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Sample records for 2-step thermal decomposition

  1. Thermal decomposition products of butyraldehyde

    NASA Astrophysics Data System (ADS)

    Hatten, Courtney D.; Kaskey, Kevin R.; Warner, Brian J.; Wright, Emily M.; McCunn, Laura R.

    2013-12-01

    The thermal decomposition of gas-phase butyraldehyde, CH3CH2CH2CHO, was studied in the 1300-1600 K range with a hyperthermal nozzle. Products were identified via matrix-isolation Fourier transform infrared spectroscopy and photoionization mass spectrometry in separate experiments. There are at least six major initial reactions contributing to the decomposition of butyraldehyde: a radical decomposition channel leading to propyl radical + CO + H; molecular elimination to form H2 + ethylketene; a keto-enol tautomerism followed by elimination of H2O producing 1-butyne; an intramolecular hydrogen shift and elimination producing vinyl alcohol and ethylene, a β-C-C bond scission yielding ethyl and vinoxy radicals; and a γ-C-C bond scission yielding methyl and CH2CH2CHO radicals. The first three reactions are analogous to those observed in the thermal decomposition of acetaldehyde, but the latter three reactions are made possible by the longer alkyl chain structure of butyraldehyde. The products identified following thermal decomposition of butyraldehyde are CO, HCO, CH3CH2CH2, CH3CH2CH=C=O, H2O, CH3CH2C≡CH, CH2CH2, CH2=CHOH, CH2CHO, CH3, HC≡CH, CH2CCH, CH3C≡CH, CH3CH=CH2, H2C=C=O, CH3CH2CH3, CH2=CHCHO, C4H2, C4H4, and C4H8. The first ten products listed are direct products of the six reactions listed above. The remaining products can be attributed to further decomposition reactions or bimolecular reactions in the nozzle.

  2. Thermal decomposition mechanism of disilane.

    PubMed

    Yoshida, Kazumasa; Matsumoto, Keiji; Oguchi, Tatsuo; Tonokura, Kenichi; Koshi, Mitsuo

    2006-04-13

    Thermal decomposition of disilane was investigated using time-of-flight (TOF) mass spectrometry coupled with vacuum ultraviolet single-photon ionization (VUV-SPI) at a temperature range of 675-740 K and total pressure of 20-40 Torr. Si(n)H(m) species were photoionized by VUV radiation at 10.5 eV (118 nm). Concentrations of disilane and trisilane during thermal decomposition of disilane were quantitatively measured using the VUV-SPI method. Formation of Si(2)H(4) species was also examined. On the basis of pressure-dependent rate constants of disilane dissociation reported by Matsumoto et al. [J. Phys. Chem. A 2005, 109, 4911], kinetic simulation including gas-phase and surface reactions was performed to analyze thermal decomposition mechanisms of disilane. The branching ratio for (R1) Si(2)H(6) --> SiH(4) + SiH(2)/(R2) Si(2)H(6) --> H(2) + H(3)SiSiH was derived by the pressure-dependent rate constants. Temperature and reaction time dependences of disilane loss and formation of trisilane were well represented by the kinetic simulation. Comparison between the experimental results and the kinetic simulation results suggested that about 70% of consumed disilane was converted to trisilane, which was observed as one of the main reaction products under the present experimental conditions. PMID:16599440

  3. Thermal Decomposition Mechanism of Butyraldehyde

    NASA Astrophysics Data System (ADS)

    Hatten, Courtney D.; Warner, Brian; Wright, Emily; Kaskey, Kevin; McCunn, Laura R.

    2013-06-01

    The thermal decomposition of butyraldehyde, CH_3CH_2CH_2C(O)H, has been studied in a resistively heated SiC tubular reactor. Products of pyrolysis were identified via matrix-isolation FTIR spectroscopy and photoionization mass spectrometry in separate experiments. Carbon monoxide, ethene, acetylene, water and ethylketene were among the products detected. To unravel the mechanism of decomposition, pyrolysis of a partially deuterated sample of butyraldehyde was studied. Also, the concentration of butyraldehyde in the carrier gas was varied in experiments to determine the presence of bimolecular reactions. The results of these experiments can be compared to the dissociation pathways observed in similar aldehydes and are relevant to the processing of biomass, foods, and tobacco.

  4. Thermal decomposition of isooctyl nitrate

    SciTech Connect

    Pritchard, H.O.

    1989-03-01

    The diesel ignition improver DII-3, made by Ethyl Corporation, also known as isooctyl nitrate, is a mixture whose principal constituent (about 95%) is 2-ethyl hexyl nitrate. This note describes an investigation of the thermal decomposition that is not exhaustive, but that is intended to provide sufficient information on the rate and the mechanism so as to make possible the educated guesses needed for modeling the effect of isooctyl nitrate on the diesel ignition process. As is the case with other alkyl nitrates, the decomposition of the neat material is a complex one giving a complicated pressure versus time curve, unsuitable for a quick derivation of the rate constant. However, in the presence of toluene, whose intended purpose is to trap reactive free radicals and thereby simplify the overall mechanism, the pressure rises approximately exponentially to a limit; thus, on the assumption that the reaction is homogeneous and of first order, the rate constants can be determined from the half-life.

  5. Thermal decomposition of allylbenzene ozonide

    SciTech Connect

    Ewing, J.C.; Church, D.F.; Pryor, W.A. )

    1989-07-19

    Thermal decomposition of allylbenzene ozonide (ABO) at 98{degree}C in the liquid phase yields toluene, bibenzyl, phenylacetaldehyde, formic acid, and (benzyloxy)methyl formate as major products; benzyl chloride is formed when chlorinated solvents are employed. These products, as well as benzyl formate, are formed when ABO is decomposed at 37{degree}C. When the decomposition of ABO is carried out in the presence of 1-butanethiol, the product distribution changes: yields of toluene increase, no bibenzyl is formed, and decreases in yields of (benzyloxy)methyl formate, phenylacetladehyde, and benzyl chloride are observed. The decomposition of 1-octene ozonide (OTO) also was studied for comparison. The activation parameters for both ABO and OTO are similar (28.2 kcal/mol, log A = 13.6 and 26.6 kcal/mol, log A = 12.5, respectively); these data suggest that ozonides decompose by homolysis of the O-O bond, rather than by an alternative synchronous two-bond scission process. When ABO is decomposed at 37{degree}C in the presence of the spin traps 5,5-dimethyl-1-pyrroline N-oxide (DMPO) or 3,3,5,5-tetramethyl-1-pyrroline N-oxide (M{sub 4}PO), ESR signals are observed that are consistent with the trapping of benzyl and other carbon- and oxygen-centered radicals. A mechanism for the thermal decomposition of ABO that involves peroxide bond homolysis and subsequent {beta}-scission is proposed. Thus, Criegee ozonides decompose to give free radicals at quite modest temperatures.

  6. Thermal Decomposition Kinetics of HMX

    SciTech Connect

    Burnham, A K; Weese, R K

    2004-11-18

    Nucleation-growth kinetic expressions are derived for thermal decomposition of HMX from a variety of thermal analysis data types, including mass loss for isothermal and constant rate heating in an open pan and heat flow for isothermal and constant rate heating in open and closed pans. Conditions are identified in which thermal runaway is small to nonexistent, which typically means temperatures less than 255 C and heating rates less than 1 C/min. Activation energies are typically in the 140 to 165 kJ/mol range for open pan experiments and about 150 to 165 kJ/mol for sealed pan experiments. Our activation energies tend to be slightly lower than those derived from data supplied by the University of Utah, which we consider the best previous thermal analysis work. The reaction clearly displays more than one process, and most likely three processes, which are most clearly evident in open pan experiments. The reaction is accelerated in closed pan experiments, and one global reaction appears to fit the data well. Comparison of our rate measurements with additional literature sources for open and closed low temperature pyrolysis from Sandia gives a likely activation energy of 165 kJ/mol at 10% conversion.

  7. Thermal decomposition of HN(3).

    PubMed

    Knyazev, Vadim D; Korobeinichev, Oleg P

    2010-01-21

    The two-channel thermal decomposition of hydrogen azide, HN(3), was studied computationally. The reaction produces triplet or singlet NH and N(2). A model of the reaction was created on the basis of the theoretical study of the reaction potential-energy surface and microscopic reaction rates by Besora and Harvey (Besora, M.; Harvey, J. N. J. Chem. Phys. 2008, 129, 044303) and the experimental data on the energy-dependent rate constants reported by Foy et al. (Foy, B. R.; Casassa, M. P.; Stephenson, J. C.; King, D. S. J. Chem. Phys. 1990, 92, 2782) The properties of the model were adjusted to fit the calculated k(E) dependence to the experimental one. The experiments on thermal decomposition of HN(3) described in the literature were analyzed via kinetic modeling; the results of the analysis demonstrate that all but one of the existing studies were affected by contributions from secondary kinetics. The model of the reaction was then used in master-equation calculations of the pressure effects and the value of the critical energy transfer parameter, DeltaE(down), was adjusted based on agreement with the experimental k(T,P) data. Finally, the model was used to determine pressure- and temperature-dependent rate constants for both channels of reaction 1, which do not conform to the traditional formalism of low-pressure-limit and falloff description. Uncertainties of the model and their influence on the calculated thermal rate constant values were analyzed. Finally, parametrized expression for rate coefficients were provided for a wide range of temperatures and pressures. PMID:19916540

  8. Thermal Decomposition Kinetics of HMX

    SciTech Connect

    Burnham, A K; Weese, R K

    2004-05-05

    Nucleation-growth kinetic expressions are derived for thermal decomposition of HMX from a variety of types of data, including mass loss for isothermal and constant rate heating in an open pan, and heat flow for isothermal and constant rate heating in open and closed pans. Conditions are identified in which thermal runaway is small to nonexistent, which typically means temperatures less than 255 C and heating rates less than 1 C/min. Activation energies are typically in the 140 to 150 kJ/mol regime for open pan experiments and about 160 kJ/mol for sealed pan experiments. Our activation energies are about 10% lower than those derived from data supplied by the University of Utah, which we consider the best previous work. The reaction clearly displays more than one process, and most likely three processes, which are most clearly evident in open pan experiments. The reaction is accelerated for closed pan experiments, and one global reaction appears to fit the data well.

  9. Thermal Decomposition Kinetics of HMX

    SciTech Connect

    Burnham, A K; Weese, R K

    2005-03-17

    Nucleation-growth kinetic expressions are derived for thermal decomposition of HMX from a variety of types of data, including mass loss for isothermal and constant rate heating in an open pan, and heat flow for isothermal and constant rate heating in open and closed pans. Conditions are identified in which thermal runaway is small to nonexistent, which typically means temperatures less than 255 C and heating rates less than 1 C/min. Activation energies are typically in the 140 to 165 kJ/mol regime for open pan experiments and about 150-165 kJ/mol for sealed-pan experiments. The reaction clearly displays more than one process, and most likely three processes, which are most clearly evident in open pan experiments. The reaction is accelerated for closed pan experiments, and one global reaction fits the data fairly well. Our A-E values lie in the middle of the values given in a compensation-law plot by Brill et al. (1994). Comparison with additional open and closed low temperature pyrolysis experiments support an activation energy of 165 kJ/mol at 10% conversion.

  10. Unimolecular thermal decomposition of dimethoxybenzenes

    NASA Astrophysics Data System (ADS)

    Robichaud, David J.; Scheer, Adam M.; Mukarakate, Calvin; Ormond, Thomas K.; Buckingham, Grant T.; Ellison, G. Barney; Nimlos, Mark R.

    2014-06-01

    The unimolecular thermal decomposition mechanisms of o-, m-, and p-dimethoxybenzene (CH3O-C6H4-OCH3) have been studied using a high temperature, microtubular (μtubular) SiC reactor with a residence time of 100 μs. Product detection was carried out using single photon ionization (SPI, 10.487 eV) and resonance enhanced multiphoton ionization (REMPI) time-of-flight mass spectrometry and matrix infrared absorption spectroscopy from 400 K to 1600 K. The initial pyrolytic step for each isomer is methoxy bond homolysis to eliminate methyl radical. Subsequent thermolysis is unique for each isomer. In the case of o-CH3O-C6H4-OCH3, intramolecular H-transfer dominates leading to the formation of o-hydroxybenzaldehyde (o-HO-C6H4-CHO) and phenol (C6H5OH). Para-CH3O-C6H4-OCH3 immediately breaks the second methoxy bond to form p-benzoquinone, which decomposes further to cyclopentadienone (C5H4=O). Finally, the m-CH3O-C6H4-OCH3 isomer will predominantly follow a ring-reduction/CO-elimination mechanism to form C5H4=O. Electronic structure calculations and transition state theory are used to confirm mechanisms and comment on kinetics. Implications for lignin pyrolysis are discussed.

  11. Unimolecular thermal decomposition of dimethoxybenzenes

    SciTech Connect

    Robichaud, David J. Mukarakate, Calvin; Nimlos, Mark R.; Scheer, Adam M.; Ormond, Thomas K.; Buckingham, Grant T.; Ellison, G. Barney

    2014-06-21

    The unimolecular thermal decomposition mechanisms of o-, m-, and p-dimethoxybenzene (CH{sub 3}O-C{sub 6}H{sub 4}-OCH{sub 3}) have been studied using a high temperature, microtubular (μtubular) SiC reactor with a residence time of 100 μs. Product detection was carried out using single photon ionization (SPI, 10.487 eV) and resonance enhanced multiphoton ionization (REMPI) time-of-flight mass spectrometry and matrix infrared absorption spectroscopy from 400 K to 1600 K. The initial pyrolytic step for each isomer is methoxy bond homolysis to eliminate methyl radical. Subsequent thermolysis is unique for each isomer. In the case of o-CH{sub 3}O-C{sub 6}H{sub 4}-OCH{sub 3}, intramolecular H-transfer dominates leading to the formation of o-hydroxybenzaldehyde (o-HO-C{sub 6}H{sub 4}-CHO) and phenol (C{sub 6}H{sub 5}OH). Para-CH{sub 3}O-C{sub 6}H{sub 4}-OCH{sub 3} immediately breaks the second methoxy bond to form p-benzoquinone, which decomposes further to cyclopentadienone (C{sub 5}H{sub 4}=O). Finally, the m-CH{sub 3}O-C{sub 6}H{sub 4}-OCH{sub 3} isomer will predominantly follow a ring-reduction/CO-elimination mechanism to form C{sub 5}H{sub 4}=O. Electronic structure calculations and transition state theory are used to confirm mechanisms and comment on kinetics. Implications for lignin pyrolysis are discussed.

  12. Thermal decomposition of magnesium and calcium sulfates

    SciTech Connect

    Roche, S L

    1982-04-01

    The effect of catalyst on the thermal decomposition of MgSO/sub 4/ and CaSO/sub 4/ in vacuum was studied as a function of time in Knudsen cells and for MgSO/sub 4/, in open crucibles in vacuum in a Thermal Gravimetric Apparatus. Platinum and Fe/sub 2/O/sub 3/ were used as catalysts. The CaSO/sub 4/ decomposition rate was approximately doubled when Fe/sub 2/O/sub 3/ was present in a Knudsen cell. Platinum did not catalyze the CaSO/sub 4/ decomposition reaction. The initial decomposition rate for MgSO/sub 4/ was approximately 5 times greater than when additives were present in Knudsen cells but only about 1.5 times greater when decomposition was done in an open crucible.

  13. Mechanical, thermal and morphological characterization of polycarbonate/oxidized carbon nanofiber composites produced with a lean 2-step manufacturing process.

    PubMed

    Lively, Brooks; Kumar, Sandeep; Tian, Liu; Li, Bin; Zhong, Wei-Hong

    2011-05-01

    In this study we report the advantages of a 2-step method that incorporates an additional process pre-conditioning step for rapid and precise blending of the constituents prior to the commonly used melt compounding method for preparing polycarbonate/oxidized carbon nanofiber composites. This additional step (equivalent to a manufacturing cell) involves the formation of a highly concentrated solid nano-nectar of polycarbonate/carbon nanofiber composite using a solution mixing process followed by melt mixing with pure polycarbonate. This combined method yields excellent dispersion and improved mechanical and thermal properties as compared to the 1-step melt mixing method. The test results indicated that inclusion of carbon nanofibers into composites via the 2-step method resulted in dramatically reduced ( 48% lower) coefficient of thermal expansion compared to that of pure polycarbonate and 30% lower than that from the 1-step processing, at the same loading of 1.0 wt%. Improvements were also found in dynamic mechanical analysis and flexural mechanical properties. The 2-step approach is more precise and leads to better dispersion, higher quality, consistency, and improved performance in critical application areas. It is also consistent with Lean Manufacturing principles in which manufacturing cells are linked together using less of the key resources and creates a smoother production flow. Therefore, this 2-step process can be more attractive for industry. PMID:21780388

  14. Thermal decomposition hazard evaluation of hydroxylamine nitrate.

    PubMed

    Wei, Chunyang; Rogers, William J; Mannan, M Sam

    2006-03-17

    Hydroxylamine nitrate (HAN) is an important member of the hydroxylamine family and it is a liquid propellant when combined with alkylammonium nitrate fuel in an aqueous solution. Low concentrations of HAN are used primarily in the nuclear industry as a reductant in nuclear material processing and for decontamination of equipment. Also, HAN has been involved in several incidents because of its instability and autocatalytic decomposition behavior. This paper presents calorimetric measurement for the thermal decomposition of 24 mass% HAN/water. Gas phase enthalpy of formation of HAN is calculated using both semi-empirical methods with MOPAC and high-level quantum chemical methods of Gaussian 03. CHETAH is used to estimate the energy release potential of HAN. A Reactive System Screening Tool (RSST) and an Automatic Pressure Tracking Adiabatic Calorimeter (APTAC) are used to characterize thermal decomposition of HAN and to provide guidance about safe conditions for handling and storing of HAN. PMID:16154263

  15. THERMAL DECOMPOSITION OF URANIUM COMPOUNDS

    DOEpatents

    Magel, T.T.; Brewer, L.

    1959-02-10

    A method is presented of preparing uranium metal of high purity consisting contacting impure U metal with halogen vapor at between 450 and 550 C to form uranium halide vapor, contacting the uranium halide vapor in the presence of H/sub 2/ with a refractory surface at about 1400 C to thermally decompose the uranium halides and deposit molten U on the refractory surface and collecting the molten U dripping from the surface. The entire operation is carried on at a sub-atmospheric pressure of below 1 mm mercury.

  16. Thermal decomposition of carbon tetrachloride

    SciTech Connect

    Michael, J.V.; Lim, K.P. ); Kumaran, S.S.; Kiefer, J.H. )

    1993-03-04

    The first rate measurements of the thermal dissociation of CCl[sub 4] are reported. Three detection techniques were used in monitoring the reaction rate for various dilutions over a wide temperature range: (i) ARAS of product Cl atoms in reflected shock waves using 3.2--6.4 ppM of CCl[sub 4] in Ar over 1084--1705 K and 150--908 Torr, (ii) decay of CCl[sub 4] by molecular absorption of O-atom resonance radiation in reflected shock waves using 48--173 ppM of CCl[sub 4] in Ar over 1192--1733 K and 219--855 Torr, and (iii) laser schlieren density gradients in incident shock waves using 0.5 and 2% CCl[sub 4] in Kr over 1470--2186 K and 90--660 Torr. The second-order rates from ARAS and molecular absorption measurements for the bond fission reaction CCl[sub 4] [yields] CCl[sub 3] + Cl are in complete agreement with the laser schlieren results where they overlap. The temperature and pressure dependence of these rates is well characterized by Gorin model RRKM calculations using current [Delta]H[degrees][sub 0] = 67.71 kcal/mol for E[sub 0], derived from [Delta][sub f]H[degrees][sub 298] = 17.0 kcal/mol for for CCl[sub 3]. The low-pressure rate constant (k[sub 0]) derived from this RRKM fit is log k[sub 0] (cm[sup 3]/(mol s)) = 54.980 [minus] 10.624 log T [minus] 74.796 (kcal/mol)/2.303RT. These low-pressure rates require unusually large [beta][sub c] corresponding to a [l angle][Delta]E[r angle][sub down] = 1200 cm[sup [minus]1]. This may be a general feature of chlorocarbon dissociations. The ARAS data indicate that two Cl atoms are ultimately produced for each CCl[sub 4] that dissociates, with the second Cl atom forming slower than the first. Here all the measurements are consistent with a further dissociation of CCl[sub 3], CCl[sub 3] [yields] CCl[sub 2] + Cl, as the dominant source of secondary Cl-atom at a rate about 0.1 that of the primary fission. 31 refs., 9 figs., 2 tabs.

