions. The production of the excess direct photons approximately agrees with the theoretical prediction of the thermal photon production from the initial temperature from 300 to 600 MeV QGP. In the present explanatory text, the direct photon measurements at the RHENIX experiments of RHIC are described starting from the discovery of high density matter by RHIC. The photon measurements which give direct evidence of the high temperature state and the virtual photon measurement method are reported briefly. The measurements of the direct photons and the estimation of the initial temperature at RHIC are described in detail with illustrations. Finally, some recent results are added and the ALICE experiments of LHC are referred. (S. Funahashi)

The Role of Surface Protection for High-Temperature Performance of TiAl Alloys

Science.gov (United States)

Schütze, Michael

2017-12-01

In the temperature range where TiAl alloys are currently being used in jet engine and automotive industries, surface reaction with the operating environment is not yet a critical issue. Surface treatment may, however, be needed in order to provide improved abrasion resistance. Development routes currently aim at a further increase in operation temperatures in gas turbines up to 800°C and higher, and in automotive applications for turbocharger rotors, even up to 1050°C. In this case, oxidation rates may reach levels where significant metal consumption of the load-bearing cross-section can occur. Another possibly even more critical issue can be high-temperature-induced oxygen and nitrogen up-take into the metal subsurface zone with subsequent massive ambient temperature embrittlement. Solutions for these problems are based on a deliberate phase change of the metal subsurface zone by diffusion treatments and by using effects such as the halogen effect to change the oxidation mechanism at high temperatures. Other topics of relevance for the use of TiAl alloys in high-temperature applications can be high-temperature abrasion resistance, thermal barrier coatings on TiAl and surface quality in additive manufacturing, in all these cases-focusing on the role of the operation environment. This paper addresses the recent developments in these areas and the requirements for future work.

Oxidation of boron carbide at high temperatures

International Nuclear Information System (INIS)

Steinbrueck, Martin

2005-01-01

The oxidation kinetics of various types of boron carbides (pellets, powder) were investigated in the temperature range between 1073 and 1873 K. Oxidation rates were measured in transient and isothermal tests by means of mass spectrometric gas analysis. Oxidation of boron carbide is controlled by the formation of superficial liquid boron oxide and its loss due to the reaction with surplus steam to volatile boric acids and/or direct evaporation at temperatures above 1770 K. The overall reaction kinetics is paralinear. Linear oxidation kinetics established soon after the initiation of oxidation under the test conditions described in this report. Oxidation is strongly influenced by the thermohydraulic boundary conditions and in particular by the steam partial pressure and flow rate. On the other hand, the microstructure of the B 4 C samples has a limited influence on oxidation. Very low amounts of methane were produced in these tests

High temperature structural silicides

International Nuclear Information System (INIS)

Petrovic, J.J.

1997-01-01

Structural silicides have important high temperature applications in oxidizing and aggressive environments. Most prominent are MoSi 2 -based materials, which are borderline ceramic-intermetallic compounds. MoSi 2 single crystals exhibit macroscopic compressive ductility at temperatures below room temperature in some orientations. Polycrystalline MoSi 2 possesses elevated temperature creep behavior which is highly sensitive to grain size. MoSi 2 -Si 3 N 4 composites show an important combination of oxidation resistance, creep resistance, and low temperature fracture toughness. Current potential applications of MoSi 2 -based materials include furnace heating elements, molten metal lances, industrial gas burners, aerospace turbine engine components, diesel engine glow plugs, and materials for glass processing

A novel fabrication technology of in situ TiB{sub 2}/6063Al composites: High energy ball milling and melt in situ reaction

Energy Technology Data Exchange (ETDEWEB)

Zhang, S.-L.; Yang, J. [School of Materials Science and Engineering, Jiangsu University, Zhenjiang, Jiangsu 212013 (China); Zhang, B.-R. [School of Mechanical Engineering, Qilu University of Technology, Jinan, Shandong 250022 (China); Zhao, Y.-T., E-mail: 278075525@qq.com [School of Materials Science and Engineering, Jiangsu University, Zhenjiang, Jiangsu 212013 (China); Chen, G.; Shi, X.-X.; Liang, Z.-P. [School of Materials Science and Engineering, Jiangsu University, Zhenjiang, Jiangsu 212013 (China)

2015-08-05

Highlights: • This paper presents a novel technology to fabricate the TiB{sub 2}/6063Al composites. • The novel technology decreases in situ reaction temperature and shortens the time. • The reaction mechanism of in situ reaction at the low temperature is discussed. • Effect of ball milling time and in situ reaction time on the composites is studied. - Abstract: TiB{sub 2}/6063Al matrix composites are fabricated from Al–TiO{sub 2}–B{sub 2}O{sub 3} system by the technology combining high energy ball milling with melt in situ reaction. The microstructure and tensile properties of the composites are investigated by XRD, SEM, EDS, TEM and electronic tensile testing. The results indicate that high energy ball milling technology decreases the in situ reaction temperature and shortens the reaction time for Al–TiO{sub 2}–B{sub 2}O{sub 3} system in contrast with the conventional melt in situ synthesis. The morphology of in situ TiB{sub 2} particles is exhibited in irregular shape or nearly circular shape, and the average size of the particles is less than 700 nm, thereinto the minimum size is approximately 200 nm. In addition, the morphology and size of the reinforced particles are affected by the time of ball milling and in situ reaction. TEM images indicate that the interface between 6063Al matrix and TiB{sub 2} particles is clear and no interfacial outgrowth is observed. Tensile testing results show that the as-cast TiB{sub 2}/6063Al composites exhibit a much higher strength, reaching 191 MPa, which is 1.23 times as high as the as-cast 6063Al matrix. Besides, the tensile fracture surface of the composites displays the dimple-fracture character.

High temperature resistive phase transition in A15 high temperature superconductors

International Nuclear Information System (INIS)

Chu, C.W.; Huang, C.Y.; Schmidt, P.H.; Sugawara, K.

1976-01-01

Resistive measurements were made on A15 high temperature superconductors. Anomalies indicative of a phase transition were observed at 433 0 K in a single crystal Nb 3 Sn and at 485 0 K in an unbacked Nb 3 Ge sputtered thin film. Results are compared with the high temperature transmission electron diffraction studies of Nb 3 Ge films by Schmidt et al. A possible instability in the electron energy spectrum is discussed

High-temperature effect of hydrogen on sintered alpha-silicon carbide

Science.gov (United States)

Hallum, G. W.; Herbell, T. P.

1986-01-01

Sintered alpha-silicon carbide was exposed to pure, dry hydrogen at high temperatures for times up to 500 hr. Weight loss and corrosion were seen after 50 hr at temperatures as low as 1000 C. Corrosion of SiC by hydrogen produced grain boundary deterioration at 1100 C and a mixture of grain and grain boundary deterioration at 1300 C. Statistically significant strength reductions were seen in samples exposed to hydrogen for times greater than 50 hr and temperatures above 1100 C. Critical fracture origins were identified by fractography as either general grain boundary corrision at 1100 C or as corrosion pits at 1300 C. A maximum strength decrease of approximately 33 percent was seen at 1100 and 1300 C after 500 hr exposure to hydrogen. A computer assisted thermodynamic program was also used to predict possible reaction species of SiC and hydrogen.

Nuclear reactions induced by high-energy alpha particles

Science.gov (United States)

Shen, B. S. P.

1974-01-01

Experimental and theoretical studies of nuclear reactions induced by high energy protons and heavier ions are included. Fundamental data needed in the shielding, dosimetry, and radiobiology of high energy particles produced by accelerators were generated, along with data on cosmic ray interaction with matter. The mechanism of high energy nucleon-nucleus reactions is also examined, especially for light target nuclei of mass number comparable to that of biological tissue.

General method and thermodynamic tables for computation of equilibrium composition and temperature of chemical reactions

Science.gov (United States)

Huff, Vearl N; Gordon, Sanford; Morrell, Virginia E

1951-01-01

A rapidly convergent successive approximation process is described that simultaneously determines both composition and temperature resulting from a chemical reaction. This method is suitable for use with any set of reactants over the complete range of mixture ratios as long as the products of reaction are ideal gases. An approximate treatment of limited amounts of liquids and solids is also included. This method is particularly suited to problems having a large number of products of reaction and to problems that require determination of such properties as specific heat or velocity of sound of a dissociating mixture. The method presented is applicable to a wide variety of problems that include (1) combustion at constant pressure or volume; and (2) isentropic expansion to an assigned pressure, temperature, or Mach number. Tables of thermodynamic functions needed with this method are included for 42 substances for convenience in numerical computations.

Temperature escalation in PWR fuel rod simulators due to the zircaloy/steam reaction: Tests ESSI-1,2,3

International Nuclear Information System (INIS)

Hagen, S.; Malauschek, H.; Wallenfels, K.P.; Peck, S.O.

1983-08-01

This report discusses the test conduct, results, and posttest appearance of three scoping tests (ESSI-1,2,3) investigating temperature escalation in zircaloy clad fuel rods. The experiments are part of an out-of-pile program using electrically heated fuel rod simulators to investigate PWR fuel element behavior up to temperatures of 2000 0 C. These experiments are part of the PNS Severe Fuel Damage Program. The temperature escalation is caused by the exothermal zircaloy/steam reaction, whose reaction rate increases exponentially with the temperature. The tests were performed using different initial oxide layers as a major parameter, obtained by varying the heatup rates and steam exposure times. (orig./RW) [de

Temperature dependence of Ni3S2 nanostructures with high electrochemical performance

Science.gov (United States)

Wang, Y. L.; Wei, X. Q.; Li, M. B.; Hou, P. Y.; Xu, X. J.

2018-04-01

Different Ni3S2 nanostructures have been successfully synthesized at different temperatures by a facile and efficient solvothermal method. The Ni3S2 nanostructures with three-dimensional (3D) nanosheets array and silkworm eggs-like morphologies were obtained by adjusting the reaction temperature. A large number of 3D nanosheets are interconnected to form an open network structure with porous of Ni3S2 at 180 °C, and electrochemical tests showed that the special structure exhibited the outstanding specific capacitance (1357 F g -1 at 1 A g-1) and excellent cycling stability (maintained 91% after 3000 cycles). In comparison, the performance of Ni3S2 silkworm eggs-like structure is not very perfect. This may be due to the fact that the 3D nanosheets with porous structure can improve the electrochemical performance by shortening effectively the diffusion path of electrolyte ions and increasing the active sites during charging and discharging. Among them, the reaction temperature is the main factor to control the formation of the 3D nanosheets array. These results indicated the Ni3S2 nanosheets promising applications as high-performance supercapacitor electrode materials.

Interfacial Kinetics of High-Al-Containing Ultra-Lightweight Steels with Calcium Silicate-Based Molten Oxides at High Temperature

Science.gov (United States)

Kim, Gi Hyun; Sohn, Il

2016-06-01

The kinetics of the high-temperature reaction between high-Al- and -Mn-containing steels and synthesized molten calcium silicate-based fluxes from 1623 K to 1643 K (1350 °C to 1370 °C) was studied. Cylindrical steel rods were rotated in the molten fluxes for 300 to 1200 seconds at various temperatures below the melting point of the steels. The rods were connected to a rheometer, and the initial reaction rates were estimated from the torque variations. The dissolution of the steel into the molten slag was correlated to the variation in torque. The kinetics of the reaction between the rods and the slag estimated from the torque and subsequently from the viscosity were confirmed from the mass balance and from the variation in the chemical compositions of the rods and the molten slags, respectively. The liquid-phase mass transfer coefficient of Al2O3 was calculated to be 1.14 × 10-2 cm/s at 1623 K (1350 °C) and 1.52 × 10-2 cm/s at 1633 K (1360 °C). The kinetics calculated assuming liquid-phase mass transfer control was observed to be similar to the aforementioned kinetics determined from the dynamic viscosity variations. On the basis of dimensionless analysis of the Sherwood number (Sh = 0.05·Re0.65Sc0.31), liquid-phase mass transfer from the metal/flux interface was observed to be the rate-controlling step.

Temperature influence on the malonic acid decomposition in the Belousov-Zhabotinsky reaction

Science.gov (United States)

Blagojević, S. M.; Anić, S. R.; Čupić, Ž. D.; Pejić, N. D.; Kolar-Anić, Lj. Z.