  17. Mechanism of the Thermal Decomposition of Furan

    NASA Astrophysics Data System (ADS)

    Vasiliou, Angayle; Ellison, G. Barney; Nimlos, Mark R.; Daily, John W.

    2009-06-01

    Both furan (C_4H_4O) and furfural (C_4H_3O-CHO) areimportant products in biomass pyrolysis. We have used a resistively-heated SiC tubular reactor with a 30 microseconds residence time to study the thermal cracking of furan. The decomposition products are identified by two independent techniques: 118.2 nm VUV photoionization mass spectroscopy and infrared spectroscopy. We observe three different thermal dissociation channels leading to: a) CH_3CCH + CO b) HCCH + CH_2CO c) HCCCH_2.

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

    SciTech Connect

    Maharrey, Sean; Wiese-Smith, Deneille; Highley, Aaron M.; Steill, Jeffrey D.; Behrens, Richard; Kay, Jeffrey J.

    2015-04-01

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

  19. Treatment of nitrocellulose by thermal decomposition

    SciTech Connect

    Campbell, R.K.; Freedman, D.L.; Kim, B.J.

    1999-07-01

    Waste fines generated during the manufacture of nitrocellulose (NC) are classified as a RCRA K044 hazardous waste due to their explosive properties. The objective of this study was to evaluate controlled thermal treatment of NC in order to render it nonhazardous and allow for more economical ultimate disposal. The results indicate that controlled thermal decomposition at 130--150 C is a technically feasible process. Rates improved significantly at higher temperatures. At 150 C, only 10 hours were needed to reduce the nitrogen content of NC from 13.7% to below 10% (versus 105 h at 130 C), a level found in many commercial, nonhazardous grades of NC. The air flow rate over the heated NC, and the moisture content of the NC or air above it had no discernible effect on rates of nitrogen removal. Greater mass loss from the NC than what was attributable to the nitro groups alone indicated that decomposition of the polymer backbone also occurred. This was confirmed by FTIR analyses, the appearance of CO{sub 2} in the off-gas, and a lack of correlation between percent nitrogen and heat of combustion. Samples of thermally treated NC containing 9.7% nitrogen failed three of the basic tests used by the Bureau of Explosives to ascertain explosive characteristics, indicating that the product was no longer hazardous based on its energetic properties. Although technically feasible, use of thermal decomposition to treat NC fines will most likely be restricted by safety concerns. Operating close to 130 C would mitigate the risk, but considerably extends the time required for treatment. The most suitable application of this technology may instead by treatment of NC-contaminated soils.

  20. Evaluation of a 2-step thermal method for separating organic and elemental carbon for radiocarbon analysis

    NASA Astrophysics Data System (ADS)

    Dusek, U.; Monaco, M.; Prokopiou, M.; Gongriep, F.; Hitzenberger, R.; Meijer, H. A. J.; Röckmann, T.

    2014-01-01

    We thoroughly characterized a system for thermal separation of organic carbon (OC) and elemental carbon (EC) for subsequent radiocarbon analysis. Different organic compounds as well as ambient aerosol filter samples were introduced into an oven system and combusted to CO2 in pure O2. The main objective was to test which combustion times and temperatures are best suited to separate OC and EC. The final separation step for OC was combustion at 360 °C for 15 min. Combustion at this temperature proved enough to remove several organic test substances from the filter (including high molecular weight humic acid) but did not remove substantial amounts of EC. For isolation of EC, OC first needs to be completely removed from the filter. This was achieved by water extraction of the filter, followed by combustion of the water insoluble OC at 360 °C and combustion at an intermediate temperature step of 2 min at 450 °C. This last step removed the most refractory OC together with some EC. Finally, the remaining EC was combusted to CO2 at 650 °C. The recovery of black carbon after the intermediate 450 °C step was approximately 80%. Several tests provided strong evidence that OC was removed efficiently during the intermediate temperature step: (i) brown carbon, indicative of refractory OC, was removed; (ii) the fraction modern of EC did not decrease significantly if the temperature of the intermediate step was further increased. Based on tests with various organic compounds, we estimated that charred organic carbon could contribute 4-8% to an elemental carbon sample that was isolated according to our method.

  1. Thermal Decomposition of Furan Generates Propargyl Radicals

    SciTech Connect

    Vasiliou, A.; Nimlos, M. R.; Daily, J. W.; Ellison, G. B.

    2009-07-01

    The thermal decomposition of furan has been studied by a 1 mm x 2 cm tubular silicon carbide reactor, C{sub 4}H{sub 4}O + {Delta} {yields} products. Unlike previous studies, these experiments are able to identify the initial furan decomposition products. Furan is entrained in either He or Ar carrier gas and is passed through a heated (1600 K) SiC tubular reactor. Furan decomposes during transit through the tubular reactor (approximately 65 {micro}s) and exits to a vacuum chamber. Within one nozzle diameter of leaving the nozzle, the gases cool to less than 50 K, and all reactions cease. The resultant molecular beam is interrogated by photoionization mass spectroscopy as well as infrared spectroscopy. Earlier G2(MP2) electronic structure calculations predicted that furan will thermally decompose to acetylene, ketene, carbon monoxide, and propyne at lower temperatures. At higher temperatures, these calculations forecast that propargyl radical could result. We observe all of these species (see Scheme 1). As the pressure in the tubular reactor is raised, the photoionization mass spectra show clear evidence for the formation of aromatic hydrocarbons.

  2. Steadily propagating slip pulses driven by thermal decomposition

    NASA Astrophysics Data System (ADS)

    Platt, John D.; Viesca, Robert C.; Garagash, Dmitry I.

    2015-09-01

    Geophysical observations suggest that mature faults weaken significantly at seismic slip rates. Thermal pressurization and thermal decomposition are two mechanisms commonly used to explain this dynamic weakening. Both rely on pore fluid pressurization with thermal pressurization achieving this through thermal expansion of native solids and pore fluid and thermal decomposition by releasing additional pore fluid during a reaction. Several recent papers have looked at the role thermal pressurization plays during a dynamically propagating earthquake, but no previous models have studied the role of thermal decomposition. In this paper we present the first solutions accounting for thermal decomposition during dynamic rupture, solving for steady state self-healing slip pulses propagating at a constant rupture velocity. First, we show that thermal decomposition leads to longer slip durations, larger total slips, and a distinctive along-fault slip rate profile. Next, we show that accounting for more than one weakening mechanism allows multiple steady slip pulses to exist at a given background stress, with some solutions corresponding to different balances between thermal pressurization and thermal decomposition, and others corresponding to activating a single reaction multiple times. Finally, we study how the rupture properties depend on the fault properties and show that the impact of thermal decomposition is largely controlled by the ratio of the hydraulic and thermal diffusivities χ = αhy/αth and the ratio of pore pressure generated to temperature rise buffered by the reaction Pr/Er.

  3. Thermal decomposition studies of halogenated organic compounds

    SciTech Connect

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

    1997-06-01

    Thermal decomposition results for CCl{sub 4}, CHCl{sub 3}, CH{sub 2}Cl{sub 2}, CH{sub 3}Cl, C{sub 3}H{sub 3}Cl, CFCl{sub 3}, CF{sub 2}Cl{sub 2}, CF{sub 3}Cl, CF{sub 2}HCl, CF{sub 3}I, CH{sub 3}I, C{sub 2}H{sub 5}I, C{sub 6}H{sub 5}I, and CCl{sub 2}O are presented. The results were obtained by shock tube techniques coupled with optical spectroscopic detection of transient species formed from dissociation. The method is illustrated with the CH{sub 3}I (+ Kr) {yields} CH{sub 3} + I (+ Kr) reaction where decomposition was monitored using I-atomic resonance absorption spectrometry (ARAS). Modern unimolecular rate theoretical analysis has been carried out on the present cases, and the conclusions from these calculations are discussed. Lastly, the possible destruction of halo-organics by incineration is considered and some implications are discussed.

  4. The Thermal Decomposition of Basic Copper(II) Sulfate.

    ERIC Educational Resources Information Center

    Tanaka, Haruhiko; Koga, Nobuyoshi

    1990-01-01

    Discussed is the preparation of synthetic brochantite from solution and a thermogravimetric-differential thermal analysis study of the thermal decomposition of this compound. Other analyses included are chemical analysis and IR spectroscopy. Experimental procedures and results are presented. (CW)

  5. Kinetics of thermal decomposition of surrogate solid wastes

    SciTech Connect

    Missoum, A.; Gupta, A.K.; Chen, J.; Keating, E.L.

    1996-12-31

    Decomposition behavior of different materials in a controlled environment at different heating rates are presented. The surrogate materials used are cellulose, polyethylene, polystyrene, polypropylene, nylon and bisphenol-A-polycarbonate. A series of tests were performed using a Perkin-Elmer 7 series thermal analysis system. Two heating rates of 10 C/minute and 100 C/minute were used. The temperature dependence and mass load characteristics of materials was obtained and used to obtain Arrhenius kinetic parameters and therefore the decomposition rates under defined conditions of pressure, temperature, environment, heating rate and waste composition. This information is helpful in characterizing and understanding the thermal decomposition properties of these materials during their thermal destruction. The decomposition rates are affected by the heating rate. The higher the heating rate the faster the decomposition. The results show that an increase in heating rate shifted thermal decomposition to higher temperatures and that the temperature at which maximum devolatilization began and ended was affected by heating rate. The kinetic parameters were calculated and the char yield from the different samples was less than 2% by weight except for polycarbonate which was around 5%. The remaining char in nylon and polycarbonate is attributed to the inert impurities in these materials. The thermal decomposition of the materials studied here could be related to their composition. It was found that polyethylene, polypropylene and polycarbonate have comparable decomposition rates over the same temperature range. Cellulose has the lowest decomposition rate and polystyrene has the highest.

  6. Thermal decomposition of bioactive sodium titanate surfaces

    NASA Astrophysics Data System (ADS)

    Ravelingien, Matthieu; Mullens, Steven; Luyten, Jan; Meynen, Vera; Vinck, Evi; Vervaet, Chris; Remon, Jean Paul

    2009-09-01

    Alkali-treated orthopaedic titanium surfaces have earlier shown to induce apatite deposition. A subsequent heat treatment under air improved the adhesion of the sodium titanate layer but decreased the rate of apatite deposition. Furthermore, insufficient attention was paid to the sensitivity of titanium substrates to oxidation and nitriding during heat treatment under air. Therefore, in the present study, alkali-treated titanium samples were heat-treated under air, argon flow or vacuum. The microstructure and composition of their surfaces were characterized to clarify what mechanism is responsible for inhibiting in vitro calcium phosphate deposition after heat treatment. All heat treatments under various atmospheres turned out to be detrimental for apatite deposition. They led to the thermal decomposition of the dense sodium titanate basis near the interface with the titanium substrate. Depending on the atmosphere, several forms of Ti yO z were formed and Na 2O was sublimated. Consequently, less exchangeable sodium ions remained available. This pointed to the importance of the ion exchange capacity of the sodium titanate layer for in vitro bioactivity.

  7. Thermal decomposition of metal p-hydroxybenzoates

    SciTech Connect

    Musaev, F.N.; Nadzhafov, G.N.; Mamedov, Kh.S.

    1986-11-01

    The thermal decomposition of the p-hydroxybenzoato complexes of divalent Mg, Mn, Co, Ni, Zn, Cu, Cd, and Ba has been studied under dynamic conditions in air in the 20-1000/sup 0/C temperature range. It has been found that the polyaquo complexes of Mg, Mn, Co, Ni, Zn, and Cu form a series of isomorphous compounds, whose structures consist of octahedral (M(H/sub 2/O)/sub 6//sup 2 +/ aquo ions /or an (Cd(H/sub 2/O)/sub 5/(PHB))/sub 2//sup +/ ion in the case of the Cd complex/, two anions of the acid, and two molecules of water of crystallization. The temperature ranges for the existence of the intermediate phases with low water contents and anhydrous phases have been established. The destruction of the anhydrous complexes takes place with the release of p-hydroxybenzoic acid and the formation of stable intermediates. The Mn, Cd, and Ni complexes decompose with the release of 1 mole of p-hydroxybenzoic acid, while the Mg, Co, and Zn complexes decompose with the release of 0.5 mole of the acid. The thermal stability of the anhydrous complexes decreases along the series Cd > Mn > Mg > Co > Cu > Zn > Ni. The stable phases have been identified by the methods of thin-layer chromatography, chemical analysis, x-ray diffraction analysis, and x-ray structural analysis, the crystal structure of the intermediate triaquo(hydroxybenzoato)manganese has been interpreted, and a structure has been proposed for anhydrous zinc p-hydroxybenzoate. It has been shown that the polyaquo Mn, Cd, and Zn complexes are converted into isomeric hydrates at 35-55/sup 0/C as a consequence of the displacement of the two weakly bound water molecules located in trans positions to one another to the hydration shell of the metal by O atoms of the COO groups of two p-hydroxybenzoate anions. The final thermolysis products are the oxides of the respective metals and BaCO/sub 3/. The Ni, Co, and Cu complexes initially decompose to the free metal, which then undergoes oxidation.

  8. Effect of mechanical dispersion of lignite on its thermal decomposition

    SciTech Connect

    Yusupov, T.S.; Shumskaya, L.G.; Burdukov, A.P.

    2007-09-15

    It is studied how the high-rate mechanical grinding affects thermal decomposition of lignite extracted from the Kansk-Achinsk Coal Basin. It has been shown that dispersion of lignite in the high energy intensive vibration-centrifugal and planetary mills causes formation of structures exhibiting lower thermal stability. That results in the shift of primary decomposition phenomena into the low-temperature region and, thus, in the higher reactivity of coals.

  9. Thermal Decomposition Characteristics of Orthorhombic Ammonium Perchlorate (o-AP)

    SciTech Connect

    Behrens, R.; Minier, L.

    1999-03-01

    Preliminary STMBMS and SEM results of the thermal decomposition of AP in the orthorhombic phase are presented. The overall decomposition is shown to be complex and controlled by both physical and chemical processes. The data show that the physical and chemical processes can be probed and characterized utilizing SEM and STMBMS. The overall decomposition is characterized by three distinguishing features: an induction period, and accelerator period and a deceleratory period. The major decomposition event occurs in the subsurface of the AP particles and propagates towards the center of the particle with time. The amount of total decomposition is dependent upon particle size and increases from 23% for {approximately}50{micro}m-diameter AP to 33% for {approximately}200{micro}m-diameter AP. A conceptual model of the physical processes is presented. Insight into the chemical processes is provided by the gas formation rates that are measured for the gaseous products. To our knowledge, this is the first presentation of data showing that the chemical and physical decomposition processes can be identified from one another, probed and characterized at the level that is required to better understand the thermal decomposition behavior of AP. Future work is planned with the goal of obtaining data that can be used to develop a mathematical description for the thermal decomposition of o-AP.

  10. Analysis of cured carbon-phenolic decomposition products to investigate the thermal decomposition of nozzle materials

    NASA Technical Reports Server (NTRS)

    Thompson, James M.; Daniel, Janice D.

    1989-01-01

    The development of a mass spectrometer/thermal analyzer/computer (MS/TA/Computer) system capable of providing simultaneous thermogravimetry (TG), differential thermal analysis (DTA), derivative thermogravimetry (DTG) and evolved gas detection and analysis (EGD and EGA) under both atmospheric and high pressure conditions is described. The combined system was used to study the thermal decomposition of the nozzle material that constitutes the throat of the solid rocket boosters (SRB).

  11. Thermal Decomposition of Copper (II) Calcium (II) Formate

    NASA Astrophysics Data System (ADS)

    Leyva, A. G.; Polla, G.; de Perazzo, P. K.; Lanza, H.; de Benyacar, M. A. R.

    1996-05-01

    The presence of different stages in the thermal decomposition process of CuCa(HCOO) 4has been established by means of TGA at different heating rates, X-ray powder diffraction of quenched samples, and DSC methods. During the first stage, decomposition of one of the two copper formate structural units contained in the unit cell takes place. The presence of CuCa 2(HCOO) 6has been detected. Calcium formate structural units break down at higher temperatures; the last decomposition peak corresponds to the appearance of different calcium-copper oxides.

  12. The Products of the Thermal Decomposition of CH3CHO

    SciTech Connect

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

    2011-04-06

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

  13. Thermal decomposition behaviors of lignite by pyrolysis-FTIR

    SciTech Connect

    Feng, J.; Li, W.Y.; Xie, K.C.

    2006-01-21

    An in situ pyrolysis reactor combined with the Fourier transformation infrared spectrometer (PFTIR) technique is employed to study the coal structure and its thermal decomposition behaviors. The interface of pyroprobe with FTIR was designed delicately to ensure the path of the laser beam in FTIR was just 3 {mu}m above the coal sample, so any detection information of products from coal pyrolysis would be acquired previous to the secondary reaction. The PFTIR technique can be adopted to determine the activation energy of coal pyrolysis. Lignite coal has been used to evaluate this new method. The thermal decomposition behaviors of functional groups from lignite pyrolysis coincide with the first-order reaction.

  14. A coke oven model including thermal decomposition kinetics of tar

    SciTech Connect

    Munekane, Fuminori; Yamaguchi, Yukio; Tanioka, Seiichi

    1997-12-31

    A new one-dimensional coke oven model has been developed for simulating the amount and the characteristics of by-products such as tar and gas as well as coke. This model consists of both heat transfer and chemical kinetics including thermal decomposition of coal and tar. The chemical kinetics constants are obtained by estimation based on the results of experiments conducted to investigate the thermal decomposition of both coal and tar. The calculation results using the new model are in good agreement with experimental ones.

  15. Autocatalytic behavior of trimethylindium during thermal decomposition

    SciTech Connect

    McDaniel, A.H.; Allendorf, M.D.

    2000-02-01

    Pyrolysis of trimethylindium (TMIn) in a hot-wall flow-tube reactor has been investigated at temperatures between 573 and 723 K using a modulated molecular-beam mass-sampling technique and detailed numerical modeling. The TMIn was exposed to various mixtures of carrier gases: He, H{sub 2}, D{sub 2}, and C{sub 2}H{sub 4}, in an effort to elucidated the behavior exhibited by this compound in different chemical environments. The decomposition of TMIn is a heterogeneous, autocatalytic process with an induction period that is carrier-gas dependent and lasts on the order of minutes. After activation of the tube wall, the thermolysis exhibits a steady-state behavior that is surface mediated. This result is contrary to prior literature reports, which state that decomposition occurs in the gas phase via successive loss of the CH{sub 3} ligands. This finding also suggests that the bond dissociation energy for the (CH{sub 3}){sub 2}In-CH{sub 3} bond derived from flow-tube investigations is erroneous and should be reevaluated.

  16. Thermal decomposition of substituted phenols in supercritical water

    SciTech Connect

    Martino, C.J.; Savage, P.E.

    1997-05-01

    The thermal decomposition of cresols, hydroxybenzaldehydes, nitrophenols, and benzenediols was studied in dilute aqueous solutions and in the absence of oxygen at 460 C and 250 atm for residence times around 10 s. Thermolysis under these conditions produced conversions of less than 10% for o-, m-, and p-cresol, whereas hydroxybenzaldehydes and nitrophenols were much more reactive. Global rate expressions are reported for the thermolysis of each hydroxybenzaldehyde and nitrophenol isomer. Phenol was a major product from the decomposition of all of the substituted phenols studied. For a given substituent, ortho-substituted phenols reacted more rapidly than the other isomers. For a given substituted position, nitrophenols reacted more rapidly than hydroxybenzaldehydes, which in turn reacted more rapidly than cresols. These results demonstrate that the treatment of CHO- and NO{sub 2}-substituted phenols by oxidation in supercritical water will involve the oxidation of thermal decomposition products in addition to the oxidation of the original compounds.

  17. Thermal decomposition of silane to form hydrogenated amorphous Si film

    DOEpatents

    Strongin, Myron; Ghosh, Arup K.; Wiesmann, Harold J.; Rock, Edward B.; Lutz, III, Harry A.

    1980-01-01

    This invention relates to hydrogenated amorphous silicon produced by thermally decomposing silano (SiH.sub.4) or other gases comprising H and Si, at elevated temperatures of about 1700.degree.-2300.degree. C., and preferably in a vacuum of about 10.sup.-8 to 10.sup.-4 torr, to form a gaseous mixture of atomic hydrogen and atomic silicon, and depositing said gaseous mixture onto a substrate outside said source of thermal decomposition to form hydrogenated amorphous silicon.

  18. The products of the thermal decomposition of CH3CHO

    NASA Astrophysics Data System (ADS)

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

    2011-07-01

    We have used a heated 2 cm × 1 mm SiC microtubular (μtubular) reactor to decompose acetaldehyde: CH3CHO + Δ → products. Thermal decomposition is followed at pressures of 75-150 Torr and at temperatures up to 1675 K, conditions that correspond to residence times of roughly 50-100 μs in the μtubular reactor. The acetaldehyde decomposition products are identified by two independent techniques: vacuum ultraviolet photoionization mass spectroscopy (PIMS) and infrared (IR) absorption spectroscopy after isolation in a cryogenic matrix. Besides CH3CHO, we have studied three isotopologues, CH3CDO, CD3CHO, and CD3CDO. We have identified the thermal decomposition products CH3 (PIMS), CO (IR, PIMS), H (PIMS), H2 (PIMS), CH2CO (IR, PIMS), CH2=CHOH (IR, PIMS), H2O (IR, PIMS), and HC≡CH (IR, PIMS). Plausible evidence has been found to support the idea that there are at least three different thermal decomposition pathways for CH3CHO; namely, radical decomposition: CH3CHO + Δ → CH3 + [HCO] → CH3 + H + CO; elimination: CH3CHO + Δ → H2 + CH2=C=O; isomerization/elimination: CH3CHO + Δ → [CH2=CH-OH] → HC≡CH + H2O. An interesting result is that both PIMS and IR spectroscopy show compelling evidence for the participation of vinylidene, CH2=C:, as an intermediate in the decomposition of vinyl alcohol: CH2=CH-OH + Δ → [CH2=C:] + H2O → HC≡CH + H2O.

  19. Thermal Decomposition of Copper (II) Dicalcium (II) Formate

    NASA Astrophysics Data System (ADS)

    de Perazzo, P. K.; Leyva, A. G.; Polla, G.; Parisi, F.; de Benyacar, M. A. R.; Smichowski, P.; Lanza, H.

    1997-09-01

    The unit cell obtained through X-ray single crystal analysis of the synthetized CuCa 2(HCOO) 6crystals corresponds to a supercell of the basic structure described by M. Sanchis et al.( Inorg. Chem.31, 2915 (1992)). Thermal decomposition of this sample shows two stages up to 300°C; the first can be related to the superstructure, and the second corresponds to the breaking down of the remaining copper formate structural units and the simultaneous decomposition of the sample.

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

    PubMed

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

    2015-07-16

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

  1. Strain localization driven by thermal decomposition during seismic shear

    NASA Astrophysics Data System (ADS)

    Platt, John D.; Brantut, Nicolas; Rice, James R.

    2015-06-01

    Field and laboratory observations show that shear deformation is often extremely localized at seismic slip rates, with a typical deforming zone width on the order of a few tens of microns. This extreme localization can be understood in terms of thermally driven weakening mechanisms. A zone of initially high strain rate will experience more shear heating and thus weaken faster, making it more likely to accommodate subsequent deformation. Fault zones often contain thermally unstable minerals such as clays or carbonates, which devolatilize at the high temperatures attained during seismic slip. In this paper, we investigate how these thermal decomposition reactions drive strain localization when coupled to a model for thermal pressurization of in situ groundwater. Building on Rice et al. (2014), we use a linear stability analysis to predict a localized zone thickness that depends on a combination of hydraulic, frictional, and thermochemical properties of the deforming fault rock. Numerical simulations show that the onset of thermal decomposition drives additional strain localization when compared with thermal pressurization alone and predict localized zone thicknesses of ˜7 and ˜13 μm for lizardite and calcite, respectively. Finally we show how thermal diffusion and the endothermic reaction combine to limit the peak temperature of the fault and that the pore fluid released by the reaction provides additional weakening of ˜20-40% of the initial strength.

  2. Biomass pyrolysis: Thermal decomposition mechanisms of furfural and benzaldehyde

    NASA Astrophysics Data System (ADS)

    Vasiliou, AnGayle K.; Kim, Jong Hyun; Ormond, Thomas K.; Piech, Krzysztof M.; Urness, Kimberly N.; Scheer, Adam M.; Robichaud, David J.; Mukarakate, Calvin; Nimlos, Mark R.; Daily, John W.; Guan, Qi; Carstensen, Hans-Heinrich; Ellison, G. Barney

    2013-09-01

    The thermal decompositions of furfural and benzaldehyde have been studied in a heated microtubular flow reactor. The pyrolysis experiments were carried out by passing a dilute mixture of the aromatic aldehydes (roughly 0.1%-1%) entrained in a stream of buffer gas (either He or Ar) through a pulsed, heated SiC reactor that is 2-3 cm long and 1 mm in diameter. Typical pressures in the reactor are 75-150 Torr with the SiC tube wall temperature in the range of 1200-1800 K. Characteristic residence times in the reactor are 100-200 μsec after which the gas mixture emerges as a skimmed molecular beam at a pressure of approximately 10 μTorr. Products were detected using matrix infrared absorption spectroscopy, 118.2 nm (10.487 eV) photoionization mass spectroscopy and resonance enhanced multiphoton ionization. The initial steps in the thermal decomposition of furfural and benzaldehyde have been identified. Furfural undergoes unimolecular decomposition to furan + CO: C4H3O-CHO (+ M) → CO + C4H4O. Sequential decomposition of furan leads to the production of HC≡CH, CH2CO, CH3C≡CH, CO, HCCCH2, and H atoms. In contrast, benzaldehyde resists decomposition until higher temperatures when it fragments to phenyl radical plus H atoms and CO: C6H5CHO (+ M) → C6H5CO + H → C6H5 + CO + H. The H atoms trigger a chain reaction by attacking C6H5CHO: H + C6H5CHO → [C6H6CHO]* → C6H6 + CO + H. The net result is the decomposition of benzaldehyde to produce benzene and CO.

  3. Thermal decomposition of carboxylate ionic liquids: trends and mechanisms.

    PubMed

    Clough, Matthew T; Geyer, Karolin; Hunt, Patricia A; Mertes, Jürgen; Welton, Tom

    2013-12-21

    The thermal stability of a series of dialkylimidazolium carboxylate ionic liquids has been investigated using a broad range of experimental and computational techniques. Ionic liquids incorporating fluoroalkyl carboxylate anions were found to have profoundly differing thermal stabilities and decomposition mechanisms compared with their non-fluorinated analogues. 1-Ethyl-3-methylimidazolium acetate was observed to largely decompose via an S(N)2 nucleophilic substitution reaction when under inert gas conditions, predominantly at the imidazolium methyl substituent. The Arrhenius equations for thermal decomposition of 1-ethyl-3-methylimidazolium acetate, and the C(2)-methylated analogue 1-ethyl-2,3-dimethylimidazolium acetate, were determined from isothermal Thermogravimetric Analysis experiments. The low thermal stability of 1-ethyl-3-methylimidazolium acetate has important implications for biomass experiments employing this ionic liquid. For these two ionic liquids, ion pair and transition state structures were optimised using Density Functional Theory. The activation barriers for the S(N)2 nucleophilic substitution mechanisms are in good agreement with the experimentally determined values. PMID:24173605

  4. Thermal decomposition of struvite and its phase transition.

    PubMed

    Bhuiyan, M Iqbal H; Mavinic, D S; Koch, F A

    2008-02-01

    Intentional crystallization of struvite, before it forms and accumulates on wastewater treatment equipment, solves an important and costly wastewater treatment problem and on the other hand, provides an environmentally sound and renewable nutrient source to the agricultural industry. Struvite was synthesized in the laboratory; it was also produced as pellets in a pilot-scale, fluidized bed reactor, using real centrate resulting from an anaerobic digester. The thermal decomposition of both synthetic struvite and struvite pellets was studied. The decomposition of struvite was found to be dependent on the rate of heating. Through gradual loss of ammonia and water molecules, ultimately struvite was found to be transformed into amorphous magnesium hydrogen phosphate. When struvite was heated in excess water, it was partially transformed into bobierrite, through the gradual loss of ammonia. It was transformed into monohydrate, dittmarite by losing its five water molecules of crystallization, when boiled in excess water. PMID:18022212

  5. Production and analysis of thermal decomposition products from polymeric materials

    NASA Technical Reports Server (NTRS)

    Chatfield, D. A.; Einhorn, I. N.; Hileman, F. D.; Futrell, J. H.; Voorhees, K. J.

    1978-01-01

    A description is presented of a strategy for analyzing the combustion process and the degradation products which are formed. One of three primary objectives in the study of polymer degradation is related to the characterization of the material to be studied and the investigation of the thermal behavior of the material. Another objective is concerned with the definition of the nature of the decomposition process by identification and quantitation of the degradation products. The third objective involves the determination of the mechanism and kinetics of the decomposition process. The methods of sample degradation include pyrolysis, oxidative degradation, flaming combustion, and the use of large-scale combustion chambers. Methods of chemical separation and identification are considered, taking into account low-boiling volatiles, high-boiling volatiles, and ancillary techniques.

  6. Programming Enhancements for Low Temperature Thermal Decomposition Workstation

    SciTech Connect

    Igou, R.E.

    1998-10-01

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

  7. Effects of Metallo-Organic Decomposition Agents on Thermal Decomposition and Electrical Conductivity of Low-Temperature-Curing Silver Paste

    NASA Astrophysics Data System (ADS)

    Lu, Chun-An; Lin, Pang; Lin, Hong-Ching; Wang, Sea-Fue

    2006-09-01

    Six low-temperature-curing silver pastes were prepared from silver flake, α-terpineol and various metallo-organic decomposition (MOD) compounds. The thermal decomposition behaviors of the pastes were determined. The microstructures and resistivities of screen-printed films on alumina substrate after thermal treatment were characterized and discussed. Results indicated that 2-ethylhexanoate possesses the lowest decomposition temperature (190.3 °C) among the MOD agents studied, and it forms silver particles to promote the linking of silver flake powders and thus reduces the resistivity to <13 μΩ\\cdotcm at a temperature as low as 200 °C.

  8. Thermal Decomposition of Benzyl Radical via Multiple Active Pathways

    NASA Astrophysics Data System (ADS)

    Buckingham, Grant; Robichaud, David; Ormond, Thomas; Nimlos, Mark R.; Daily, John W.; Ellison, Barney

    2014-06-01

    The thermal decomposition of benzyl radical (C6H5CH2) has been investigated using a combination infrared absorption spectroscopy in a neon matrix and 118.2 (10.487 eV) photoionization mass spectrometry. Both techniques are coupled with a heated tubular reactor to allow temperature control over the decomposition to indicate relative barrier heights of fragmentation pathways. Three possible chemical mechanisms have been considered. 1) Ring expansion to cycloheptatrienyl radical (C7H7) with subsequent breakdown to HCCH and C5H5, 2) isomerization to the substituted five-membered ring fulvenallene (C5H4=C=CH2), which is of interest to kinetic theorists and finally 3) hydrogen shift to form methyl-substituted phenyl radical, which can then form ortho-benzyne, diacetylene and other fragments. Benzyl radical is generated from two precursors, C6H5CH2CH3 and C6H5CH2Br, and both lead to the appearance of HCCH and C5H5. At slightly hotter temperatures peaks are observed at m/z 90, presumed to be C5H4=C=CH2, and 89, potentially the substituted propargyl C5H4=C=CH. Additionally, decomposition of isotopically substituted parent molecules C6H5CD2CD3 and C6D5CH2CH3 indicates C7H7 as an intermediate due to H/D ratios in fragment molecules.

  9. Mercer's spectral decomposition for the characterization of thermal parameters

    NASA Astrophysics Data System (ADS)

    Ahusborde, E.; Azaïez, M.; Belgacem, F. Ben; Palomo Del Barrio, E.

    2015-08-01

    We investigate a tractable Singular Value Decomposition (SVD) method used in thermography for the characterization of thermal parameters. The inverse problem to solve is based on the model of transient heat transfer. The most significant advantage is the transformation of the dynamic identification problem into a steady identification equation. The time dependence is accounted for by the SVD in a performing way. We lay down a mathematical foundation well fitted to this approach, which relies on the spectral expansion of Mercer kernels. This enables us to shed more light on most of its important features. Given its potentialities, the analysis we propose here might help users understanding the way the SVD algorithm, or the TSVD, its truncated version, operate in the thermal parameters estimation and why it is relevant and attractive. When useful, the study is complemented by some analytical and numerical illustrations realized within MATLAB's code.

  10. Thermal stability and kinetic of decomposition of nitrated HTPB.

    PubMed

    Wang, Qingfa; Wang, Li; Zhang, Xiangwen; Mi, Zhentao

    2009-12-30

    Nitrated HTPB (NHTPB) is a potential energetic binder to replace the conventional inert binder, HTPB, for the composite solid propellants and plastic bonded explosives (PBXs). The thermal stability of the NHTPB sample with 10% double bonds converted to dinitrate ester group (10% NHTPB) was evaluated by high-pressure differential scanning calorimeter (PDSC) measurement. The influences of pressure (0.1, 2.5 and 5.0 MPa) and the heating rate (4, 6, 8 and 10 degrees C min(-1)) on the DSC behavior of the 10% NHTPB sample were investigated. The decomposition temperature of this compound decreased with the increase of pressure, meanwhile, increased as the heating rate increasing. The thermal decomposition at 150-250 degrees C followed a first-order law. The kinetic parameters and thermodynamic parameters for the 10% NHTPB sample at 150-250 degrees C under ambient pressure were obtained from the DSC data by non-isothermal methods proposed by ASTM E698 and Flynn-Wall-Ozawa. The critical temperature for this compound was estimated at about 154 degrees C. PMID:19740607

  11. Thermal Decomposition of 3-Bromopropene. A Theoretical Kinetic Investigation.

    PubMed

    Tucceri, María E; Badenes, María P; Bracco, Larisa L B; Cobos, Carlos J

    2016-04-21

    A detailed kinetic study of the gas-phase thermal decomposition of 3-bromopropene over wide temperature and pressure ranges was performed. Quantum chemical calculations employing the density functional theory methods B3LYP, BMK, and M06-2X and the CBS-QB3 and G4 ab initio composite models provide the relevant part of the potential energy surfaces and the molecular properties of the species involved in the CH2═CH-CH2Br → CH2═C═CH2 + HBr (1) and CH2═CH-CH2Br → CH2═CH-CH2 + Br (2) reaction channels. Transition-state theory and unimolecular reaction rate theory calculations show that the simple bond fission reaction ( 2 ) is the predominant decomposition channel and that all reported experimental studies are very close to the high-pressure limit of this process. Over the 500-1400 K range a rate constant for the primary dissociation of k2,∞ = 4.8 × 10(14) exp(-55.0 kcal mol(-1)/RT) s(-1) is predicted at the G4 level. The calculated k1,∞ values lie between 50 to 260 times smaller. A value of 10.6 ± 1.5 kcal mol(-1) for the standard enthalpy of formation of 3-bromopropene at 298 K was estimated from G4 thermochemical calculations. PMID:27023718

  12. Reaction pathways for the thermal decomposition of methyl butanoate.

    PubMed

    Akbar Ali, Mohamad; Violi, Angela

    2013-06-21

    In recent years, biodiesel fuels, consisting of long-chain alkyl (methyl, ethyl, propyl) esters, have emerged as viable alternatives to petroleum-based fuels. From a combustion chemistry standpoint, there is great interest in developing accurate reaction models for these new molecules that can be used to predict their behaviors in various regimes. In this paper, we report a detailed study of the unimolecular decomposition pathways of methyl butanoate (MB), a short-chain ester that contains the basic chemical structure of biodiesel fuels. Using ab initio/DFT methods, we identified five homolytic fissions of C-C and C-O bonds and five hydrogen transfer reactions. Rate constants were determined using the G3B3 theory coupled with both variational transition state theory and Rice-Ramsperger-Kassel-Marcus/master equation simulations with hindered rotation corrections. Branching ratios in the temperature range 1500-2200 K indicate that the main pathway for thermal decomposition of MB is the reaction CH3CH2CH2C(═O)OCH3 → C2H5 + CH2C(═O)OCH3. The results, in terms of reaction pathways and rate constants, can be used for future development of mechanisms for long alkyl-chain esters. PMID:23679139

  13. Decomposition model for phonon thermal conductivity of a monatomic lattice

    NASA Astrophysics Data System (ADS)

    Evteev, Alexander V.; Momenzadeh, Leila; Levchenko, Elena V.; Belova, Irina V.; Murch, Graeme E.

    2014-12-01

    An analytical treatment of decomposition of the phonon thermal conductivity of a crystal with a monatomic unit cell is developed on the basis of a two-stage decay of the heat current autocorrelation function observed in molecular dynamics simulations. It is demonstrated that the contributions from the acoustic short- and long-range phonon modes to the total phonon thermal conductivity can be presented in the form of simple kinetic formulas, consisting of products of the heat capacity and the average relaxation time of the considered phonon modes as well as the square of the average phonon velocity. On the basis of molecular dynamics calculations of the heat current autocorrelation function, this treatment allows for a self-consistent numerical evaluation of the aforementioned variables. In addition, the presented analysis allows, within the Debye approximation, for the identification of the temperature range where classical molecular dynamics simulations can be employed for the prediction of phonon thermal transport properties. As a case example, Cu is considered.

  14. Mechanism of thermal decomposition of 2-furyl radical

    NASA Astrophysics Data System (ADS)

    Poskrebyshev, Gregory A.