2009-09-01

The kinetic investigations of the malonic acid decomposition (8.00 × 10-3 mol dm-3 ≤ [CH2(COOH)2]0 ≤ 4.30 × 10-2 mol dm-3) in the Belousov-Zhabotinsky (BZ) system in the presence of bromate, bromide, sulfuric acid and cerium sulfate, were performed in the isothermal closed well stirred reactor at different temperatures (25.0°C ≤ T ≤ 45.0°C). The formal kinetics of the overall BZ reaction, and particularly kinetics in characteristic periods of BZ reaction, based on the analyses of the bromide oscillograms, was accomplished. The evolution as well as the rate constants and the apparent activation energies of the reactions, which exist in the preoscillatory and oscillatory periods, are also successfully calculated by numerical simulations. Simulations are based on the model including the Br2O species.

Enhancing chemical reactions

Science.gov (United States)

Morrey, John R.

1978-01-01

Methods of enhancing selected chemical reactions. The population of a selected high vibrational energy state of a reactant molecule is increased substantially above its population at thermal equilibrium by directing onto the molecule a beam of radiant energy from a laser having a combination of frequency and intensity selected to pump the selected energy state, and the reaction is carried out with the temperature, pressure, and concentrations of reactants maintained at a combination of values selected to optimize the reaction in preference to thermal degradation by transforming the absorbed energy into translational motion. The reaction temperature is selected to optimize the reaction. Typically a laser and a frequency doubler emit radiant energy at frequencies of .nu. and 2.nu. into an optical dye within an optical cavity capable of being tuned to a wanted frequency .delta. or a parametric oscillator comprising a non-centrosymmetric crystal having two indices of refraction, to emit radiant energy at the frequencies of .nu., 2.nu., and .delta. (and, with a parametric oscillator, also at 2.nu.-.delta.). Each unwanted frequency is filtered out, and each desired frequency is focused to the desired radiation flux within a reaction chamber and is reflected repeatedly through the chamber while reactants are fed into the chamber and reaction products are removed therefrom.

In Situ Solid-State Reactions Monitored by X-ray Absorption Spectroscopy: Temperature-Induced Proton Transfer Leads to Chemical Shifts.

Science.gov (United States)

Stevens, Joanna S; Walczak, Monika; Jaye, Cherno; Fischer, Daniel A

2016-10-24

The dramatic colour and phase alteration with the solid-state, temperature-dependent reaction between squaric acid and 4,4'-bipyridine has been probed in situ with X-ray absorption spectroscopy. The electronic and chemical sensitivity to the local atomic environment through chemical shifts in the near-edge X-ray absorption fine structure (NEXAFS) revealed proton transfer from the acid to the bipyridine base through the change in nitrogen protonation state in the high-temperature form. Direct detection of proton transfer coupled with structural analysis elucidates the nature of the solid-state process, with intermolecular proton transfer occurring along an acid-base chain followed by a domino effect to the subsequent acid-base chains, leading to the rapid migration along the length of the crystal. NEXAFS thereby conveys the ability to monitor the nature of solid-state chemical reactions in situ, without the need for a priori information or long-range order. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-entropy alloys as high-temperature thermoelectric materials

Energy Technology Data Exchange (ETDEWEB)

Shafeie, Samrand [Surface and Microstructure Engineering Group, Materials and Manufacturing Technology, Chalmers University of Technology, SE-41296 Gothenburg (Sweden); Department of Chemistry and Chemical Engineering, Chalmers University of Technology, SE-41296 Gothenburg (Sweden); Guo, Sheng, E-mail: sheng.guo@chalmers.se [Surface and Microstructure Engineering Group, Materials and Manufacturing Technology, Chalmers University of Technology, SE-41296 Gothenburg (Sweden); Hu, Qiang [Institute of Applied Physics, Jiangxi Academy of Sciences, Nanchang 330029 (China); Fahlquist, Henrik [Bruker AXS Nordic AB, 17067 Solna (Sweden); Erhart, Paul [Department of Applied Physics, Chalmers University of Technology, SE-41296 Gothenburg (Sweden); Palmqvist, Anders, E-mail: anders.palmqvist@chalmers.se [Department of Chemistry and Chemical Engineering, Chalmers University of Technology, SE-41296 Gothenburg (Sweden)

2015-11-14

Thermoelectric (TE) generators that efficiently recycle a large portion of waste heat will be an important complementary energy technology in the future. While many efficient TE materials exist in the lower temperature region, few are efficient at high temperatures. Here, we present the high temperature properties of high-entropy alloys (HEAs), as a potential new class of high temperature TE materials. We show that their TE properties can be controlled significantly by changing the valence electron concentration (VEC) of the system with appropriate substitutional elements. Both the electrical and thermal transport properties in this system were found to decrease with a lower VEC number. Overall, the large microstructural complexity and lower average VEC in these types of alloys can potentially be used to lower both the total and the lattice thermal conductivity. These findings highlight the possibility to exploit HEAs as a new class of future high temperature TE materials.

Specialists' meeting on high temperature metallic materials for application in gas-cooled reactors

International Nuclear Information System (INIS)

At the meeting overviews of current programmes for the development of high temperature materials in Japan, F.R. Germany and the United States of America were presented. Some papers were presented dealing with various aspects of microstructural studies, surface reactions and the changes of microstructure and dimensions due mainly to the associated interfacial material transports, protective surface coatings for HTGR and AGR applications. Other topics presented were mechanical properties of materials and also the influence of materials' properties data on design at temperatures in the creep region where time dependent behaviour must be considered

Laboratory study on the high-temperature capture of HCl gas by dry-injection of calcium-based sorbents.

Science.gov (United States)

Shemwell, B; Levendis, Y A; Simons, G A

2001-01-01

This is a laboratory study on the reduction of combustion-generated hydrochloric acid (HCl) emissions by in-furnace dry-injection of calcium-based sorbents. HCl is a hazardous gaseous pollutant emitted in significant quantities by municipal and hazardous waste incinerators, coal-fired power plants, and other industrial furnaces. Experiments were conducted in a laboratory furnace at gas temperatures of 600-1000 degrees C. HCl gas diluted with N2, and sorbent powders fluidized in a stream of air were introduced into the furnace concurrently. Chlorination of the sorbents occurred in the hot zone of the furnace at gas residence times approximately 1 s. The sorbents chosen for these experiments were calcium formate (CF), calcium magnesium acetate (CMA), calcium propionate (CP), calcium oxide (CX), and calcium carbonate (CC). Upon release of organic volatiles, sorbents calcine to CaO at approximately 700 degrees C, and react with the HCl according to the reaction CaO + 2HCl CaCl2 + H2O. At the lowest temperature case examined herein, 600 degrees C, direct reaction of HCl with CaCO3 may also be expected. The effectiveness of the sorbents to capture HCl was interpreted using the "pore tree" mathematical model for heterogeneous diffusion reactions. Results show that the thin-walled, highly porous cenospheres formed from the pyrolysis and calcination of CF, CMA, and CP exhibited high relative calcium utilization at the upper temperatures of this study. Relative utilizations under these conditions reached 80%. The less costly low-porosity sorbents, calcium carbonate and calcium oxide also performed well. Calcium carbonate reached a relative utilization of 54% in the mid-temperature range, while the calcium oxide reached an 80% relative utilization at the lowest temperature examined. The data matched theoretical predictions of sorbent utilization using the mathematical model, with activation energy and pre-exponential factors for the calcination reaction of 17,000 K and 300