    2016-02-01

    Mechanism of thermal decomposition of 2-furyl radical is studied using UB3LYP, UBHandHLYP and UMP2/6-311++G(d, p) approaches. Thermodynamic properties of considered intermediates and products of 2-furyl radical decomposition are calculated. Two the most kinetically favorable channels of 2-furyl decomposition are found: cis-cis-5-radC(H)dbnd C(H)C(H)CO (P1) → C2H2 + radCHCO (1) and cis-trans-5-radC(H)dbnd C(H)(H)Cdbnd CO (P2) → CO + C3H3rad (2), where P1 and P2 are the intermediate products of 2-furyl radical decomposition C4H3Orad → P1 ↔ P2 ↔ trans-trans-5-radC(H)dbnd (H)CC(H)CO (P3). The values of equilibrium (Kp) and high pressure limits rate (k∞) constants of the reactions considered in the present work are calculated. The important values of k∞ = 2.85 ×1013(T/298.15) 1.05e -138.7/RT and = 2.7 ×1012(T/298.15) 1.05e -175.7/RTs-1 are estimated, respectively, for reactions P1 → C2H2 + radCHCO and P2 → H2C = radCC(H)CO (P4) → CO + C3H3rad. The values of Kp = 3.7 ×105(T/298.15) 4.14e -11.9/RT and 3.35(T/298.15) - 0.201e - 1.34/RT , respectively, for reactions C4H3Orad ↔ P1 and P1 ↔ P2 are determined. In addition, the importance of formation of most thermodynamically favorable intermediate P3 is reported and the value of Kp = 3.45 ×10-2(T/298.15) 0.317e 4.5/RT for reaction P2 ↔ P3 is calculated.

  15. Adsorption and thermal decomposition of phenol on Ni(110)

    NASA Astrophysics Data System (ADS)

    Russell, J. N.; Sarvis, S. S.; Morris, R. E.

    1995-09-01

    The thermal decomposition of phenol on Ni(110) between 150 and 800 K was investigated with temperature programmed desorption (TPD), low energy electron diffraction (LEED), and Auger electron spectroscopy (AES). After adsorption at 150 K, the phenol monolayer completely decomposed into H 2, CO, and adsorbed carbon upon heating to 800 K. Molecular phenol desorbed from an unreactive state at 225 K and from the multilayer at 200 K. The saturated reactive monolayer resulted in four H 2 desorption states, β1- β4. The β1-H 2 state observed between 250 and 350 K, resulted from OH bond scission and demonstrated the formation of a phenoxy species. A deuterium kinetic isotope effect (DKIE) for β1-hydrogen desorption indicated that OH bond scission occurs between 250 and 350 K. However, the absence of a DKIE in the reactive adsorption at 290 K of OH/OD and CH/CD labeled phenol showed that phenol chemisorbed on Ni(110) via the π bonds of the ring. The β2- β4-H 2 desorption states occurred in a continuum between 370 and 650 K and resulted from decomposition of the phenyl ring. The observation of a deuterium kinetic isotope effect for β2-H 2 desorption from 2,4,6- d3-phenol, compared to h6-phenol, and 3,5- d2-phenol indicated that scission of the CH bond in either the (2,6) or the 4 position on the ring was the rate limiting step. CO desorption began near 400 K, and continued to about 650 K, exhibiting the same general thermal desorption distribution as the β2- β4-H 2 desorption spectrum. In CO desorption, a DKIE indicated CH bond scission influenced the decomposition of the CC bonds in the ring which resulted in CO production. 13C labeling revealed that 60% of the CO bond units remained intact. At 650 K, the carbon residue had a graphitic Auger lineshape, and exhibited a LEED pattern that is consistent with graphite microcrystallites. The surface C dissolved into the bulk above 700 K.

  16. Investigation of the thermal decomposition of sulfuric acid containing inorganic impurities

    SciTech Connect

    Kogtev, S.E.; Nikandrov, I.S.; Borisenko, A.S.; Peretrutov, A.A.

    1986-09-20

    Oleum is recovered by thermal decomposition of sulfuric acid wastes to sulfur dioxide with conversion of the sulfur dioxide to oleum. The organic substances in sulfuric acid wastes can affect the thermal-decomposition indexes of sulfuric acid wastes. They studied the effect of toluene, nitrotoluene, benzoic acid, and carbon on the yield of sulfur dioxide and also the possibility of reduction of acid vapors by products of pyrolysis and incomplete combustion of hydrocarbons. It is shown that the yield of sulfur dioxide in thermal decomposition of hydrocarbon-containing sulfuric acid wastes can be increased if the process assumes the nature of reductive decomposition.

  17. Analysis of Siderite Thermal Decomposition by Differential Scanning Calorimetry

    NASA Technical Reports Server (NTRS)

    Bell, M. S.; Lin, I.-C.; McKay, D. S.

    2000-01-01

    Characterization of carbonate devolitilization has important implications for atmospheric interactions and climatic effects related to large meteorite impacts in platform sediments. On a smaller scale, meteorites contain carbonates which have witnessed shock metamorphic events and may record pressure/temperature histories of impact(s). ALH84001 meteorite contains zoned Ca-Mg-Fe-carbonates which formed on Mars. Magnetite crystals are found in the rims and cores of these carbonates and some are associated with void spaces leading to the suggestion by Brearley et al. that the crystals were produced by thermal decomposition of the carbonate at high temperature, possibly by incipient shock melting or devolitilization. Golden et al. recently synthesized spherical Mg-Fe-Ca-carbonates from solution under mild hydrothermal conditions that have similar carbonate compositional zoning to those of ALH84001. They have shown experimental evidence that the carbonate-sulfide-magnetite assemblage in ALH84001 can result from a multistep inorganic process involving heating possibly due to shock events. Experimental shock studies on calcium carbonate prove its stability to approx. 60 GPa, well in excess of the approx. 45 GPa peak pressures indicated by other shock features in ALH84001. In addition, Raman spectroscopy of carbonate globules in ALH84001 indicates no presence of CaO and MgO. Such oxide phases should be found associated with the magnetites in voids if these magnetites are high temperature shock products, the voids resulting from devolitilization of CO2 from calcium or magnesium carbonate. However, if the starting material was siderite (FeCO3), thermal breakdown of the ALH84001 carbonate at 470 C would produce iron oxide + CO2. As no documentation of shock effects in siderite exists, we have begun shock experiments to determine whether or not magnetite is produced by the decomposition of siderite within the < 45GPa pressure window and by the resultant thermal pulse to approx

  18. PCB decomposition and formation in thermal treatment plant equipment.

    PubMed

    Ishikawa, Yukari; Noma, Yukio; Yamamoto, Takashi; Mori, Yoshihito; Sakai, Shin-ichi

    2007-04-01

    In this study we investigated both the decomposition and unintentional formation of polychlorinated biphenyl congeners during combustion experiments of refuse-derived fuel (RDF) and automobile shredder residue (ASR) at several stages in thermal treatment plant equipment composed of a primary combustion chamber, a secondary combustion chamber, and other equipments for flue gas treatment. In both experiments, the unintentional formation of PCB occurred in the primary combustion chamber at the same time as the decomposition of PCB in input samples. By combusting RDF, non-ortho-PCB predominantly formed, whereas ortho-PCB and symmetric chlorinated biphenyls (e.g., #52/69, #87/108, and #151) tended to be decomposed. ASR formed the higher chlorinated biphenyls more than RDF. These by-products from ASR had no structural relation with ortho-chlorine. Lower chlorinated biphenyls appeared as predominant homologues at the final exit site, while all congeners from lower to higher chlorinated PCB were unintentionally formed as by-products in the primary combustion chamber. This result showed that the flue gas treatment equipments effectively removed higher chlorinated PCB. Input marker congeners of RDF were #11, #39, and #68, while those for ASR were #11, #101, #110/120, and #118. Otherwise, combustion marker congeners of RDF were #13/12, #35, #77, and #126, while those for ASR were #170, #194, #206, and #209. While the concentration of PCB increased significantly in the primary combustion chamber, the value of toxicity equivalency quantity for dioxin-like PCB decreased in the secondary combustion chamber and the flue gas treatment equipments. PMID:17134732

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

    SciTech Connect

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

    2010-12-10

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

  20. Thermal decomposition of ammonium nitrate in supercritical water

    SciTech Connect

    Luan, Li; Proesmans, P.I.; Buelow, S.J.

    1996-10-01

    Thermal decomposition of neat NH{sub 4}NO{sub 3} has been the subject of many investigations over the past years. The reaction process is surprisingly complicated and depends largely on the reaction environment. For example, trace amounts of NH{sub 3}, HNO{sub 3} and H{sub 2}O are shown to affect the reaction significantly. In this research, NH{sub 4}NO{sub 3} decompostion was investigated in supercritical water. Reactions were evaluated in the presence of additional components such as organic compounds (CH{sub 3}OH, CH{sub 3}COOH, phenol), KN(NO{sub 2}){sub 2}, H{sub 2}O{sub 2}. Experiments were performed at varying temperatures, reaction times, NH{sub 4}NO{sub 3}, H{sub 2}O{sub 2} and organic compound concentrations. Gaseous, liquid and solid products were collected and analysed. The experimental results provided insight of the reaction chemistry which will be discussed in detail.

  1. Kinetics of the Thermal Decomposition of Solid PETN

    SciTech Connect

    Miller, G. D.; Haws, L. D.; Dinegar, R. H.

    1982-08-01

    The thermal decomposition of PETN below its melting point has been investigated. Separate monitoring of six product gases allowed individual initial rates of reaction and activation energies to be calculated. The activation energies for the production of both N2O and H2O area between 50 and 56 kcal*mol-1, pointing to a single process operant over the entire temperature range 363 - 408 K. The other four observed products have activation energies that are significantly higher. The activation energies for CO2 and N2 formation are 65-66 kcal*mol-1 while those for the production of CO and [NO+NO2] are 71-75 kcal*mol-1. Whether these values represent two or only one additional mechanism is not clear; however, for the 2s width uncertainty limits overlap. The processes or process involved in the formation of CO2, N2, CO, and [NO + NO2] appear(s) to change at 373K, as a dramatic drop in activation energies is observed at lower temperatures.

  2. Thermal decomposition of Ti getter films from the DITE tokamak

    SciTech Connect

    Malinowski, M.E.

    1981-04-01

    The potential application of Ti gettering in tritium-using tokamaks will result in unacceptably high in-torus tritium inventories if the tritium cannot be recovered from the Ti thin films. To help assess the feasibility of tritium recovery by outgassing such films, several samples of getter films evaporated in the DITE tokamak were thermally decomposed in vacuum. Film samples from four different azimuthal torus positions were heated at approx.1/sup 0/C s/sup -1/ and all exhibited decomposition rate peaks at 410/sup 0/ +- 10/sup 0/C; every film had been fully decomposed by the time 475/sup 0/C was reached. Separate experiments showed that isothermal desorption at temperatures as low as 350/sup 0/C was sufficient to outgas such films in 10 min. Together with previous work on clean films, the present results indicated that films which have not been as heavily contaminated as the DITE samples could be desorbed in vacuum at temperatures between 250--350/sup 0/C in acceptably short times, and demonstrate that in situ outgassing of tritided films would be feasible.

  3. Thermal Decomposition of New and Aged LX-04 and PBX 9501

    SciTech Connect

    Tran, T D; Tarver, C; Idar, D J; Rodin, W A

    2002-04-09

    One-Dimensional-Time-To-Explosion (ODTX) experiments were conducted to study the thermal decomposition of new and aged LX-04, PBX 9501, HMX class 1 and class 2, Estane and EstaneBDNPA-F (PBX 950 1 plasticized-binder) materials. New and aged LX-04 showed comparable decomposition kinetics. The data for aged PBX 9501 showed slightly longer explosion times at equivalent temperatures. Analysis of the error in time measurement is complicated by several experimental factors but the small time change appears to be experimentally significant. The results suggest that aged PBX 9501 is slightly more thermally stable. The thermal decomposition of these materials were modeled using a coupled thermal and heat transport code (chemical TOPAZ) using separate kinetics for HMX and binder decomposition. The current kinetic models describe the longer explosion times by the loss of plasticizer-binder constituent, which was more thermally reactive.

  4. Thermal decomposition and oxidation of CH3OH.

    PubMed

    Lee, Pei-Fang; Matsui, Hiroyuki; Xu, Ding-Wei; Wang, Niann-Shiah

    2013-01-24

    Thermal decomposition of CH(3)OH diluted in Ar has been studied by monitoring H atoms behind reflected shock waves of 100 ppm CH(3)OH + Ar. The total decomposition rate k(1) for CH(3)OH + M → products obtained in this study is expressed as, ln(k(1)/cm(3) molecule(-1) s(-1)) = -(14.81 ± 1.22) - (38.86 ± 1.82) × 10(3)/T, over 1359-1644 K. The present result on k(1) is indicated to be substantially smaller than the extrapolation of the most of the previous experimental data but consistent with the published theoretical results [Faraday Discuss. 2002, 119, 191-205 and J. Phys. Chem. A 2007, 111, 3932-3950]. Oxidation of CH(3)OH has been studied also by monitoring H atoms behind shock waves of (0.35-100) ppm CH(3)OH + (100-400) ppm O(2) + Ar. For the low concentration CH(3)OH (below 10 ppm) + O(2) mixtures, the initial concentration of CH(3)OH is evaluated by comparing evolutions of H atoms in the same concentration of CH(3)OH with addition of 300 ppm H(2) diluted in Ar. The branching fraction for CH(3)OH + Ar → (1)CH(2) + H(2)O + Ar has been quantitatively evaluated from this comparative measurements with using recent experimental result on the yield of H atoms in the reaction of (1,3)CH(2) + O(2) [J. Phys. Chem. A 2012, 116, 9245-9254]; i.e., the branching fraction for the above reaction is evaluated as, φ(1a) = 0.20 ± 0.04 at T = 1880-2050 K, in the 1.3 and 3.5 ppm CH(3)OH + 100 ppm O(2) samples. An extended reaction mechanism for the pyrolysis and oxidation of CH(3)OH is constructed based on the results of the present study combined with the oxidation mechanism of natural gas [GRI-Mech 3.0]; evolution of H atoms can be predicted very well with this new reaction scheme over a wide concentration range for the pyrolysis (0.36-100 ppm CH(3)OH), and oxidation (0.36-100 ppm CH(3)OH + 100/400 ppm O(2)) of methanol. PMID:23244587

  5. Thermal decomposition of potassium and sodium ethylxanthates and the influence of nitrobenzene on this process

    SciTech Connect

    Gorbatov, V.V.; Gerega, V.F.; Bordzilovskii, V.Ya.; Borovoi, A.A.; Dergunov, Yu.I.

    1988-02-10

    The thermal decomposition of the alkylxanthates was described by a first-order kinetic equation up to a degree of conversion of 50%. Thermal decomposition studies of potassium alkylxanthates indicated that the rate constants of the decomposition of ROCS/sub 2/K in isopentyl alcohol increased and the activation energies decreased as the group R changed along the series CH/sub 3/, C/sub 2/H/sub 5/, C/sub 3/H/sub 7/, C/sub 4/H/sub 9/, (CH/sub 3/)/sub 3/CCH/sub 2/, and iso-C/sub 3/H/sub 7/. In this study of the influence of additions of nitrobenzene on the decomposition of potassium and sodium alkylxanthates its additions had an accelerating action on the thermal decomposition of ROCS/sub 2/M in isopentyl alcohol.

  6. Vaporisation and thermal decomposition of dialkylimidazolium halide ion ionic liquids.

    PubMed

    Lovelock, Kevin R J; Armstrong, James P; Licence, Peter; Jones, Robert G

    2014-01-28

    Vaporisation and liquid phase thermal decomposition, TD, of two halide ion ionic liquids, 1-octyl-3-methylimidazolium chloride, [C8C1Im]Cl, and 1-octyl-3-methylimidazolium iodide, [C8C1Im]I, are investigated using temperature programmed desorption (TPD) line of sight mass spectrometry (LOSMS) at ultra-high vacuum (UHV). The ability to use MS to distinguish between vaporisation and TD allows the thermodynamics/kinetics of both vaporisation and TD to be investigated within the same experiments. Vaporisation of both halide ion ionic liquids is demonstrated. For both [C8C1Im]Cl and [C8C1Im]I the vapour is shown to be composed of neutral ion pairs (NIPs). The enthalpy of vaporisation at temperature T, ΔvapHT, was experimentally determined as ΔvapH455 = 151 ± 10 kJ mol(-1) for [C8C1Im]Cl and ΔvapH480 = 149 ± 8 kJ mol(-1) for [C8C1Im]I. Extrapolation of ΔvapHT to the reference temperature, 298 K, gave ΔvapH298 = 166 ± 10 kJ mol(-1) for [C8C1Im]Cl and ΔvapH298 = 167 ± 8 kJ mol(-1) for [C8C1Im]I, higher than most ΔvapH298 values measured to date for other [C8C1Im](+)-containing ionic liquids. In addition, predictions of ΔvapH298 for other halide ion ionic liquids are made. Liquid phase TD is shown to proceed via nucleophilic substitution to give two sets of products: 1-octylimidazole and methylhalide, and 1-methylimidazole and 1-octylhalide. The activation energy of TD at a temperature T, Ea,TD,T, is measured for the nucleophilic substitution of [C8C1Im]I to give methyliodide; Ea,TD,480 = 136 ± 15 kJ mol(-1). Ea,TD,T is measured for the nucleophilic substitution of [C8C1Im]Cl to give methylchloride; Ea,TD,455 = 132 ± 10 kJ mol(-1). The fact that ΔvapHT and Ea,TD,T are the same (within error) for both ionic liquids is commented upon, and conclusions are drawn as to the thermal stability of these ionic liquids. PMID:24105256

  7. Thermal behaviors, nonisothermal decomposition reaction kinetics, thermal safety and burning rates of BTATz-CMDB propellant.

    PubMed

    Yi, Jian-Hua; Zhao, Feng-Qi; Wang, Bo-Zhou; Liu, Qian; Zhou, Cheng; Hu, Rong-Zu; Ren, Ying-Hui; Xu, Si-Yu; Xu, Kang-Zhen; Ren, Xiao-Ning

    2010-09-15

    The composite modified double base (CMDB) propellants (nos. RB0601 and RB0602) containing 3,6-bis (1H-1,2,3,4-tetrazol-5-yl-amino)-1,2,4,5-tetrazine (BTATz) without and with the ballistic modifier were prepared and their thermal behaviors, nonisothermal decomposition reaction kinetics, thermal safety and burning rates were investigated. The results show that there are three mass-loss stages in TG curve and two exothermic peaks in DSC curve for the BTATz-CMDB propellant. The first two mass-loss stages occur in succession and the temperature ranges are near apart, and the decomposition peaks of the two stages overlap each other, inducing only one visible exothermic peak appear in DSC curve during 350-550 K. The reaction mechanisms of the main exothermal decomposition processes of RB0601 and RB0602 are all classified as chemical reaction, the mechanism functions are f(alpha)=(1-alpha)(2), and the kinetic equations are dalpha/dt = 10(19.24)(1-alpha)(2)e(-2.32x10(4)/T) and dalpha/dt = 10(20.32)(1-alpha)(2)e(-2.32x10(4)/T). The thermal safety evaluation on the BTATz-CMDB propellants was obtained. With the substitution of 26% RDX by BTATz and with the help of the ballistic modifier in the CMDB propellant formulation, the burning rate can be improved by 89.0% at 8 MPa and 47.1% at 22 MPa, the pressure exponent can be reduced to 0.353 at 14-20 MPa. PMID:20542638

  8. Low-temperature thermal decomposition of large single crystals of ammonium perchlorate

    NASA Astrophysics Data System (ADS)

    Majda, Dorota; Korobov, Alexander; Filek, Urszula; Sulikowski, Bogdan; Midgley, Paul; Vowles, David; Klinowski, Jacek

    2008-03-01

    Similarities and differences in the thermal behaviour of deuterated and nondeuterated ammonium perchlorate provide insights into the mechanism of its thermal decomposition. Thermal decomposition of NHClO and NDClO always begins in the bulk of the crystals. In both cases decomposition stops when the degree of conversion is about 30%, giving porous products which undergo the same phase transition as the parent single crystals. Thermal decomposition of the deuterated sample is slower, the volume fraction of pores appears to be lower and the sample has a small quantity of 'snow' on the surface. These effects are best rationalized as caused by proton transfer at the intersections of dislocations in the bulk of the crystals.

  9. Decomposition

    USGS Publications Warehouse

    Middleton, Beth A.

    2014-01-01

    A cornerstone of ecosystem ecology, decomposition was recognized as a fundamental process driving the exchange of energy in ecosystems by early ecologists such as Lindeman 1942 and Odum 1960). In the history of ecology, studies of decomposition were incorporated into the International Biological Program in the 1960s to compare the nature of organic matter breakdown in various ecosystem types. Such studies still have an important role in ecological studies of today. More recent refinements have brought debates on the relative role microbes, invertebrates and environment in the breakdown and release of carbon into the atmosphere, as well as how nutrient cycling, production and other ecosystem processes regulated by decomposition may shift with climate change. Therefore, this bibliography examines the primary literature related to organic matter breakdown, but it also explores topics in which decomposition plays a key supporting role including vegetation composition, latitudinal gradients, altered ecosystems, anthropogenic impacts, carbon storage, and climate change models. Knowledge of these topics is relevant to both the study of ecosystem ecology as well projections of future conditions for human societies.

  10. Thermal decomposition pathways for 1,1-diamino-2,2-dinitroethene (FOX-7)

    NASA Astrophysics Data System (ADS)

    Booth, Ryan S.; Butler, Laurie J.

    2014-10-01

    In this study, we computationally investigate the initial and subsequent steps in the chemical mechanism for the gas-phase thermal decomposition of 1,1-diamino-2,2-dinitroethene (FOX-7). We determine the key exothermic step in the gas-phase thermal decomposition of FOX-7 and explore the similarities and differences between FOX-7 and other geminal dinitro energetic materials. The calculations reveal a mechanism for NO loss involving a 3-member cyclic intermediate, rather than a nitro-nitrite isomerization, that occurs in the radical intermediates formed throughout the decomposition mechanism.

  11. Formation of meteorite hydrocarbons from thermal decomposition of siderite (FeCO 3)

    NASA Astrophysics Data System (ADS)

    McCollom, Thomas M.

    2003-01-01

    Thermal decomposition of siderite has been proposed as a source of magnetite in martian meteorites. Laboratory experiments were conducted to evaluate the possibility that this process might also result in abiotic synthesis of organic compounds. Siderite decomposition in the presence of water vapor at 300°C generated a variety of organic products dominated by alkylated and hydroxylated aromatic compounds. The results suggest that formation of magnetite by thermal decomposition of siderite on the precursor rock of the martian meteorite ALH84001 would have been accompanied by formation of organic compounds and may represent a source of extraterrestrial organic matter in the meteorite and on Mars. The results also suggest that thermal decomposition of siderite during metamorphism could account for some of the reduced carbon observed in metasedimentary rocks from the early Earth.

  12. Thermal Decomposition Behavior of Ammonium Perchlorate and of an Ammonium-Perchlorate-Based Composite Propellant

    NASA Technical Reports Server (NTRS)

    Behrens, R.; Minier, L.

    1998-01-01

    The thermal decomposition of ammonium perchlorate (AP) and ammonium-perchlorate-based composite propellants is studied using the simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS) technique. The main objective of the present work is to evaluate whether the STMBMS can provide new data on these materials that will have sufficient detail on the reaction mechanisms and associated reaction kinetics to permit creation of a detailed model of the thermal decomposition process. Such a model is a necessary ingredient to engineering models of ignition and slow-cookoff for these AP-based composite propellants. Results show that the decomposition of pure AP is controlled by two processes. One occurs at lower temperatures (240 to 270 C), produces mainly H2O, O2, Cl2, N2O and HCl, and is shown to occur in the solid phase within the AP particles. 200(micro) diameter AP particles undergo 25% decomposition in the solid phase, whereas 20(micro) diameter AP particles undergo only 13% decomposition. The second process is dissociative sublimation of AP to NH3 + HClO4 followed by the decomposition of, and reaction between, these two products in the gas phase. The dissociative sublimation process occurs over the entire temperature range of AP decomposition, but only becomes dominant at temperatures above those for the solid-phase decomposition. AP-based composite propellants are used extensively in both small tactical rocket motors and large strategic rocket systems.

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

    SciTech Connect

    Behrens, R.; Minier, L.

    1998-03-24

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

  14. Thermal Decomposition of New and Aged LX-04 and PBX 9501

    SciTech Connect

    Tran, T D; Tarver, C; Idar, D J

    2002-03-25

    One-Dimensional-Time-To-Explosion (ODTX) experiments were conducted to study the thermal decomposition of aged LX-04, aged PBX 9501, HMX class 1 and class 2, Estane and Estane/BDNPA-F (PBX 950 1 plasticized-binder) materials. The tests involved heating 12.7 mm diameter spherical samples in pre-heated aluminum anvils until explosion. The times to explosion at different heating temperatures were compared to historical data on new LX-04 and PBX 9501 compounds to study any changes to their thermal stability. New and aged LX-04 showed comparable decomposition kinetics. The data for aged PBX 9501 showed slightly longer explosion times at equivalent temperatures. Analysis of the error in time measurement is limited and complicated by several experimental factors but the small time change appears to be experimentally significant. The thermal decomposition of these PBXs were modeled using a coupled thermal and heat transport code (chemical TOPAZ) using separate kinetics for HMX and binder decomposition. Separate decomposition models were developed for HMX and the reactive PBX 9501 binder component (1:1 Estane:BDNPA/F) based on the measured explosion times. Thermal aging models can describe longer explosion times by the loss of plasticizer-binder constituent which was more thermally reactive.

  15. Relationship between impact ignition sensitivity and kinetics of the thermal decomposition of solid propellants

    SciTech Connect

    Ho, S.Y.; Fong, C.W.

    1989-02-01

    The impact ignition sensitivities of a series of composite propellants and a cast double base (nitrocellulose-nitroglycerine) propellant were measured and related to the fracture behavior and thermal properties (decomposition kinetics, thermal stability, and burning rate) of the propellants. The kinetics of the thermal degradation of the propellants were studied over a temperature range of 30-450/sup 0/C at various heating rates. The composite propellants showed a two-step decomposition mechanism, the initial decomposition being due mainly to reactions involving the oxidizer. The major decomposition, which takes place at higher temperatures, was due to several simultaneous reactions involving the oxidizer, the binder, and their decomposition products. At heating rates of 5-15/sup 0/C min/sup -1/, the second-step decomposition followed 0.5-1-order kinetics, but at heating rates above 20/sup 0/C min/sup -1/, the reaction became zero order (attributed to autocatalysis). The critical impact velocity showed a very strong dependence on the fracture toughness of the propellant, whereas the slope of the plot of ignition probability versus impact velocity showed good correlation with the decomposition kinetics and thermal stability and, to some extent, with the burning rate of the propellant. The authors results suggest that two distinct mechanisms are involved in impact ignition: (1) an initiation step where fracture, viscoelastic/plastic deformation and cracking occur, and are means by which hot spots are formed (mechanical properties of the propellant predominate in this initiation step); and (2) a flame propagation step, which involves burning and is governed by several interrelated factors, such as the decomposition kinetics, thermal stability, and burning rate of the propellant.

  16. Low-temperature thermal decomposition of crystalline partly and completely deuterated ammonium perchlorate

    NASA Astrophysics Data System (ADS)

    Majda, Dorota; Korobov, Alexander; Filek, Urszula; Sulikowski, Bogdan; Midgley, Paul; Nicol, David A.; Klinowski, Jacek

    2011-03-01

    Although ammonium perchlorate, widely used as a rocket propellant, has been extensively investigated for many years, the mechanism of its thermal decomposition at low temperatures remains controversial. Examination of the thermal behaviour of large crystals of partly and completely deuterated ammonium perchlorate by DSC, SEM, TG and QMS reveals that the rates of thermal decomposition depend on the degree of deuteration and decrease in the sequence N[H/D] 4ClO 4 > NH 4ClO 4 > ND 4ClO 4.

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

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

  18. Thermal Decomposition of Gaseous Ammonium Nitrate at Low Pressure: Kinetic Modeling of Product Formation and Heterogeneous Decomposition of Nitric Acid

    NASA Astrophysics Data System (ADS)

    Park, J.; Lin, M. C.

    2009-10-01

    The thermal decomposition of ammonium nitrate, NH4NO3 (AN), in the gas phase has been studied at 423-56 K by pyrolysis/mass spectrometry under low-pressure conditions using a Saalfeld reactor coated with boric acid. The sublimation of NH4NO3 at 423 K was proposed to produce equal amounts of NH3 and HNO3, followed by the decomposition reaction of HNO3, HNO3 + M → OH + NO2 + M (where M = third-body and reactor surface). The absolute yields of N2, N2O, H2O, and NH3, which can be unambiguously measured and quantitatively calibrated under a constant pressure at 5-6.2 torr He are kinetically modeled using the detailed [H,N,O]-mechanism established earlier for the simulation of NH3-NO2 (Park, J.; Lin, M. C. Technologies and Combustion for a Clean Environment. Proc. 4th Int. Conf. 1997, 34-1, 1-5) and ADN decomposition reactions (Park, J.; Chakraborty, D.; Lin, M. C. Proc. Combust. Inst. 1998, 27, 2351-2357). Since the homogeneous decomposition reaction of HNO3 itself was found to be too slow to account for the consumption of reactants and the formation of products, we also introduced the heterogeneous decomposition of HNO3 in our kinetic modeling. The heterogeneous decomposition rate of HNO3, HNO3 + (B2O3/SiO2) → OH + NO2 + (B2O3/SiO2), was determined by varying its rate to match the modeled result to the measured concentrations of NH3 and H2O; the rate could be represented by k2b = 7.91 × 107 exp(-12 600/T) s-1, which appears to be consistent with those reported by Johnston and co-workers (Johnston, H. S.; Foering, L.; Tao, Y.-S.; Messerly, G. H. J. Am. Chem. Soc. 1951, 73, 2319-2321) for HNO3 decomposition on glass reactors at higher temperatures. Notably, the concentration profiles of all species measured could be satisfactorily predicted by the existing [H,N,O]-mechanism with the heterogeneous initiation process.

  19. Determination of the Thermal Decomposition Products of Terephthalic Acid by Using Curie-Point Pyrolyzer

    NASA Astrophysics Data System (ADS)

    Begüm Elmas Kimyonok, A.; Ulutürk, Mehmet

    2016-04-01

    The thermal decomposition behavior of terephthalic acid (TA) was investigated by thermogravimetry/differential thermal analysis (TG/DTA) and Curie-point pyrolysis. TG/DTA analysis showed that TA is sublimed at 276°C prior to decomposition. Pyrolysis studies were carried out at various temperatures ranging from 160 to 764°C. Decomposition products were analyzed and their structures were determined by gas chromatography-mass spectrometry (GC-MS). A total of 11 degradation products were identified at 764°C, whereas no peak was observed below 445°C. Benzene, benzoic acid, and 1,1‧-biphenyl were identified as the major decomposition products, and other degradation products such as toluene, benzophenone, diphenylmethane, styrene, benzaldehyde, phenol, 9H-fluorene, and 9-phenyl 9H-fluorene were also detected. A pyrolysis mechanism was proposed based on the findings.

  20. Thermal stability and decomposition mechanism of YBa 2Cu 4O 8

    NASA Astrophysics Data System (ADS)

    Isobe, M.; Suzuki, M.; Ami, T.; Tanaka, M.

    1991-12-01

    The thermal stability and decomposition mechanism of YBa 2Cu 4O 8 were studied by using TG, DTA and X-ray diffractometry. The results clearly show the correspondence between oxygen deficiency and phase stability. The decomposition activation energy at Po 2=1 atm was estimated as 2.18∗10 6J/mol by a kinetic analysis of the thermal gravity. This value indicates that the decomposition is very slow. The time dependence of mass loss could be also estimated at 900°C. We conclude that the Y 2Ba 4Cu 7O 15 phase appears only as an intermediate phase in the YBa 2Cu 4O 8 decomposition process, and that the Y 2Ba 4Cu 7O 15 phase is metastable at Po 2=1 atm.

  1. Thermal Decomposition Behaviors and Burning Characteristics of AN/Nitramine-Based Composite Propellant

    NASA Astrophysics Data System (ADS)

    Naya, Tomoki; Kohga, Makoto

    2015-04-01

    Ammonium nitrate (AN) has attracted much attention due to its clean burning nature as an oxidizer. However, an AN-based composite propellant has the disadvantages of low burning rate and poor ignitability. In this study, we added nitramine of cyclotrimethylene trinitramine (RDX) or cyclotetramethylene tetranitramine (HMX) as a high-energy material to AN propellants to overcome these disadvantages. The thermal decomposition and burning rate characteristics of the prepared propellants were examined as the ratio of AN and nitramine was varied. In the thermal decomposition process, AN/RDX propellants showed unique mass loss peaks in the lower temperature range that were not observed for AN or RDX propellants alone. AN and RDX decomposed continuously as an almost single oxidizer in the AN/RDX propellant. In contrast, AN/HMX propellants exhibited thermal decomposition characteristics similar to those of AN and HMX, which decomposed almost separately in the thermal decomposition of the AN/HMX propellant. The ignitability was improved and the burning rate increased by the addition of nitramine for both AN/RDX and AN/HMX propellants. The increased burning rates of AN/RDX propellants were greater than those of AN/HMX. The difference in the thermal decomposition and burning characteristics was caused by the interaction between AN and RDX.

  2. Numerical study of the accumulation dynamics of oil shale thermal decomposition products in the vicinity of a heating element

    NASA Astrophysics Data System (ADS)

    Knyazeva, A. G.; Maslov, A. L.

    2015-10-01

    This study proposes the model of thermal decomposition of oil shale heated by electrodes. Differences in thermal physical properties of phases (solid core and gas, reagents and decomposition products), flow of generated gases in pores, and thermal effects of decomposition reactions are taken into account. The consideration of concentration expansion phenomenon is one of the features of the described model. The solution was carried out numerically. The concentration change of intermediate and final reaction products were studied for various heating conditions.

  3. Thermal decomposition of energetic materials viewed via dynamic x-ray radiography

    SciTech Connect

    Smilowitz, L.; Henson, B. F.; Romero, J. J.; Oschwald, D.

    2014-01-13

    We describe the evolution of solid density, leading up to ignition in the slow thermal decomposition of the solid organic secondary explosive octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine. This work describes an x-ray radiographic diagnostic, allowing the study of solid density in a fully encased explosive heated to thermal explosion. The result of this study is the ability to observe and manipulate the ignition volume in a thermal explosion.

  4. Thermal decomposition of high-nitrogen energetic compounds: TAGzT and GUzT

    NASA Astrophysics Data System (ADS)

    Hayden, Heather F.

    The U.S. Navy is exploring high-nitrogen compounds as burning-rate additives to meet the growing demands of future high-performance gun systems. Two high-nitrogen compounds investigated as potential burning-rate additives are bis(triaminoguanidinium) 5,5-azobitetrazolate (TAGzT) and bis(guanidinium) 5,5'-azobitetrazolate (GUzT). Small-scale tests showed that formulations containing TAGzT exhibit significant increases in the burning rates of RDX-based gun propellants. However, when GUzT, a similarly structured molecule was incorporated into the formulation, there was essentially no effect on the burning rate of the propellant. Through the use of simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS) and Fourier-Transform ion cyclotron resonance (FTICR) mass spectrometry methods, an investigation of the underlying chemical and physical processes that control the thermal decomposition behavior of TAGzT and GUzT alone and in the presence of RDX, was conducted. The objective was to determine why GUzT is not as good a burning-rate enhancer in RDX-based gun propellants as compared to TAGzT. The results show that TAGzT is an effective burning-rate modifier in the presence of RDX because the decomposition of TAGzT alters the initial stages of the decomposition of RDX. Hydrazine, formed in the decomposition of TAGzT, reacts faster with RDX than RDX can decompose itself. The reactions occur at temperatures below the melting point of RDX and thus the TAGzT decomposition products react with RDX in the gas phase. Although there is no hydrazine formed in the decomposition of GUzT, amines formed in the decomposition of GUzT react with aldehydes, formed in the decomposition of RDX, resulting in an increased reaction rate of RDX in the presence of GUzT. However, GUzT is not an effective burning-rate modifier because its decomposition does not alter the initial gas-phase decomposition of RDX. The decomposition of GUzT occurs at temperatures above the melting point

  5. Thermal decomposition and vibrational spectroscopic aspects of pyridinium hexafluorophosphate (C5H5NHPF6)

    NASA Astrophysics Data System (ADS)

    Lekgoathi, M. D. S.; Kock, L. D.

    2016-12-01

    Thermal decomposition and vibrational spectroscopic properties of pyridinium hexafluorophosphate (C5H5NHPF6) have been studied. The structure of the compound is better interpreted as having a cubic space group, based on Raman and infrared vibrational spectroscopy experiments and group theoretical correlation data between site symmetry species and the spectroscopic space group. The 13C NMR data shows three significant signals corresponding to the three chemical environments expected on the pyridinium ring i.e. γ, β and α carbons, suggesting that the position of the anion must be symmetrical with respect to the pyridinium ring's C2v symmetry. The process of thermal decomposition of the compound using TGA methods was found to follow a contracting volume model. The activation energy associated with the thermal decomposition reaction of the compound is 108.5 kJ mol-1, while the pre exponential factor is 1.51 × 109 sec-1.

  6. Using mass defect plots as a discovery tool to identify novel fluoropolymer thermal decomposition products.

    PubMed

    Myers, Anne L; Jobst, Karl J; Mabury, Scott A; Reiner, Eric J

    2014-04-01

    Fire events involving halogenated materials, such as plastics and electronics, produce complex mixtures that include unidentified toxic and environmentally persistent contaminants. Ultrahigh-resolution mass spectrometry and mass defect filtering can facilitate compound identification within these complex mixtures. In this study, thermal decomposition products of polychlorotrifluoroethylene (PCTFE, [-CClF-CF2 -]n), a common commercial polymer, were analyzed by Fourier transform ion cyclotron resonance mass spectrometry. Using the mass defect plot as a guide, novel PCTFE thermal decomposition products were identified, including 29 perhalogenated carboxylic acid (PXCA, X = Cl,F) congener classes and 21 chlorine/fluorine substituted polycyclic aromatic hydrocarbon (X-PAH, X = Cl,F) congener classes. This study showcases the complexity of fluoropolymer thermal decomposition and the potential of mass defect filtering to characterize complex environmental samples. PMID:24719344

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

    PubMed

    Sotiriou, Georgios A; Singh, Dilpreet; Zhang, Fang; Chalbot, Marie-Cecile G; Spielman-Sun, Eleanor; Hoering, Lutz; Kavouras, Ilias G; Lowry, Gregory V; Wohlleben, Wendel; Demokritou, Philip

    2016-03-15

    Nano-enabled products (NEPs) are currently part of our life prompting for detailed investigation of potential nano-release across their life-cycle. Particularly interesting is their end-of-life thermal decomposition scenario. Here, we examine the thermal decomposition of widely used NEPs, namely thermoplastic nanocomposites, and assess the properties of the byproducts (released aerosol and residual ash) and possible environmental health and safety implications. We focus on establishing a fundamental understanding on the effect of thermal decomposition parameters, such as polymer matrix, nanofiller properties, decomposition temperature, on the properties of byproducts using a recently-developed lab-based experimental integrated platform. Our results indicate that thermoplastic polymer matrix strongly influences size and morphology of released aerosol, while there was minimal but detectable nano-release, especially when inorganic nanofillers were used. The chemical composition of the released aerosol was found not to be strongly influenced by the presence of nanofiller at least for the low, industry-relevant loadings assessed here. Furthermore, the morphology and composition of residual ash was found to be strongly influenced by the presence of nanofiller. The findings presented here on thermal decomposition/incineration of NEPs raise important questions and concerns regarding the potential fate and transport of released engineered nanomaterials in environmental media and potential environmental health and safety implications. PMID:26642449

  8. The Autocatalytic Behavior of Trimethylindium During Thermal Decomposition

    SciTech Connect

    Anthony H. McDaniel; M. D. Allendorf

    2000-02-02

    Pyrolysis of trimethylindium (TMIn) in a hot-wall flow-tube reactor has been investigated at temperatures between 573 and 723 K using a modulated molecular-beam mass-sampling technique and detailed numerical modeling. The TMIn was exposed to various mixtures of carrier gases: He, H{sub 2}, D{sub 2}, and C{sub 2}H{sub 4}, in an effort to elucidate the behavior exhibited by this compound in different chemical environments. The decomposition of TMIn is a heterogeneous, autocatalytic process with an induction period that is carrier-gas dependent and lasts on the order of minutes. After activation of the tube wall, the thermolysis exhibits a steady-state behavior that is surface mediated. This result is contrary to prior literature reports, which state that decomposition occurs in the gas phase via successive loss of the CH{sub 3} ligands. This finding also suggests that the bond dissociation energy for the (CH{sub 3}){sub 2}In-CH{sub 3} bond derived from flow-tube investigations is erroneous and should be reevaluated.