Combustion Chemistry of Fuels: Quantitative Speciation Data Obtained from an Atmospheric High-temperature Flow Reactor with Coupled Molecular-beam Mass Spectrometer.

Science.gov (United States)

Köhler, Markus; Oßwald, Patrick; Krueger, Dominik; Whitside, Ryan

2018-02-19

This manuscript describes a high-temperature flow reactor experiment coupled to the powerful molecular beam mass spectrometry (MBMS) technique. This flexible tool offers a detailed observation of chemical gas-phase kinetics in reacting flows under well-controlled conditions. The vast range of operating conditions available in a laminar flow reactor enables access to extraordinary combustion applications that are typically not achievable by flame experiments. These include rich conditions at high temperatures relevant for gasification processes, the peroxy chemistry governing the low temperature oxidation regime or investigations of complex technical fuels. The presented setup allows measurements of quantitative speciation data for reaction model validation of combustion, gasification and pyrolysis processes, while enabling a systematic general understanding of the reaction chemistry. Validation of kinetic reaction models is generally performed by investigating combustion processes of pure compounds. The flow reactor has been enhanced to be suitable for technical fuels (e.g. multi-component mixtures like Jet A-1) to allow for phenomenological analysis of occurring combustion intermediates like soot precursors or pollutants. The controlled and comparable boundary conditions provided by the experimental design allow for predictions of pollutant formation tendencies. Cold reactants are fed premixed into the reactor that are highly diluted (in around 99 vol% in Ar) in order to suppress self-sustaining combustion reactions. The laminar flowing reactant mixture passes through a known temperature field, while the gas composition is determined at the reactors exhaust as a function of the oven temperature. The flow reactor is operated at atmospheric pressures with temperatures up to 1,800 K. The measurements themselves are performed by decreasing the temperature monotonically at a rate of -200 K/h. With the sensitive MBMS technique, detailed speciation data is acquired and

High temperature vapors science and technology

CERN Document Server

Hastie, John

2012-01-01

High Temperature Vapors: Science and Technology focuses on the relationship of the basic science of high-temperature vapors to some areas of discernible practical importance in modern science and technology. The major high-temperature problem areas selected for discussion include chemical vapor transport and deposition; the vapor phase aspects of corrosion, combustion, and energy systems; and extraterrestrial high-temperature species. This book is comprised of seven chapters and begins with an introduction to the nature of the high-temperature vapor state, the scope and literature of high-temp

Evaluation of high temperature pressure sensors

International Nuclear Information System (INIS)

Choi, In-Mook; Woo, Sam-Yong; Kim, Yong-Kyu

2011-01-01

It is becoming more important to measure the pressure in high temperature environments in many industrial fields. However, there is no appropriate evaluation system and compensation method for high temperature pressure sensors since most pressure standards have been established at room temperature. In order to evaluate the high temperature pressure sensors used in harsh environments, such as high temperatures above 250 deg. C, a specialized system has been constructed and evaluated in this study. The pressure standard established at room temperature is connected to a high temperature pressure sensor through a chiller. The sensor can be evaluated in conditions of changing standard pressures at constant temperatures and of changing temperatures at constant pressures. According to the evaluation conditions, two compensation methods are proposed to eliminate deviation due to sensitivity changes and nonlinear behaviors except thermal hysteresis.

Fusion chain reaction - a chain reaction with charged particles

International Nuclear Information System (INIS)

Peres, A.; Shvarts, D.

1975-01-01

When a DT-plasma is compressed to very high density, the particles resulting from nuclear reactions give their energy mostly to D and T ions, by nuclear collisions, rather than to electrons as usual. Fusion can thus proceed as a chain reaction, without the need of thermonuclear temperatures. In this paper, we derive relations for the suprathermal ion population created by a fusion reaction. Numerical integration of these equations shows that a chain reaction can proceed in a cold infinite DT-plasma at densities above 8.4x10 27 ions.cm -3 . Seeding the plasma with a small amount of 6 Li reduces the critical density to 7.2x10 27 ions.cm -3 (140000times the normal solid density). (author)

Temperature effect on radiation induced reactions in ethylene and tetrafluoroethylene copolymer (ETFE)

International Nuclear Information System (INIS)

Oshima, Akihiro; Tabata, Yoneho; Ikeda, Shigetoshi; Seguchi, Tadao

1997-01-01

Ethylene and tetrafluoroethylene copolymer (ETFE) was irradiated by γ-rays or electron beam (EB) under oxygen-free atmosphere at various temperatures ranging from 77 to 573 K. Mechanical and thermal properties, and absorption spectra of the irradiated ETFEs were measured. The mechanical properties of the film have been observed to change by irradiation. The modulus and yield strength increase with increasing dose, and these phenomena are clearly distinguished above the melting temperature of ETFE (533 K). Heat of crystallization changes drastically as a function of irradiation dose around the melting , compared with other temperatures. The absorption band around 250 nm of irradiated ETFE shifts to a longer wavelength region with increase of irradiation temperature. Therefore, it was concluded from those experimental results mentioned above that crosslinking takes place and conjugated double bonds formation proceeds in a wide range of irradiation temperatures. Those reactions are enhanced by increasing temperature. The homogeneous crosslinking takes place in the molten state, while the heterogeneous crosslinking does in the crystalline solid state. (author)

Gas phase chemical kinetics at high temperature of carbonaceous molecules: application to circumstellar envelopes

Science.gov (United States)

Biennier, L.; Gardez, A.; Saidani, G.; Georges, R.; Rowe, B.; Reddy, K. P. J.

2011-05-01

Circumstellar shells of evolved stars are a theater of extremely rich physical and chemical processes. More than seventy molecules of varied nature have been identified in the envelopes through their spectral fingerprints in the microwave or far infrared regions. Many of them are carbon chain molecules and radicals and a significant number are unique to the circumstellar medium. However, observational data remain scarce and more than half of the detected species have been observed in only one object, the nearby carbon star IRC + 10216. Chemical kinetic models are needed to describe the formation of molecules in evolved circumstellar outflows. Upcoming terrestrial telescopes such as ALMA will increase the spatial resolution by several orders of magnitude and provide a wealth of data. The determination of relevant laboratory kinetics data is critical to keep up with the development of the observations and of the refinement of chemical models. Today, the majority of reactions studied in the laboratory are the ones involved in combustion and concerning light hydrocarbons. Our objective is to provide the scientific community with rate coefficients of reactions between abundant species in these warm environments. Cyanopolyynes from HC_2N to HC_9N have all been detected in carbon rich circumstellar envelopes in up to 10 sources for HC_3N. Neutral-neutral reactions of the CN radical with unsaturated hydrocarbons could be a dominant route in the formation of cyanopolyynes, even at low temperatures. Our approach aims to bridge the temperature gap between resistively heated flow tubes and shock tubes. The present kinetic measurements are obtained using a new reactor combining a high enthalpy source (Moudens et al. 2011) with a flow tube and a pulsed laser photolysis and laser induced fluorescence system to probe the undergoing chemical reactions. The high enthalpy flow tube has been used to measure the rate constant of the reaction of the CN radical with propane, propene

Zircaloy-steam reaction under a simulated loss-of-coolant accident

International Nuclear Information System (INIS)

Kawasaki, Satoru; Furuta, Teruo; Hashimoto, Masao

1975-07-01

Under a simulated loss-of-coolant condition, the reaction between zircaloy and steam and the embrittlement of the zircaloy oxidized by this reaction have been studied. The parabolic rate constant, ksub(p), in the zircaloy-steam reaction is represented as ksub(p)=3.24x10 6 exp(-40500/RT) (mg 2 /cm 4 . sec) Ring compression test was made on the steam-reacted zircaloy tubes, and following results were obtained: Embrittlement of the steam-reacted zircaloy tube increases with oxidation at each oxidation temperature. For a given quantity of the oxidation, the incursion of α-phase into β-phase is more remarkable in the specimens reacted at low temperatures than those at high temperatures. The embrittlement, however, is larger in the specimens oxidized at high temperatures than those at low temperatures. (auth.)

Nanostructures of Boron, Carbon and Magnesium Diboride for High Temperature Superconductivity

Energy Technology Data Exchange (ETDEWEB)

Pfefferle, Lisa [Yale Univ., New Haven, CT (United States); Fang, Fang [Yale Univ., New Haven, CT (United States); Iyyamperumal, Eswarmoorthi [Yale Univ., New Haven, CT (United States); Keskar, Gayatri [Yale Univ., New Haven, CT (United States)

2013-12-23

Direct fabrication of MgxBy nanostructures is achieved by employing metal (Ni,Mg) incorporated MCM-41 in the Hybrid Physical-Chemical Vapor Deposition (HPCVD) reaction. Different reaction conditions are tested to optimize the fabrication process. TEM analysis shows the fabrication of MgxBy nanostructures starting at the reaction temperature of 600oC, with the yield of the nanostructures increasing with increasing reaction temperature. The as-synthesized MgxBy nanostructures have the diameters in the range of 3-5nm, which do not increase with the reaction temperature consistent with templated synthesis. EELS analysis of the template removed nanostructures confirms the existence of B and Mg with possible contamination of Si and O. NEXAFS and Raman spectroscopy analysis suggested a concentric layer-by-layer MgxBy nanowire/nanotube growth model for our as-synthesized nanostructures. Ni k-edge XAS indicates that the formation of MgNi alloy particles is important for the Vapor-Liquid-Solid (VLS) growth of MgxBy nanostructures with fine diameters, and the presence of Mg vapor not just Mg in the catalyst is crucial for the formation of Ni-Mg clusters. Physical templating by the MCM-41 pores was shown to confine the diameter of the nanostructures. DC magnetization measurements indicate possible superconductive behaviors in the as-synthesized samples.

Interaction between zircaloy tube and inconel spacer grid at high temperature

International Nuclear Information System (INIS)

Nagase, Fumihisa; Otomo, Takashi; Uetsuka, Hiroshi; Furuta, Teruo

1990-09-01

In order to investigate the interaction between fuel cladding and spacer grid of the pressurized water reactor during a severe accident, isothermal reaction tests were performed at the temperature range from 1248 to 1673K. A specimen consisted of a short Zircaloy-4 cladding tube and a piece of spacer grid of Inconel-718. In the tests in an argon atmosphere, eutectic reaction between Zircaloy and Inconel was observed at the contact points at 1248K. Rapid reaction was observed at higher test temperatures. For example, in the test at 1373K for 300s, Zircaloy reacted with Inconel over the entire thickness (0.62mm) of the tube in the vicinity of the contact point. In the present tests, Zircaloy which has higher melting point than Inconel was dissolved preferentially due to eutectic formation. In the tests in an oxygen atmosphere, no eutectic reaction was observed at temperatures below 1437K. A trace of interaction was found at the contact point of specimen heated at 1573 and 1623K. However, decrease in Zircaloy thickness was not measured. The possibility of eutectic reaction between Zircaloy cladding and Inconel spacer grid seems to be quite limited when sufficient oxygen is supplied. (author)

Reactions of metal-substituted myoglobins with excess electrons studied by pulse radiolysis and low-temperature gamma-radiolysis

International Nuclear Information System (INIS)