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

    PubMed

    Sun, Hongyan; Vaghjiani, Ghanshyam L

    2015-05-28

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

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

    NASA Astrophysics Data System (ADS)

    Sun, Hongyan; Vaghjiani, Ghanshyam L.

    2015-05-01

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

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

    SciTech Connect

    Sun, Hongyan; Vaghjiani, Ghanshyam G.

    2015-05-26

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

  12. Effect of nanoparticle size on the thermal decomposition thermodynamics in theory and experiment

    NASA Astrophysics Data System (ADS)

    Li, Wenjiao; Cui, Zixiang; Duan, Huijuan; Xue, Yongqiang

    2016-02-01

    Thermal decomposition reactions of nanoparticles are often concerned in the processes of preparation and application of nanomaterials. However, it is the nanoparticle size that leads to great difference in thermal decomposition thermodynamics between nanoparticles and corresponding bulk substances. In this paper, the decomposition model of a nanoparticle was established to investigate the theoretical size-dependent thermodynamics in nanoscale decomposition system, and the theoretical relations of the thermodynamic properties with particle size were, respectively, derived. In experiment, the decomposition thermodynamics of nanosized zinc carbonate particles was studied, and the influence regularities of particle size on thermodynamic quantities were obtained. The experimental results are in accordance with the corresponding theoretical thermodynamic relations. These results show that there is a striking effect of particle size on the decomposition thermodynamics. The thermodynamic properties decrease with the decrease of particle size, whereas the equilibrium constant and the molar heat capacity of reaction at constant volume increase; logarithm of the equilibrium constant, the heat capacity of reaction and the thermodynamic properties are linearly related to reciprocal of the particle diameter, respectively. In addition, the temperature coefficient of the heat capacity of reaction also has strong size dependence; that is, the temperature coefficient becomes smaller with the particle size decreasing.

  13. Thermal decomposition mechanisms of alkylimidazolium ionic liquids with cyano-functionalized anions.

    PubMed

    Chambreau, Steven D; Schenk, Adam C; Sheppard, Anna J; Yandek, Gregory R; Vaghjiani, Ghanshyam L; Maciejewski, John; Koh, Christine J; Golan, Amir; Leone, Stephen R

    2014-11-26

    Because of the unusually high heats of vaporization of room-temperature ionic liquids (RTILs), volatilization of RTILs through thermal decomposition and vaporization of the decomposition products can be significant. Upon heating of cyano-functionalized anionic RTILs in vacuum, their gaseous products were detected experimentally via tunable vacuum ultraviolet photoionization mass spectrometry performed at the Chemical Dynamics Beamline 9.0.2 at the Advanced Light Source. Experimental evidence for di- and trialkylimidazolium cations and cyano-functionalized anionic RTILs confirms thermal decomposition occurs primarily through two pathways: deprotonation of the cation by the anion and dealkylation of the imidazolium cation by the anion. Secondary reactions include possible cyclization of the cation and C2 substitution on the imidazolium, and their proposed reaction mechanisms are introduced here. Additional evidence supporting these mechanisms was obtained using thermal gravimetric analysis-mass spectrometry, gas chromatography-mass spectrometry, and temperature-jump infrared spectroscopy. In order to predict the overall thermal stability in these ionic liquids, the ability to accurately calculate both the basicity of the anions and their nucleophilicity in the ionic liquid is critical. Both gas phase and condensed phase (generic ionic liquid (GIL) model) density functional theory calculations support the decomposition mechanisms, and the GIL model could provide a highly accurate means to determine thermal stabilities for ionic liquids in general. PMID:25381899

  14. Polytypic transformations during the thermal decomposition of cobalt hydroxide and cobalt hydroxynitrate

    SciTech Connect

    Ramesh, Thimmasandra Narayan

    2010-06-15

    The isothermal decomposition of cobalt hydroxide and cobalt hydroxynitrate at different intervals of temperature leads to the formation of Co{sub 3}O{sub 4}. The phase evolution during the decomposition process was monitored using powder X-ray diffraction. The transformation of cobalt hydroxide to cobalt oxide occurs via three phase mixture while cobalt hydroxynitrate to cobalt oxide occurs through a two phase mixture. The nature of the sample and its preparation method controls the decomposition mechanism. The comparison of topotactical relationship between the precursors to the decomposed product has been reported in relation to polytypism. - Graphical abstract: Isothermal thermal decomposition studies of cobalt hydroxide and cobalt hydroxynitrate at different intervals of temperature show the metastable phase formed prior to Co{sub 3}O{sub 4} phase.

  15. Nitrated graphene oxide and its catalytic activity in thermal decomposition of ammonium perchlorate

    SciTech Connect

    Zhang, Wenwen; Luo, Qingping; Duan, Xiaohui; Zhou, Yong; Pei, Chonghua

    2014-02-01

    Highlights: • The NGO was synthesized by nitrifying homemade GO. • The N content of resulted NGO is up to 1.45 wt.%. • The NGO can facilitate the decomposition of AP and release much heat. - Abstract: Nitrated graphene oxide (NGO) was synthesized by nitrifying homemade GO with nitro-sulfuric acid. Fourier transform infrared spectroscopy (FTIR), laser Raman spectroscopy, CP/MAS {sup 13}C NMR spectra and X-ray photoelectron spectroscopy (XPS) were used to characterize the structure of NGO. The thickness and the compositions of GO and NGO were analyzed by atomic force microscopy (AFM) and elemental analysis (EA), respectively. The catalytic effect of the NGO for the thermal decomposition of ammonium perchlorate (AP) was investigated by differential scanning calorimetry (DSC). Adding 10% of NGO to AP decreases the decomposition temperature by 106 °C and increases the apparent decomposition heat from 875 to 3236 J/g.

  16. Organic and inorganic decomposition products from the thermal desorption of atmospheric particles

    NASA Astrophysics Data System (ADS)

    Williams, B. J.; Zhang, Y.; Zuo, X.; Martinez, R. E.; Walker, M. J.; Kreisberg, N. M.; Goldstein, A. H.; Docherty, K. S.; Jimenez, J. L.

    2015-12-01

    Atmospheric aerosol composition is often analyzed using thermal desorption techniques to evaporate samples and deliver organic or inorganic molecules to various designs of detectors for identification and quantification. The organic aerosol (OA) fraction is composed of thousands of individual compounds, some with nitrogen- and sulfur-containing functionality, and often contains oligomeric material, much of which may be susceptible to decomposition upon heating. Here we analyze thermal decomposition products as measured by a thermal desorption aerosol gas chromatograph (TAG) capable of separating thermal decomposition products from thermally stable molecules. The TAG impacts particles onto a collection and thermal desorption (CTD) cell, and upon completion of sample collection, heats and transfers the sample in a helium flow up to 310 °C. Desorbed molecules are refocused at the head of a GC column that is held at 45 °C and any volatile decomposition products pass directly through the column and into an electron impact quadrupole mass spectrometer (MS). Analysis of the sample introduction (thermal decomposition) period reveals contributions of NO+ (m/z 30), NO2+ (m/z 46), SO+ (m/z 48), and SO2+ (m/z 64), derived from either inorganic or organic particle-phase nitrate and sulfate. CO2+ (m/z 44) makes up a major component of the decomposition signal, along with smaller contributions from other organic components that vary with the type of aerosol contributing to the signal (e.g., m/z 53, 82 observed here for isoprene-derived secondary OA). All of these ions are important for ambient aerosol analyzed with the aerosol mass spectrometer (AMS), suggesting similarity of the thermal desorption processes in both instruments. Ambient observations of these decomposition products compared to organic, nitrate, and sulfate mass concentrations measured by an AMS reveal good correlation, with improved correlations for OA when compared to the AMS oxygenated OA (OOA) component. TAG

  17. Organic and inorganic decomposition products from the thermal desorption of atmospheric particles

    NASA Astrophysics Data System (ADS)

    Williams, Brent J.; Zhang, Yaping; Zuo, Xiaochen; Martinez, Raul E.; Walker, Michael J.; Kreisberg, Nathan M.; Goldstein, Allen H.; Docherty, Kenneth S.; Jimenez, Jose L.

    2016-04-01

    Atmospheric aerosol composition is often analyzed using thermal desorption techniques to evaporate samples and deliver organic or inorganic molecules to various designs of detectors for identification and quantification. The organic aerosol (OA) fraction is composed of thousands of individual compounds, some with nitrogen- and sulfur-containing functionality and, often contains oligomeric material, much of which may be susceptible to decomposition upon heating. Here we analyze thermal decomposition products as measured by a thermal desorption aerosol gas chromatograph (TAG) capable of separating thermal decomposition products from thermally stable molecules. The TAG impacts particles onto a collection and thermal desorption (CTD) cell, and upon completion of sample collection, heats and transfers the sample in a helium flow up to 310 °C. Desorbed molecules are refocused at the head of a gas chromatography column that is held at 45 °C and any volatile decomposition products pass directly through the column and into an electron impact quadrupole mass spectrometer. Analysis of the sample introduction (thermal decomposition) period reveals contributions of NO+ (m/z 30), NO2+ (m/z 46), SO+ (m/z 48), and SO2+ (m/z 64), derived from either inorganic or organic particle-phase nitrate and sulfate. CO2+ (m/z 44) makes up a major component of the decomposition signal, along with smaller contributions from other organic components that vary with the type of aerosol contributing to the signal (e.g., m/z 53, 82 observed here for isoprene-derived secondary OA). All of these ions are important for ambient aerosol analyzed with the aerosol mass spectrometer (AMS), suggesting similarity of the thermal desorption processes in both instruments. Ambient observations of these decomposition products compared to organic, nitrate, and sulfate mass concentrations measured by an AMS reveal good correlation, with improved correlations for OA when compared to the AMS oxygenated OA (OOA

  18. Fabrication of Porous Copper with Directional Pores through Thermal Decomposition of Compounds

    NASA Astrophysics Data System (ADS)

    Nakajima, Hideo; Ide, Takuya

    2008-02-01

    Lotus-type porous copper with aligned long cylindrical pores was fabricated by unidirectional solidification in an argon atmosphere. The hydrogen dissolved in molten copper through thermal decomposition of titanium hydride contained in the mold, which then formed hydrogen gas that evolved into the gas pores in the solidified copper. On the other hand, titanium may form oxides in the melt that serve as nucleation sites for insoluble hydrogen. The porosity and pore size decreased with increasing atmospheric argon pressure during the solidification, which can be explained by the Boyle-Charles law and the possible suppression of the decomposition due to external pressure. The addition of titanium hydride was more effective when it was added just before the melt solidified than when it was added to the melt. Moreover, the thermal decomposition method (TDM) is superior to the conventional fabrication method, which requires high pressure hydrogen gas. Thus, TDM is a promising fabrication technique for various lotus metals.

  19. The effect of a detonation nanodiamond coating on the thermal decomposition properties of RDX explosives.

    PubMed

    Tong, Yi; Liu, Rui; Zhang, Tonglai

    2014-09-01

    A well-dispersed and uniformly shaped detonation nanodiamond (DND) was produced and coated over micron scale RDX in various amounts to form four kinds of DND coating composites (NDRs). In order to confirm the optimal coating amount and its effect on the thermal properties, the thermal decomposition and kinetics were studied by DSC, TG and DPTA techniques. The critical temperature of thermal explosion (Tb) and the self accelerating decomposition temperature (T(SADT)) both exhibit an interesting volcano-shaped changing trend and rank in an increasing order of NDR4 < NDR1 < RDX < NDR3 < NDR2. This indicates that the DND coating amount, ranging from 1/7 to 1/5, provides NDRs with better thermal safety than RDX. The thermolytic kinetic parameters (Ea and A) and activation thermodynamic parameters (ΔS(≠), ΔH(≠) and ΔG(≠)) are sorted in the following order: NDR1 < NDR4 < NDR2 < NDR3. The gas emission and reaction rate constant of the initial thermal decomposition have the same order. The results show that the DND coating could improve the reactivity of the NDRs and the effect is proportional to the coating amount. However, excessive coating that is more than 1/3 conversely hinders decomposition and gas diffusion, like a layer of protective shell. The isoconversional activation energy (Ea) varies with the conversion extent (α) at the initial stage of α = 0.1-0.5, which indicates that the thermal decomposition of the NDRs is a multi-step process including the secondary reaction or catalytic reaction. However, the Ea values are almost independent of α when α = 0.6-0.9, with the mean values in an increasing order of NDR1 < NDR4 < NDR2 < NDR3. PMID:25027243

  20. Cellophane and filter paper as cellulosic support for silver nanoparticles and its thermal decomposition catalysis.

    PubMed

    da Silva Pereira, Bruna; Silva, Marcela Fernandes; Bittencourt, Paulo Rodrigo Stival; de Oliveira, Daniela Martins Fernandes; Pineda, Edgardo Alfonso Gómez; Hechenleitner, Ana Adelina Winkler

    2015-11-20

    Silver nanoparticles (AgNPs) have attracted great attention due to its optical, electrical and thermal properties. Cellulosic supports for these nanoparticles are of particular interest because of its availability, flexibility and biocompatibility. In this work, AgNPs were synthesized using two cellulosic materials, cellophane (CP) and filter paper (FP), as matrix support. Cellulosic materials were immersed in an aqueous solution of silver nitrate containing polyvinylpyrrolidone (PVP) and then reduced with hydroxylamine. The obtained nanocomposites (CP-AgNPs and FP-AgNPs) were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (DRX) and scanning electron microscopy (SEM). AgNPs of near 15nm anchored onto cellulosic surfaces were detected. The thermal properties of these materials were investigated through thermogravimetry (TG). Their kinetic of thermal decomposition was studied by the Vyasovkin method of dynamic isoconvertion, which indicated a catalytic effect of AgNPs in the cellulose thermal decomposition reaction. PMID:26344282

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Urea is well known to have a synergistic action with phosphorus-based flame retardants such as diammonium phosphate (DAP) in enhancing the flame retardant performance of cellulosic materials, but its effect on their thermal decomposition kinetics has not been thoroughly studied. In this study, the ...

  2. Effect of phosphorus and nitrogen on thermal decomposition kinetics of flame retardant cotton

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Four kinetic methods, Kissinger, Friedman, Flynn-Wall-Ozawa, and modified Coats-Redfern, were used to study the activation energy, Ea, of the thermal decomposition of greige cotton nonwoven fabric treated with diammonium phosphate (DAP) and urea. The results show that the Ea is significantly influen...

  3. Thermal decomposition reactions of cotton fabric treated with piperazine-phosphonates derivatives as a flame retardant

    Technology Transfer Automated Retrieval System (TEKTRAN)

    There has been a great scientific interest in exploring the great potential of the piperazine-phosphonates in flame retardant (FR) application on cotton fabric by investigating the thermal decomposition of cotton fabric treated with them. This research tries to understand the mode of action of the t...

  4. Method of forming semiconducting amorphous silicon films from the thermal decomposition of fluorohydridodisilanes

    DOEpatents

    Sharp, Kenneth G.; D'Errico, John J.

    1988-01-01

    The invention relates to a method of forming amorphous, photoconductive, and semiconductive silicon films on a substrate by the vapor phase thermal decomposition of a fluorohydridodisilane or a mixture of fluorohydridodisilanes. The invention is useful for the protection of surfaces including electronic devices.

  5. Thermal decomposition dynamics and severity of microalgae residues in torrefaction.

    PubMed

    Chen, Wei-Hsin; Huang, Ming-Yueh; Chang, Jo-Shu; Chen, Chun-Yen

    2014-10-01

    To figure out the torrefaction characteristics and weight loss dynamics of microalgae residues, the thermogravimetric analyses of two microalgae (Chlamydomonas sp. JSC4 and Chlorella sorokiniana CY1) residues are carried out. A parameter of torrefaction severity index (TSI) in the range of 0-1, in terms of weight loss ratio between a certain operation and a reference operation, is defined to indicate the degree of biomass thermal degradation due to torrefaction. The TSI profiles of the two residues are similar to each other; therefore, the parameter may be used to describe the torrefaction extents of various biomass materials. The curvature of TSI profile along light torrefaction is slight, elucidating its slight impact on biomass thermal degradation. The sharp curvature along severe torrefaction in the initial pretreatment period reveals that biomass upgraded with high temperature and short duration is more effective than using low temperature with long duration. PMID:25058302

  6. 2-Step IMAT and 2-Step IMRT in three dimensions

    SciTech Connect

    Bratengeier, Klaus

    2005-12-15

    In two dimensions, 2-Step Intensity Modulated Arc Therapy (2-Step IMAT) and 2-Step Intensity Modulated Radiation Therapy (IMRT) were shown to be powerful methods for the optimization of plans with organs at risk (OAR) (partially) surrounded by a target volume (PTV). In three dimensions, some additional boundary conditions have to be considered to establish 2-Step IMAT as an optimization method. A further aim was to create rules for ad hoc adaptations of an IMRT plan to a daily changing PTV-OAR constellation. As a test model, a cylindrically symmetric PTV-OAR combination was used. The centrally placed OAR can adapt arbitrary diameters with different gap widths toward the PTV. Along the rotation axis the OAR diameter can vary, the OAR can even vanish at some axis positions, leaving a circular PTV. The width and weight of the second segment were the free parameters to optimize. The objective function f to minimize was the root of the integral of the squared difference of the dose in the target volume and a reference dose. For the problem, two local minima exist. Therefore, as a secondary criteria, the magnitude of hot and cold spots were taken into account. As a result, the solution with a larger segment width was recommended. From plane to plane for varying radii of PTV and OAR and for different gaps between them, different sets of weights and widths were optimal. Because only one weight for one segment shall be used for all planes (respectively leaf pairs), a strategy for complex three-dimensional (3-D) cases was established to choose a global weight. In a second step, a suitable segment width was chosen, minimizing f for this global weight. The concept was demonstrated in a planning study for a cylindrically symmetric example with a large range of different radii of an OAR along the patient axis. The method is discussed for some classes of tumor/organ at risk combinations. Noncylindrically symmetric cases were treated exemplarily. The product of width and weight of

  7. Thermal decomposition of silane to form hydrogenated amorphous Si

    DOEpatents

    Strongin, M.; Ghosh, A.K.; Wiesmann, H.J.; Rock, E.B.; Lutz, H.A. III

    Hydrogenated amorphous silicon is produced by thermally decomposing silane (SiH/sub 4/) or other gases comprising H and Si, at elevated temperatures of about 1700 to 2300/sup 0/C, in a vacuum of about 10/sup -8/ to 10/sup -4/ torr. A gaseous mixture is formed of atomic hydrogen and atomic silicon. The gaseous mixture is deposited onto a substrate to form hydrogenated amorphous silicon.