Miki, Hideho; Nakajima, Atushi; Ogasawara, Masaaki; Tamura, Mamoru

1990-01-01

Reactions of metal-substituted myoglobins with excess electrons in electron-pulse-irradiated aqueous solutions at room temperature and γ-irradiated aqueous matrices at 77 K were studied for the purpose of probing the functional role of heme iron. The rate constants for the reactions of various myoglobins with hydrated electrons were not much different from each other, and were close to those of diffusion-controlled reactions. In contrast, the reduction rates of myoglobins with dithionite depended markedly on the kind of central metals in the myoglobins. The difference was interpreted in terms of Marcus' theory for electron-transfer reactions. Effects of the 6-coordinate structure of the cobalt(III) species on the reaction with dithionite was also discussed. The steady-state optical-absorption measurements of γ-irradiated matrices containing cobaltimyoglobin at 77 K demonstrated the reduction of cobalt(III) species by excess electrons produced by the action of ionizing radiation. It was shown, by electron-spin resonance spectroscopy, that a 6-coordinated cobalt(II) species produced at 77 K transformed to a 5-coordinate one at higher temperatures, as reported previously. However, structural relaxation was not observed by optical spectroscopy either in the solutions or in the low-temperature matrices. It was concluded, therefore, that the intermediate 6-coordinate cobalt(II) species gave an optical absorption spectrum which was indistinguishable from that of the relaxed 5-coordinate cobalt(II) species. (author)

High temperature energy storage performances of methane reforming with carbon dioxide in a tubular packed reactor

International Nuclear Information System (INIS)

Lu, Jianfeng; Chen, Yuan; Ding, Jing; Wang, Weilong

2016-01-01

Highlights: • Energy storage of methane reforming in a tubular packed reactor is investigated. • Thermochemical storage efficiency approaches maximum at optimal temperature. • Sensible heat and heat loss play important roles in the energy storage system. • The reaction and energy storage models of methane reforming reactor are established. • The simulated methane conversion and energy storage efficiency fit with experiments. - Abstract: High temperature heat transfer and energy storage performances of methane reforming with carbon dioxide in tubular packed reactor are investigated under different operating conditions. Experimental results show that the methane reforming in tubular packed reactor can efficiently store high temperature thermal energy, and the sensible heat and heat loss besides thermochemical energy storage play important role in the total energy storage process. When the operating temperature is increased, the thermochemical storage efficiency first increases for methane conversion rising and then decreases for heat loss rising. As the operating temperate is 800 °C, the methane conversion is 79.6%, and the thermochemical storage efficiency and total energy efficiency can be higher than 47% and 70%. According to the experimental system, the flow and reaction model of methane reforming is established using the laminar finite-rate model and Arrhenius expression, and the simulated methane conversion and energy storage efficiency fit with experimental data. Along the flow direction, the fluid temperature in the catalyst bed first decreases because of the endothermic reaction and then increases for the heat transfer from reactor wall. As a conclusion, the maximum thermochemical storage efficiency will be obtained under optimal operating temperature and optimal flow rate, and the total energy efficiency can be increased by the increase of bed conductivity and decrease of heat loss coefficient.

Characteristics and mechanism of explosive reactions of Purex solvents with Nitric Acid at elevated temperatures

Energy Technology Data Exchange (ETDEWEB)

Miyata, Teijiro [Radiation Application Development Association, Tokai, Ibaraki (Japan); Takada, Junichi; Koike, Tadao; Tsukamoto, Michio; Watanabe, Koji [Department of Fuel Cycle Safety Research, Nuclear Safety Research Center, Tokai Research Establishment, Japan Atomic Energy Research Institute, Tokai, Ibaraki (Japan); Ida, Masaaki [JGC PLANTECH CO., LTD (Japan); Nakagiri, Naotaka [JGC Corp., Tokyo (Japan); Nishio, Gunji [Research Organization for Information Science and Technology, Tokai, Ibaraki (Japan)

2000-03-01

This investigation was undertaken to make clear the energetic properties and mechanism of explosive decomposition of Purex solvent systems (TBP/n-Dodecane/HNO{sub 3}) by Nitric Acid at elevated temperatures using a calorimetric technique (DSC, ARC) and a chromatographic technique (GC, GC/MS). The measurement of exothermic events of solvent-HNO{sub 3} reactions using DSC with a stainless steel sealed cell showed distinct two peaks with maxima at around 170 and 320degC, respectively. The peak at around 170degC was mainly attributed to the reactions of dealkylation products (n-butyl nitrate) of TBP and the solvent with nitric acid, and the peak at around 320degC was attributed to the exothermic decomposition of nitrated dodecanes formed in the foregoing exothermic reaction of dodecane with nitric acid. By using the data obtained in ARC experiments, activation energies of 123.2 and 152.5 kJ/mol were determined for the exothermic reaction of TBP with nitric acid and for the exothermic pyrolysis of n-butyl nitrate, respectively. Some possible pathways were considered for the explosive decomposition of TBP by nitric acid at elevated temperatures. (author)

Experimental and Numerical Studies on Self-Propagating High-Temperature Synthesis of Ta5Si3 Intermetallics

Directory of Open Access Journals (Sweden)

Chun-Liang Yeh

2015-09-01

Full Text Available Formation of Ta5Si3 by self-propagating high-temperature synthesis (SHS from elemental powder compacts of Ta:Si = 5:3 was experimentally and numerically studied. Experimental evidence showed that the increase of either sample density or preheating temperature led to the increase of combustion wave velocity and reaction temperature. The apparent activation energy, Ea ≈ 108 kJ/mol, was determined for the synthesis reaction. Based upon numerical simulation, the Arrhenius factor of the rate function, K0 = 2.5 × 107 s−1, was obtained for the 5Ta + 3Si combustion system. In addition, the influence of sample density on combustion wave kinetics was correlated with the effective thermal conductivity (keff of the powder compact. By adopting 0.005 ≤ keff/kbulk ≤ 0.016 in the computation model, the calculated combustion velocity and temperature were in good agreement with experimental data of the samples with compaction densities between 35% and 45% theoretical maximum density (TMD.

High-Temperature Structural Analysis Model of the Process Heat Exchanger for Helium Gas Loop (II)

International Nuclear Information System (INIS)

Song, Kee Nam; Lee, Heong Yeon; Kim, Chan Soo; Hong, Seong Duk; Park, Hong Yoon

2010-01-01

PHE (Process Heat Exchanger) is a key component required to transfer heat energy of 950 .deg. C generated in a VHTR (Very High Temperature Reactor) to the chemical reaction that yields a large quantity of hydrogen. Korea Atomic Energy Research Institute established the helium gas loop for the performance test of components, which are used in the VHTR, and they manufactured a PHE prototype to be tested in the loop. In this study, as part of the high temperature structural-integrity evaluation of the PHE prototype, which is scheduled to be tested in the helium gas loop, we carried out high-temperature structural-analysis modeling, thermal analysis, and thermal expansion analysis of the PHE prototype. The results obtained in this study will be used to design the performance test setup for the PHE prototype

Catalysis in high-temperature fuel cells.