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

    SciTech Connect

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

    2011-07-07

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

  9. Thermal Decomposition of the Solid Phase of Nitromethane: Ab Initio Molecular Dynamics Simulations

    NASA Astrophysics Data System (ADS)

    Chang, Jing; Lian, Peng; Wei, Dong-Qing; Chen, Xiang-Rong; Zhang, Qing-Ming; Gong, Zi-Zheng

    2010-10-01

    The Car-Parrinello molecular dynamics simulations were employed to investigate thermal decomposition of the solid nitromethane. It is found that it undergoes chemical decomposition at about 2200 K under ambient pressure. The initiation of reactions involves both proton transfer and commonly known C-N bond cleavage. About 75 species and 100 elementary reactions were observed with the final products being H2O, CO2, N2, and CNCNC. It represents the first complete simulation of solid-phase explosive reactions reported to date, which is of far-reaching implication for design and development of new energetic materials.

  10. Thermal decomposition pathway and desorption study of isopropanol and tert-butanol on Si(100)

    NASA Astrophysics Data System (ADS)

    Kim, Jaehyun; Kim, Kwansoo; Yong, Kijung

    2002-09-01

    Thermal decomposition pathway and desorption of isopropanol (IPA) and tert-butanol on Si(100) were studied using temperature programed desorption. Adsorbed alcohols studied were decomposed into atomic hydrogen and alkoxy on the surface. During heating the sample up to 1000 K, acetone, propylene, and hydrogen were desorbed as decomposition products of IPA on Si(100). Desorption pathways of IPA on Si(100) were largely consistent with those on metal surfaces: beta-hydride elimination reaction to acetone and C-O scission to propylene. For tert-butanol, which has no beta-hydrogen, isobutene and hydrogen were observed as main desorption products. copyright 2002 American Vacuum Society.

  11. gamma-Irradiation effects on the thermal decomposition behaviour and IR absorption spectra of piperacillin

    NASA Astrophysics Data System (ADS)

    Mahfouz, R. M.; Gaffar, M. A.; Abu El-Fadl, A.; Hamad, Ar. G. K.

    2003-11-01

    The thermal decomposition behaviour of unirradiated and pre-gamma-irradiated piperacillin (pipril) as a semi-synthetic penicillin antibiotic has been studied in the temperature range of (273-1072 K). The decomposition was found to proceed through three major steps both for unirradiated and gamma-irradiated samples. Neither appearance nor disappearance of new bands in the IR spectrum of piperacillin was recorded as a result of gamma-irradiation but only a decrease in the intensity of most bands was observed. A degradation mechanism was suggested to explain the bond rupture and the decrease in the intensities of IR bands of gamma-irradiated piperacillin.

  12. Catalytically enhanced thermal decomposition of chemically grown silicon oxide layers on Si(001)

    NASA Astrophysics Data System (ADS)

    Leroy, F.; Passanante, T.; Cheynis, F.; Curiotto, S.; Bussmann, E. B.; Müller, P.

    2016-03-01

    The thermal decomposition of Si dioxide layers formed by wet chemical treatment on Si(001) has been studied by low-energy electron microscopy. Independent nucleations of voids occur into the Si oxide layers that open by reaction at the void periphery. Depending on the voids, the reaction rates exhibit large differences via the occurrence of a nonlinear growth of the void radius. This non-steady state regime is attributed to the accumulation of defects and silicon hydroxyl species at the SiO2/Si interface that enhances the silicon oxide decomposition at the void periphery.

  13. Study of thermal decomposition of methyl ethyl ketone peroxide using DSC and simulation.

    PubMed

    Tseng, Jo-Ming; Chang, Ying-Yu; Su, Teh-Sheng; Shu, Chi-Min

    2007-04-11

    Methyl ethyl ketone peroxide (MEKPO) is a typical organic peroxide with thermally unstable nature that has been broadly employed in the manufacturing process of acrylic resins, as a hardening agent for fiberglass-reinforced plastics, and as a curing agent for unsaturated polyester resins. The aim of this study was to identify the characteristics of MEKPO 31 wt.% while mixing with contaminants, such as H(2)SO(4), HCl, and NaCl under runaway conditions. To acquire the thermal runaway data, DSC and a simulation were used for thermal analysis. The results showed that the thermal decomposition of MEKPO and MEKPO+H(2)SO(4) follows two stages. The first one can be modeled by using an empirical nth order rate equation. The second stage can be modeled as autocatalytic. MEKPO+HCl and MEKPO+NaCl included two independent autocatalytic reactions. The decomposition of MEKPO in the presence of Cl- ions (added in MEKPO either in the form of HCl or NaCl) follows a significantly different path, an earlier decomposition "onset" temperature, higher amount of generated thermal power and smaller temperature of no return (T(NR)) and time to maximum rate (TMR) values. Simulations based on experimental data indicated that the effect of H(2)SO(4) was the most dangerous contaminant on MEKPO 31 wt.%. However, the impact of Cl ions was also important. It is therefore recommended that the means of fire fighting employed for this substance to be free of Cl-. PMID:16905247

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

    PubMed

    Kim, Shin Hyuk; Nyande, Baggie W; Kim, Hyoun Soo; Park, Jung Su; Lee, Woo Jin; Oh, Min

    2016-05-01

    Demilitarization of waste explosives on a commercial scale has become an important issue in many countries, and this has created a need for research in this area. TNT, RDX and Composition B have been used as military explosives, and they are very sensitive to thermal shock. For the safe waste treatment of these high-energy and highly sensitive explosives, the most plausible candidate suggested has been thermal decomposition in a rotary kiln. This research examines the safe treatment of waste TNT, RDX and Composition B in a rotary kiln type incinerator with regard to suitable operating conditions. Thermal decomposition in this study includes melting, 3 condensed phase reactions in the liquid phase and 263 gas phase reactions. Rigorous mathematical modeling and dynamic simulation for thermal decomposition were carried out for analysis of dynamic behavior in the reactor. The results showed time transient changes of the temperature, components and mass of the explosives and comparisons were made for the 3 explosives. It was concluded that waste explosives subject to heat supplied by hot air at 523.15K were incinerated safely without any thermal detonation. PMID:26808250

  15. Chemical-decomposition models for the thermal explosion of confined HMX, TATB, RDX, and TNT explosives

    SciTech Connect

    McGuire, R.R.; Tarver, C.M.

    1981-03-26

    Chemical decomposition models have been deduced from the available chemical kinetic data on the thermal decomposition of HMX, TATB, RDX, and TNT. A thermal conduction model is used in which the thermal conductivity of the reacting explosive decreases linearly with the mass fraction reacted to that of the gaseous products. These reactive heat flow models are used to predict the time to explosion versus reciprocal temperature curves from several heavily confined explosive tests. Good agreement is obtained between experimental and calculated explosion times for the pure explosives HMX, TATB, RDX, and TNT, mixtures such as RX-26-AF (HMX/TATB), Octol (HMX/TNT), and Comp B (RDX/TNT), and for PBX 9404, an HMX-based explosive containing an energetic nitrocellulose binder.

  16. Preparation and thermal decomposition of yttrium hydroxide fluorides

    NASA Astrophysics Data System (ADS)

    Nishizawa, H.; Okumoto, K.; Mitsushio, T.

    1991-06-01

    The hydrothermal treatment of Y 2O 3 in KF solution at 400°C gave single phase of yttrium hydroxide fluorides, Y(OH) 3- xF x (0.65 < x < 1.43). Rietveld refinements of X-ray powder intensity data were performed for these solid solution phases. The hexagonal UCl 3 type system was retained over the whole range of x observed. All these solid solutions were thermally decomposed to oxide fluorides up to 500°C. Single phase of metastable cubic YOF and tetragonal YO 1- XF 1+2 x were obtained at 450°C for the solid solution with x = 0.98 and x = 1.43, respectively. The interatomic distances of anions (OH -,F -), IR data, and dehydration temperature of x < 1 phases supported the existence of hydrogen bonds.

  17. Decomposition of trifluoromethane in a dielectric barrier discharge non-thermal plasma reactor.

    PubMed

    Gandhi, M Sanjeeva; Mok, Y S

    2012-01-01

    The decomposition of trifluoromethane (CHF3) was carried out using non-thermal plasma generated in a dielectric barrier discharge (DBD) reactor. The effects of reactor temperature, electric power, initial concentration and oxygen content were examined. The DBD reactor was able to completely destroy CHF3 with alumina beads as a packing material. The decomposition efficiency increased with increasing electric power and reactor temperature. The destruction of CHF3 gradually increased with the addition of O2 up to 2%, but further increase in the oxygen content led to a decrease in the decomposition efficiency. The degradation pathways were explained with the identified by-products. The main by-products from CHF3 were found to be COF2, CF4, CO2 and CO although the COF2 and CF4 disappeared when the plasma were combined with alumina catalyst. PMID:23513444

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

    SciTech Connect

    Anderson, K.; Homsy, J.; Behrens, R.; Bulusu, S.

    1998-12-31

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

  19. Thermal Decomposition and Desorption of Diethylamido of Tetrakis (Diethylamido)Zirconium (TDEAZr) on Si(100)

    NASA Astrophysics Data System (ADS)

    Jeong, Joonhee; Lim, Sungwon; Yong, Kijung

    The thermal decomposition pathway and desorption of diethylamido of tetrakis (diethylamido)zirconium [TDEAZr, Zr(N(C2H5)2) 4] on Si(100) were studied using temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS). During TPD experiments, ethylethyleneimine (C2H5N=CHCH3), diethylamine [NH(C2H5)2], acetonitrile (CH3CN), ethylene (C2H4) and hydrogen (H2) desorbed as the main decomposition products of diethylamido, which was chemisorbed on Si(100) through the scission of the zirconium-diethylamido bond in TDEAZr. After TPD runs, the formation of silicon carbide and silicon nitride was observed on the surface by XPS, indicating that a complete decomposition of diethylamido proceeded. This could be a reaction pathway of C, N incorporation in the thin film growth using TDEAZr as a Zr precursor.

  20. Structure-dependent activities of Cu2O cubes in thermal decomposition of ammonium perchlorate

    NASA Astrophysics Data System (ADS)

    Luo, Xiao-Lin; Wang, Min-Juan; Yun, Le; Yang, Jie; Chen, Ya-Shao

    2016-03-01

    Catalytic activity of three kinds of Cu2O cubes with different structures for thermal decomposition of ammonium perchlorate (AP) has been investigated in this paper. Cu2O crystals in the form of cubic aggregate, mono-dispersed cube and {100} planes etched cube have been synthesized through a microwave-assisted solvothermal method by adjusting the composition of solvent. The decomposition of AP in the presence or absence of Cu2O cubes has been investigated non-isothermally through thermogravimetry and differential scanning calorimetry (DSC). The data obtained from DSC have been applied for the calculation and comparison of the kinetic parameters of AP decomposition process through a model-free approach. The obtained kinetic parameters have been used to predict the reaction rate and progress of AP with Cu2O cubes under isothermal conditions or at temperature mode corresponding to real climate changes.

  1. Thermal stability and kinetics of decomposition of ammonium nitrate in the presence of pyrite.

    PubMed

    Gunawan, Richard; Zhang, Dongke

    2009-06-15

    The interaction between ammonium nitrate based industrial explosives and pyrite-rich minerals in mining operations can lead to the occurrence of spontaneous explosion of the explosives. In an effort to provide a scientific basis for safe applications of industrial explosives in reactive mining grounds containing pyrite, ammonium nitrate decomposition, with and without the presence of pyrite, was studied using a simultaneous Differential Scanning Calorimetry and Thermogravimetric Analyser (DSC-TGA) and a gas-sealed isothermal reactor, respectively. The activation energy and the pre-exponential factor of ammonium nitrate decomposition were determined to be 102.6 kJ mol(-1) and 4.55 x 10(7)s(-1) without the presence of pyrite and 101.8 kJ mol(-1) and 2.57 x 10(9)s(-1) with the presence of pyrite. The kinetics of ammonium nitrate decomposition was then used to calculate the critical temperatures for ammonium nitrate decomposition with and without the presence of pyrite, based on the Frank-Kamenetskii model of thermal explosion. It was shown that the presence of pyrite reduces the temperature for, and accelerates the rate of, decomposition of ammonium nitrate. It was further shown that pyrite can significantly reduce the critical temperature of ammonium nitrate decomposition, causing undesired premature detonation of the explosives. The critical temperature also decreases with increasing diameter of the blast holes charged with the explosive. The concept of using the critical temperature as indication of the thermal stability of the explosives to evaluate the risk of spontaneous explosion was verified in the gas-sealed isothermal reactor experiments. PMID:19056177

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

    PubMed

    Nakano, Masayoshi; Wada, Takeshi; Koga, Nobuyoshi

    2015-09-24

    This study focused on the kinetic modeling of the thermal decomposition of sodium percarbonate (SPC, sodium carbonate-hydrogen peroxide (2/3)). The reaction is characterized by apparently different kinetic profiles of mass-loss and exothermic behavior as recorded by thermogravimetry and differential scanning calorimetry, respectively. This phenomenon results from a combination of different kinetic features of the reaction involving two overlapping mass-loss steps controlled by the physico-geometry of the reaction and successive endothermic and exothermic processes caused by the detachment and decomposition of H2O2(g). For kinetic modeling, the overall reaction was initially separated into endothermic and exothermic processes using kinetic deconvolution analysis. Then, both of the endothermic and exothermic processes were further separated into two reaction steps accounting for the physico-geometrically controlled reaction that occurs in two steps. Kinetic modeling through kinetic deconvolution analysis clearly illustrates the appearance of the net exothermic effect is the result of a slight delay of the exothermic process to the endothermic process in each physico-geometrically controlled reaction step. This demonstrates that kinetic modeling attempted in this study is useful for interpreting the exothermic behavior of solid-state reactions such as the oxidative decomposition of solids and thermal decomposition of oxidizing agent. PMID:26371394

  3. Thermal, solution and reductive decomposition of Cu-Al layered double hydroxides into oxide products

    SciTech Connect

    Britto, Sylvia; Vishnu Kamath, P.

    2009-05-15

    Cu-Al layered double hydroxides (LDHs) with [Cu]/[Al] ratio 2 adopt a structure with monoclinic symmetry while that with the ratio 0.25 adopt a structure with orthorhombic symmetry. The poor thermodynamic stability of the Cu-Al LDHs is due in part to the low enthalpies of formation of Cu(OH){sub 2} and CuCO{sub 3} and in part to the higher solubility of the LDH. Consequently, the Cu-Al LDH can be decomposed thermally (150 deg. C), hydrothermally (150 deg. C) and reductively (ascorbic acid, ambient temperature) to yield a variety of oxide products. Thermal decomposition at low (400 deg. C) temperature yields an X-ray amorphous residue, which reconstructs back to the LDH on soaking in water or standing in the ambient. Solution decomposition under hydrothermal conditions yields tenorite at 150 deg. C itself. Reductive decomposition yields a composite of Cu{sub 2}O and Al(OH){sub 3}, which on alkali-leaching of the latter, leads to the formation of fine particles of Cu{sub 2}O (<1 {mu}m). - Graphical abstract: SEM image of (a) the Cu{sub 2}O-Al(OH){sub 3} composite obtained on reductive decomposition of CuAl{sub 4}-LDH and (b) Cu{sub 2}O obtained on leaching of Al(OH){sub 3} from (a).

  4. Synthesis and structure characterization of chromium oxide prepared by solid thermal decomposition reaction.

    PubMed

    Li, Li; Yan, Zi F; Lu, Gao Q; Zhu, Zhong H

    2006-01-12

    Mesoporous chromium oxide (Cr2O3) nanocrystals were first synthesized by the thermal decomposition reaction of Cr(NO3)3.9H2O using citric acid monohydrate (CA) as the mesoporous template agent. The texture and chemistry of chromium oxide nanocrystals were characterized by N2 adsorption-desorption isotherms, FTIR, X-ray diffraction (XRD), UV-vis, and thermoanalytical methods. It was shown that the hydrate water and CA are the crucial factors in influencing the formation of mesoporous Cr2O3 nanocrystals in the mixture system. The decomposition of CA results in the formation of a mesoporous structure with wormlike pores. The hydrate water of the mixture provides surface hydroxyls that act as binders, making the nanocrystals aggregate. The pore structures and phases of chromium oxide are affected by the ratio of precursor-to-CA, thermal temperature, and time. PMID:16471518

  5. The thermal decomposition of methanol and methanethiol on the clean and modified Fe(110) surface

    SciTech Connect

    Batteas, J.D.; Rufael, T.S.; Friend, C.M.

    1996-10-01

    The thermal decomposition of methanol and methanethiol on the clean and modified Fe(110) surface has been examined using X-ray photoelectron spectroscopy, low-energy electron diffraction and temperature programmed reaction spectroscopy. Both methanethiol and methanol adsorb on the Fe(110) surface at 100 K with immediate cleavage of the terminal hydrogen to produce methylthiolate (CH{sub 3}S) and methoxy (CH{sub 3}O) coadsorbed with atomic hydrogen on the Fe surface. Heating the sample to 800 K produces gas phase methane and hydrogen, leaving a chemisorbed S overlayer in the case of methylthiolate, while methoxy decomposes via desorbing hydrogen and CO to leave a clean Fe surface. The influence of oxygen and sulfur pre-adsorption on the thermal decomposition of these species will also be described.

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

    NASA Astrophysics Data System (ADS)

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

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

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

    PubMed

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

    2015-07-30

    The thermal decomposition of titanium tetraisopropoxide (TTIP) is investigated using quantum chemistry, statistical thermodynamics, and equilibrium composition analysis. A set of 981 Ti-containing candidate species are proposed systematically on the basis of the thermal breakage of bonds within a TTIP molecule. The ground state geometry, vibrational frequencies and hindrance potentials are calculated for each species at the B97-1/6-311+G(d,p) level of theory. Thermochemical data are computed by applying statistical thermodynamics and, if unknown, the standard enthalpy of formation is estimated using balanced reactions. Equilibrium composition calculations are performed under typical combustion conditions for premixed flames. The thermodynamically stable decomposition products for different fuel mixtures are identified. A strong positive correlation is found between the mole fractions of Ti species containing carbon and the TTIP precursor concentration. PMID:26114649

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

    SciTech Connect

    Sun, Hongyan E-mail: ghanshyam.vaghjiani@us.af.mil; Vaghjiani, Ghanshyam L. E-mail: ghanshyam.vaghjiani@us.af.mil

    2015-05-28

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

  9. Determination of nitrate in atmospheric particulate matter by thermal decomposition and chemiluminescence

    SciTech Connect

    Spicer, C.W.; Joseph, D.W.; Schumacher, P.M.

    1985-10-01

    A thermal decomposition/chemiluminescence method is presented for determining nitrate in atmospheric particular matter. Nitrate in the sample is thermally decomposed to NO/sub x/, which is then determined with a commercial chemiluminescence NO/sub x/ monitor. The nitrate in a filter sample can be determined directly by heating a segment of the filter in a furnace or after extraction of the filter by flash heating the aqueous extract in a sample loop. In either case, the sample is decomposed in a nitrogen atmosphere to avoid interference from ammonium. The NO/sub x/ peak from nitrate decomposition can be quantified by integrating the chemiluminescence signal or by integrating the gas sample in a Tedlar bag prior to the chemiluminescence measurement. The technique is straightforward, fast, and sensitive, and interferences in atmospheric samples are negligible. A comparison of the thermal decomposition/chemiluminescence method with ion chromatography using filter samples collected in ambient air showed good agreement over a wide range of concentrations. 26 references.