Science.gov (United States)

Föger, K; Ahmed, K

2005-02-17

Catalysis plays a critical role in solid oxide fuel cell systems. The electrochemical reactions within the cell--oxygen dissociation on the cathode and electrochemical fuel combustion on the anode--are catalytic reactions. The fuels used in high-temperature fuel cells, for example, natural gas, propane, or liquid hydrocarbons, need to be preprocessed to a form suitable for conversion on the anode-sulfur removal and pre-reforming. The unconverted fuel (economic fuel utilization around 85%) is commonly combusted using a catalytic burner. Ceramic Fuel Cells Ltd. has developed anodes that in addition to having electrochemical activity also are reactive for internal steam reforming of methane. This can simplify fuel preprocessing, but its main advantage is thermal management of the fuel cell stack by endothermic heat removal. Using this approach, the objective of fuel preprocessing is to produce a methane-rich fuel stream but with all higher hydrocarbons removed. Sulfur removal can be achieved by absorption or hydro-desulfurization (HDS). Depending on the system configuration, hydrogen is also required for start-up and shutdown. Reactor operating parameters are strongly tied to fuel cell operational regimes, thus often limiting optimization of the catalytic reactors. In this paper we discuss operation of an authothermal reforming reactor for hydrogen generation for HDS and start-up/shutdown, and development of a pre-reformer for converting propane to a methane-rich fuel stream.

Low and High Temperature Combustion Chemistry of Butanol Isomers in Premixed Flames and Autoignition Systems

Energy Technology Data Exchange (ETDEWEB)

Sarathy, S M; Pitz, W J; Westbrook, C K; Mehl, M; Yasunaga, K; Curran, H J; Tsujimura, T; Osswald, P; Kohse-Hoinghaus, K

2010-12-12

Butanol is a fuel that has been proposed as a bio-derived alternative to conventional petroleum derived fuels. The structural isomer in traditional 'bio-butanol' fuel is n-butanol, but newer conversion technologies produce iso-butanol as a fuel. In order to better understand the combustion chemistry of bio-butanol, this study presents a comprehensive chemical kinetic model for all the four isomers of butanol (e.g., 1-, 2-, iso- and tert-butanol). The proposed model includes detailed high temperature and low temperature reaction pathways. In this study, the primary experimental validation target for the model is premixed flat low-pressure flame species profiles obtained using molecular beam mass spectrometry (MBMS). The model is also validated against previously published data for premixed flame velocity and n-butanol rapid compression machine and shock tube ignition delay. The agreement with these data sets is reasonably good. The dominant reaction pathways at the various pressures and temperatures studied are elucidated. At low temperature conditions, we found that the reaction of alphahydroxybutyl with O{sub 2} was important in controlling the reactivity of the system, and for correctly predicting C{sub 4} aldehyde profiles in low pressure premixed flames. Enol-keto isomerization reactions assisted by HO{sub 2} were also found to be important in converting enols to aldehydes and ketones in the low pressure premixed flames. In the paper, we describe how the structural features of the four different butanol isomers lead to differences in the combustion properties of each isomer.

New aspects of high energy heavy-ion transfer reactions

International Nuclear Information System (INIS)

Scott, D.K.

1975-03-01

New aspects of heavy ion reactions at incident energies in the region of 10 MeV/nucleon are discussed with an emphasis on the peripheral nature of the collisions, which leads to simplicities in the differential cross sections. The distortion of the peripheral distribution through the interference of direct and multistep processes is used to illustrate aspects of high energy reactions unique to heavy ions. The simplicities of the distributions for reactions on lighter nuclei are exploited to give new information about nuclear structure from direct and compound reactions at high energy. (16 figures, 32 references) (U.S.)

Temperature-dependent cross sections for meson-meson nonresonant reactions in hadronic matter

International Nuclear Information System (INIS)

Zhang Yiping; Xu Xiaoming; Ge Huijun

2010-01-01

We present a potential of which the short-distance part is given by one gluon exchange plus perturbative one- and two-loop corrections and of which the large-distance part exhibits a temperature-dependent constant value. The Schroedinger equation with this temperature-dependent potential yields a temperature dependence of the mesonic quark-antiquark relative-motion wave function and of meson masses. The temperature dependence of the potential, the wave function and the meson masses brings about temperature dependence of cross sections for the nonresonant reactions ππ→ρρ for I=2, KK→K*K* for I=1, KK*→K*K* for I=1, πK→ρK* for I=3/2, πK*→ρK* for I=3/2, ρK→ρK* for I=3/2 and πK*→ρK for I=3/2. As the temperature increases, the rise or fall of peak cross sections is determined by the increased radii of initial mesons, the loosened bound states of final mesons, and the total-mass difference of the initial and final mesons. The temperature-dependent cross sections and meson masses are parametrized.

Discovery of a Significant Acetone•Hydroperoxy Adduct Chaperone Effect and Its Impact on the Determination of Room Temperature Rate Constants for Acetonylperoxy/Hydroperoxy Self-Reactions and Cross Reaction Via Infrared Kinetic Spectroscopy.

Science.gov (United States)

Grieman, F. J.; Hui, A. O.; Okumura, M.; Sander, S. P.

2017-12-01

In order to model the upper troposphere/lower stratosphere in regions containing acetone properly, the kinetics of the acetonylperoxy/hydroperoxy self-reactions and cross reaction have been studied over a wide temperature range using Infrared Kinetic Spectroscopy. We report here the determination of different rate constants for the acetonylperoxy chemistry that we obtained at 298 K compared to currently accepted values. A considerable increase in the observed HO2 self-reaction rate constant due to rate enhancement via the chaperone effect from the reaction between HO2 and the (CH3)2CO•HO2 hydrogen-bonded adduct, even at room temperature, was discovered that was previously ignored. Correct determination of the acetonylperoxy and hydroperoxy kinetics must include this dependence of the HO2 self-reaction rate on acetone concentration. Via excimer laser flash photolysis to create the radical reactants, HO2 absorption was monitored in the infrared by diode laser wavelength modulation detection simultaneously with CH3C(O)CH2O2absorption monitored in the ultraviolet at 300 nm as a function of time. Resulting decay curves were fit concurrently first over a short time scale to obtain the rate constants minimizing subsequent product reactions. Modeling/fitting with a complete reaction scheme was then performed to refine the rate constants and test their veracity. Experiments were carried out over a variety of concentrations of acetone and methanol. Although no effect due to methanol concentration was found at room temperature, the rate constant for the hydroperoxy self-reaction was found to increase linearly with acetone concentration which is interpreted as the adduct being formed and resulting in a chaperone mechanism that enhances the self-reaction rate: (CH3)2CO·HO2 + HO2 → H2O2 + O2 + (CH3)2CO Including this effect, the resulting room temperature rate constants for the cross reaction and the acetonylperoxy self-reaction were found to be 2-3 times smaller than

A High Temperature Liquid Plasma Model of the Sun

Directory of Open Access Journals (Sweden)

Robitaille P.-M.

2007-01-01

Full Text Available In this work, a liquid model of the Sun is presented wherein the entire solar mass is viewed as a high density/high energy plasma. This model challenges our current understanding of the densities associated with the internal layers of the Sun, advocating a relatively constant density, almost independent of radial position. The incompressible nature of liquids is advanced to prevent solar collapse from gravitational forces. The liquid plasma model of the Sun is a non-equilibrium approach, where nuclear reactions occur throughout the solar mass. The primary means of addressing internal heat transfer are convection and conduction. As a result of the convective processes on the solar surface, the liquid model brings into question the established temperature of the solar photosphere by highlighting a violation of Kirchhoff’s law of thermal emission. Along these lines, the model also emphasizes that radiative emission is a surface phenomenon. Evidence that the Sun is a high density/high energy plasma is based on our knowledge of Planckian thermal emission and condensed matter, including the existence of pressure ionization and liquid metallic hydrogen at high temperatures and pressures. Prior to introducing the liquid plasma model, the historic and scientific justifications for the gaseous model of the Sun are reviewed and the gaseous equations of state are also discussed.

Temperature measurements in thermonuclear plasmas; Mesures des temperatures dans les plasmas thermonucleaires

Energy Technology Data Exchange (ETDEWEB)

Breton, D [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1958-07-01

The temperatures needed to produce thermonuclear reactions are of the order of several million degrees Kelvin. Devising methods for measuring such temperatures has been the subject of research in many countries. In order to present the problem clearly and to demonstrate its importance, the author reviews the various conditions which must be fulfilled in order that reactions may be qualified as thermonuclear. The relationship between the temperature and the cross-section of the reactions is studied, and it is shown that the notion of temperature in the plasmas is complex, which leads to a consideration of the temperature of the ions and that of the electrons. None of the methods for the temperature measurements is completely satisfactory because of the hypotheses which must be made, and which are seldom fulfilled during high-intensity discharges in the plasmas. In practice it is necessary to use several methods simultaneously. (author) [French] Les temperatures necessaires pour produire des reactions thermonucleaires sont de l'ordre de plusieurs millions de degres Kelvin. Les methodes envisagees pour mesurer ces temperatures font l'objet de recherches dans de nombreux pays. Afin de preciser le probleme et de montrer son importance, l'auteur rappelle les conditions qui doivent etre reunies pour que des reactions puissent etre qualifiees thermonucleaires. Il etudie la relation entre la temperature et la section efficace des reactions et montre que la notion de temperature dans les plasmas est complexe, ce qui amene a considerer la temperature des ions et celle des electrons. Aucune des methodes de mesure des temperatures n'est completement satisfaisante en raison des hypotheses qu'elles exigent et qui sont rarement realisees lors des decharges a haute intensite dans les plasmas. En pratique, il est necessaire d'utiliser plusieurs methodes simultanement. (auteur)

Advances in catalysts for internal reforming in high temperature fuel cells

Science.gov (United States)

Dicks, A. L.

Catalytic steam reforming of natural gas is an attractive method of producing the hydrogen required by the present generation of fuel cells. The molten carbonate (MCFC) and solid oxide (SOFC) fuel cells operate at high enough temperatures for the endothermic steam reforming reaction to be carried out within the stack. For the MCFC, the conventional anodes have insufficient activity to catalyse the steam reforming of natural gas. For these cells, internal reforming can be achieved only with the addition of a separate catalyst, preferably located in close proximity to the anode. However, in the so-called `Direct Internal Reforming' configuration, attack from alkali in the MCFC may severely limit catalyst lifetime. In the case of the state-of-the-art SOFC, natural gas can be reformed directly on the nickel cermet anode. However, in the SOFC, temperature variations in the cell caused by the reforming reaction may limit the amount of internal reforming that can be allowed in practice. In addition, some external pre-reforming may be desirable to remove high molecular weight hydrocarbons from the fuel gas, which would otherwise crack to produce elemental carbon. Degradation of the SOFC anode may also be a problem when internal reforming is carried out. This has prompted several research groups to investigate the use of alternative anode materials.

Study on high temperature desulphurization (Part 1). Comparison of CaO, ZnO, and Fe sub 2 O sub 3 as absorbents at high temperatures

Energy Technology Data Exchange (ETDEWEB)

Yumura, Motoo; Furimsky, E. (National Chemical Lab. for Industry, Tsukuba, (Japan))

1989-06-29

CaO, ZnO, and Fe{sub 2}O{sub 3} were used as adsorbents for H{sub 2}S removal to compare the H{sub 2}S removal and decomposition capacities at high temperature, and their desulphurization characteritics and reaction mechanisms were clarified. Evaluation of H{sub 2}S removal capacity, with the break point used as criterion, showed that increasing the temperature from 600 to 800{sup 0}C increased the H{sub 2}S removal in the presence of CaO but decreased it in the presence of Fe{sub 2}O{sub 3}. For ZnO, the temperature change had little effect on its adsorption. The bulk adsorption capacity was the largest for Fe{sub 2}O{sub 3} followed by CaO and ZnO. When the results were normalized to a unit of surface area, the adsorption capacity for ZnO was the largest followed by Fe{sub 2}O{sub 3} and CaO. In the presence of CaO, adsorption and decomposition started in the early stages while the adsorption of H{sub 2}S was accompanied by its decomposition in the presence of ZnO or Fe{sub 2}O{sub 3}. H{sub 2}S and S are oxidized in the presence of Fe{sub 2}O{sub 3} to produce SO{sub 2}, but no such reaction occurs with CaO or ZnO because it is thermodynamically disadvantageous. 2 refs., 4 figs., 2 tabs.