  10. Evaluation of thermal decomposition rate of carbohydrazide and its reducing effect on carbon steel corrosion

    SciTech Connect

    Fujiwara, Kazutoshi; Kawamura, Hirotaka; Hirano, Hideo; Takahashi, Kanjo; Maeda, Toshihiko; Koike, Masami

    1997-12-01

    Hydrazine as an oxygen scavenger has been widely used for the feed water treatment of PWR secondary side and fossil power plants in the world. However, there is some concern over health and safety issues related to the use of hydrazine. Carbohydrazide is listed up as one of alternative oxygen scavengers. In this study, laboratory tests were performed to examine the thermal decomposition rate of carbohydrazide and its reducing effect on carbon steel corrosion in comparison with hydrazine. Test results revealed that carbohydrazide was stable below 373 K. The thermal decomposition ratios of carbohydrazide were less than 50% after 20 minutes exposure in the range of 373 K to 428 K. Its thermal decomposition rate constant was derived from experimental test data. The measurement of dissolved oxygen concentration also showed that carbohydrazide possessed a fairly good oxygen scavenger property. Judging from test results mentioned above, it was concluded that carbohydrazide is applicable as an alternative oxygen scavenger for feedwater treatment in PWR and fossil power plant.

  11. Ultrafast Preparation of Monodisperse Fe3 O4 Nanoparticles by Microwave-Assisted Thermal Decomposition.

    PubMed

    Liang, Yi-Jun; Zhang, Yu; Guo, Zhirui; Xie, Jun; Bai, Tingting; Zou, Jiemeng; Gu, Ning

    2016-08-01

    Thermal decomposition, as the main synthetic procedure for the synthesis of magnetic nanoparticles (NPs), is facing several problems, such as high reaction temperatures and time consumption. An improved a microwave-assisted thermal decomposition procedure has been developed by which monodisperse Fe3 O4 NPs could be rapidly produced at a low aging temperature with high yield (90.1 %). The as-synthesized NPs show excellent inductive heating and MRI properties in vitro. In contrast, Fe3 O4 NPs synthesized by classical thermal decomposition were obtained in very low yield (20.3 %) with an overall poor quality. It was found for the first time that, besides precursors and solvents, magnetic NPs themselves could be heated by microwave irradiation during the synthetic process. These findings were demonstrated by a series of microwave-heating experiments, Raman spectroscopy and vector-network analysis, indicating that the initially formed magnetic Fe3 O4 particles were able to transform microwave energy into heat directly and, thus, contribute to the nanoparticle growth. PMID:27381301

  12. Convex Decompositions of Thermal Equilibrium for Non-interacting Non-relativistic Particles

    NASA Astrophysics Data System (ADS)

    Chenu, Aurelia; Branczyk, Agata; Sipe, John

    2016-05-01

    We provide convex decompositions of thermal equilibrium for non-interacting non-relativistic particles in terms of localized wave packets. These quantum representations offer a new tool and provide insights that can help relate to the classical picture. Considering that thermal states are ubiquitous in a wide diversity of fields, studying different convex decompositions of the canonical ensemble is an interesting problem by itself. The usual classical and quantum pictures of thermal equilibrium of N non-interacting, non-relativistic particles in a box of volume V are quite different. The picture in classical statistical mechanics is about (localized) particles with a range of positions and velocities; in quantum statistical mechanics, one considers the particles (bosons or fermions) associated with energy eigenstates that are delocalized through the whole box. Here we provide a representation of thermal equilibrium in quantum statistical mechanics involving wave packets with a localized coordinate representation and an expectation value of velocity. In addition to derive a formalism that may help simplify particular calculations, our results can be expected to provide insights into the transition from quantum to classical features of the fully quantum thermal state.

  13. Organic and inorganic decomposition products from the thermal desorption of atmospheric particles

    DOE PAGESBeta

    Williams, Brent J.; Zhang, Yaping; Zuo, Xiaochen; Martinez, Raul E.; Walker, Michael J.; Kreisberg, Nathan M.; Goldstein, Allen H.; Docherty, Kenneth S.; Jimenez, Jose L.

    2016-04-11

    Here, atmospheric aerosol composition is often analyzed using thermal desorption techniques to evaporate samples and deliver organic or inorganic molecules to various designs of detectors for identification and quantification. The organic aerosol (OA) fraction is composed of thousands of individual compounds, some with nitrogen- and sulfur-containing functionality and, often contains oligomeric material, much of which may be susceptible to decomposition upon heating. Here we analyze thermal decomposition products as measured by a thermal desorption aerosol gas chromatograph (TAG) capable of separating thermal decomposition products from thermally stable molecules. The TAG impacts particles onto a collection and thermal desorption (CTD) cell, and upon completionmore » of sample collection, heats and transfers the sample in a helium flow up to 310 °C. Desorbed molecules are refocused at the head of a gas chromatography column that is held at 45 °C and any volatile decomposition products pass directly through the column and into an electron impact quadrupole mass spectrometer. Analysis of the sample introduction (thermal decomposition) period reveals contributions of NO+ (m/z 30), NO2+ (m/z 46), SO+ (m/z 48), and SO2+ (m/z 64), derived from either inorganic or organic particle-phase nitrate and sulfate. CO2+ (m/z 44) makes up a major component of the decomposition signal, along with smaller contributions from other organic components that vary with the type of aerosol contributing to the signal (e.g., m/z  53, 82 observed here for isoprene-derived secondary OA). All of these ions are important for ambient aerosol analyzed with the aerosol mass spectrometer (AMS), suggesting similarity of the thermal desorption processes in both instruments. Ambient observations of these decomposition products compared to organic, nitrate, and sulfate mass concentrations measured by an AMS reveal good correlation, with improved correlations for OA when compared to the AMS

  14. Kinetic analysis of the thermal decomposition of pristine and gamma-irradiated zinc uranyl acetate

    NASA Astrophysics Data System (ADS)

    Al-Muhaimid, T. I. A.; Al-Qunaibit, M. H.; Al-Farhan, K. A.; Mahfouz, R. M.

    2004-11-01

    Thermal decomposition of pristine and gamma-irradiated zinc uranyl acetate was investigated in air using isothermal and dynamic thermogravimetric techniques. The decomposition proceeded via one major process with the formation of triuranates ZnU3O10 as solid residues. Kinetic analysis of isothermal data, when compared with various solid-state reaction models, showed that the decomposition reaction is best fitted by the phase-boundary model. Kinetic analysis of the cynamic TG curves was discussed with reference to integral methods of modified Coats and Redfern equations. Kinetic and thermodynamic parameters were calculated and evaluated. IR spectroscopy and X-ray powder diffraction techniques were employed to follow the chemical composition of solid residue at different calcination temperatures. The results display that the triuranate ZnU3O10 starts forming by calcination of zinc uranyl acetate at temperatures >300 degrees C and undergoes decomposition at higher temperatures (>600 degrees C) with the formation Of U3O8. The results were evaluated regarding the utilization of zinc uranyl acetate as an important source of diuranates and triuranates.

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

    NASA Astrophysics Data System (ADS)

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

    2011-03-01

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

  16. Kinetic model for thermal decomposition of energetic materials from ReaxFF molecular dynamics

    NASA Astrophysics Data System (ADS)

    Sergeev, Oleg; Yanilkin, Alexey

    2015-06-01

    In the present work we perform molecular dynamics simulations of the thermal decomposition of isolated molecules and single crystals of PETN, RDX and HMX. For isolated molecules we use multi-replica approach with different preconditioned atomic velocities to obtain statistics of the decomposition. In this model we only consider the initial stage of the reactions, that shows first order kinetics. In the model of single crystal, we directly observe reaction pathways that result in product formation, as well as the dependences of concentrations of main chemical species on time after heating. Initial temperatures are in the range of 1000 to 2800 K. On the basis of the obtained dependences of concentrations we propose a kinetic model that describes thermal decomposition process. Reaction rate constants are well described by the Arrhenius law. Activation energies for the initial stage appear to be lowered by 30-60 kJ/mole in condensed phase compared to the isolated molecule. We compare these results between different ReaxFF parametrizations and DFT calculations. Please refer the correspondence to this author.

  17. Radiation-induced synthesis of ZrO2 nanoparticles by thermal decomposition of zirconium acetylacetonate

    NASA Astrophysics Data System (ADS)

    Mahfouz, R. M.; Ahmed, G. A.-W.; Al-Wassil, A. I.; Siddiqui, M. R. H.; Al-Otaibi, A. M.

    2013-12-01

    ZrO2 nanoparticles were obtained by the thermal decomposition of un-irradiated and γ-irradiated zirconium acetylacetonate (ZrAcAc) precursors. Several influencing factors, including absorbed dose, calcination times, calcination temperatures and addition of surfactants, were thoroughly investigated. The results showed that the best conditions for the preparation of ZrO2 nanoparticles were achieved by calcinations of ZrAcAc for 5 h at 600°C in the presence of 1 mL of benzyl alcohol as the surfactant. Different phases, morphologies and sizes for the as-prepared ZrO2 nanoparticles were obtained by varying the dose of γ-ray absorbed. ZrO2 nanoparticles obtained by thermal decomposition of un-irradiated ZrAcAc have mixture of monoclinic and tetragonal crystal systems, the particles are monodispersed with an irregular shape. In the case of γ-irradiated ZrAcAc with 10, 102 and 103 KGy, ZrO2 nanoparticles have only a tetragonal system with different morphologies depending on the γ-ray dose absorbed. Thermal stability of ZrO2 nanoparticles was studied using thermogravimetric/differential thermal analyzer techniques. Thermodynamic and kinetic parameters were evaluated and discussed.

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

    SciTech Connect

    Henson, Bryan F

    2009-01-01

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

  19. CP: AN INVESTIGATION OF COEFFICIENT OF THERMAL EXPANSION, DECOMPOSITION KINETICS, AND REACTION TO VARIOUS STIMULI

    SciTech Connect

    Weese, R K; Burnham, A K; Fontes, A T

    2005-03-23

    The properties of pentaamine (5-cyano-2H-tetrazolato-N2) cobalt (III) perchlorate (CP), which was first synthesized in 1968, continues to be of interest for predicting behavior in handling, shipping, aging, and thermal cook-off situations. We report coefficient of thermal expansion (CTE) values over four specific temperature ranges, decomposition kinetics using linear heating rates, and the reaction to three different types of stimuli: impact, spark, and friction. The CTE was measured using a Thermal Mechanical Analyzer (TMA) for samples that were uniaxially compressed at 10,000 psi and analyzed over a dynamic temperature range of -20 C to 70 C. Using differential scanning calorimetry, DSC, CP was decomposed at linear heating rates of 1, 3, and 7 C/min and the kinetic triplet calculated using the LLNL code Kinetics05. Values are also reported for spark, friction, and impact sensitivity.

  20. High temperature electrical conductivity and thermal decomposition of phenolic- and silicon-based dielectrics for fireset housings

    SciTech Connect

    Johnson, R.T. Jr.; Biefeld, R.M.

    1981-08-01

    The temperature dependence of the electrical conductivity and thermal decomposition characteristics of several phenolic- and silicone-based materials of interest for fireset case housings have been measured to 600 to 700/sup 0/C. The materials are phenolic or silicone resins reinforced with glass chopped fabric or cloth. The conductivity temperature dependence was measured during decomposition in a nitrogen atmosphere at a heating rate of approx. 10/sup 0/C/minute. Applied electric fields were from 4 x 10/sup 2/ to 4 x 10/sup 3/ volts/cm. Thermal decomposition characteristics were investigated by mass spectroscopy in vacuum and thermal gravimetric analysis in nitrogen and air. Nearly ohmic voltage-current characteristics were obtained, except where decomposition and/or outgassing was pronounced.

  1. Kinetic and microstructural studies of thermal decomposition in uranium mononitride compacts subjected to heating in high-purity helium

    NASA Astrophysics Data System (ADS)

    Lunev, A. V.; Mikhalchik, V. V.; Tenishev, A. V.; Baranov, V. G.

    2016-07-01

    Although uranium mononitride has a high melting point (≈3100 K), it often decomposes well below this temperature. The threshold and kinetics of thermal decomposition depend on samples' chemical content and on gas environment. However, most experiments with uranium nitride samples were done so far in vacuum conditions and did not allow thorough examination of reaction kinetics at high temperatures. This research focuses on studying the different stages of thermal decomposition in uranium nitride samples subjected to heating in helium. Mass loss and thermal effects are identified with simultaneous thermal analysis (STA), while scanning electron microscopy (SEM) and X-ray diffraction (XRD) are used to register phase and compositional changes. Thermal decomposition in uranium nitride samples is found to be a multi-stage process with the final stage characterized by uranium vaporization. The results are useful for estimating the high-temperature behaviour of uranium nitride fuel during its fabrication and performance in some of Gen IV reactors.

  2. Differential Scanning Calorimetry of Volatile-bearing Iron Minerals Under Mars-like Pressures: New Insights into Energetics and Mechanisms of Thermal Decomposition

    NASA Technical Reports Server (NTRS)

    Lin, I-C.; Lauer, H. V., Jr.; Golden, D. C.; Ming, D. W.

    2000-01-01

    Lepidocrocite and siderite both exhibit different enthalpic events during their decomposition at reduced pressures when compared to those at ambient pressure, allowing us looking into the mechanisms of thermal decomposition at Mars-like pressures.

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

    PubMed

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

    2011-11-01

    We report on the characterization by mass spectrometry (MS) of a rapid, reagentless and site-specific cleavage at the N-terminus of the amino acid cysteine (C) in peptides and proteins induced by the thermal decomposition at 220-250 °C for 10 s in solid samples. This thermally induced cleavage at C occurs under the same conditions and simultaneously to our previously reported thermally induced site-specific cleavage at the C-terminus of aspartic acid (D) (Zhang, S.; Basile, F. J. Proteome Res. 2007, 6, (5), 1700-1704). The C cleavage proceeds through cleavage of the nitrogen and α-carbon bond (N-terminus) of cysteine and produces modifications at the cleavage site with an amidation (-1 Da) of the N-terminal thermal decomposition product and a -32 Da mass change of the C-terminal thermal decomposition product, the latter yielding either an alanine or β-alanine residue at the N-terminus site. These modifications were confirmed by off-line thermal decomposition electrospray ionization (ESI)-MS, tandem MS (MS/MS) analyses and accurate mass measurements of standard peptides. Molecular oxygen was found to be required for the thermal decomposition and cleavage at C as it induced an initial cysteine thiol side chain oxidation to sulfinic acid. Similar to the thermally induced D cleavage, missed cleavages at C were also observed. The combined thermally induced digestion process at D and C, termed thermal decomposition/digestion (TDD), was observed on several model proteins tested under ambient conditions and the site-specificity of the method confirmed by MS/MS. PMID:21952765

  4. PROPERTIES OF CP: COEFFICIENT OF THERMAL EXPANSION, DECOMPOSITION KINETICS, AND REACTION TO SPARK, FRICTION AND IMPACT

    SciTech Connect

    Weese, R K; Burnham, A K

    2005-09-28

    The properties of pentaamine (5-cyano-2H-tetrazolato-N2) cobalt (III) perchlorate (CP), which was first synthesized in 1968, continues to be of interest for predicting behavior in handling, shipping, aging, and thermal cook-off situations. We report coefficient of thermal expansion (CTE) values over four specific temperature ranges, decomposition kinetics using linear and isothermal heating, and the reaction to three different types of stimuli: impact, spark, and friction. The CTE was measured using a Thermal Mechanical Analyzer (TMA) for samples that were uniaxially compressed at 10,000 psi and analyzed over a dynamic temperature range of -20 C to 70 C. Differential scanning calorimetry, DSC, was used to monitor CP decomposition at linear heating rates of 1-7 C min{sup -1} in perforated pans and of 0.1-1.0 C min{sup -1} in sealed pans. The kinetic triplet was calculated using the LLNL code Kinetics05, and predictions for 210 and 240 C are compared to isothermal thermogravimetric analysis (TGA) experiments. Values are also reported for spark, friction, and impact sensitivity.

  5. Kinetics of switch grass pellet thermal decomposition under inert and oxidizing atmospheres.

    PubMed

    Chandrasekaran, Sriraam R; Hopke, Philip K

    2012-12-01

    Grass pellets are a renewable resource that have energy content similar to that of wood. However, the higher ash and chlorine content affects combustion. Thermal degradation analysis of a fuel is useful in developing effective combustion. Thermogravimetric analysis (TGA) of the thermal degradation of grass pellets under inert (nitrogen) and oxidizing (air) atmospheres was conducted. Non-isothermal conditions were employed with 4 different heating rates. Kinetic parameters (activation energy and pre-exponential factors) were estimated using the iso-conversional method. Both pyrolysis and oxidative atmospheric thermal degradation exhibited two major loss process: volatilization of cellulose, hemicelluloses and lignin and burning or slow oxidation of the residual char. The activation energy and pre-exponential factors were high for the oxidizing environment. During pyrolysis, major decomposition occurred with 40% to 75% conversion of the mass to gas with an activation energy of 314 kJ/mol. In air the decomposition occurred with 30% to 55% conversion with an activation energy of 556 kJ/mol. There was a substantial effect of heating rate on mass loss and mass loss rate. The TG shifted to higher temperature ranges on increasing the heating rate. In both pyrolyzing and oxidizing conditions, average combustion and devolatilization rates increased. Enhanced combustion takes place with higher activation energy in oxidizing atmosphere compared to the inert atmosphere due to presence of air. PMID:23026316

  6. Study of thermal decomposition mechanisms and low-level detection of explosives using pulsed photoacoustic technique

    NASA Astrophysics Data System (ADS)

    Yehya, F.; Chaudhary, A. K.; Srinivas, D.; Muralidharan, K.

    2015-11-01

    We report a novel time-resolved photoacoustic-based technique for studying the thermal decomposition mechanisms of some secondary explosives such as RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), picric acid, 4,6-dinitro-5-(4-nitro-1 H-imidazol-1-yl)-1 H-benzo[ d] [1-3] triazole, and 5-chloro-1-(4-nitrophenyl)-1 H-tetrazole. A comparison of the thermal decomposition mechanisms of these secondary explosives was made by detecting NO2 molecules released under controlled pyrolysis between 25 and 350 °C. The results show excellent agreement with the thermogravimetric and differential thermal analysis (TGA-DTA) results. A specially designed PA cell made of stainless steel was filled with explosive vapor and pumped using second harmonic, i.e., λ = 532 nm, pulses of duration 7 ns at a 10 Hz repetition rate, obtained using a Q-switched Nd:YAG laser. The use of a combination of PA and TGA-DTA techniques enables the study of NO2 generation, and this method can be used to scale the performance of these explosives as rocket fuels. The minimum detection limits of the four explosives were 38 ppmv to 69 ppbv, depending on their respective vapor pressures.

  7. Thermal Decomposition of Trinitrotoluene (TNT) with a New One-Dimensional Time to Explosion (ODTX) Apparatus

    SciTech Connect

    Tran, T D; Simpson, R L; Maienschein, J; Tarver, C

    2001-03-23

    The thermal explosion of trinitrotoluene (TNT) is used as a basis for evaluating the performance of a new One-Dimensional-Time-to-Explosion (ODTX) apparatus. The ODTX experiment involves holding a 12.7 mm-diameter spherical explosive sample under confinement (150 MPa) at a constant elevated temperature until the confining pressure is exceeded by the evolution of gases during chemical decomposition. The resulting time to explosion as a function of temperature provides valuable decomposition kinetic information. A comparative analysis of the measurements obtained from the new unit and an older system is presented. Discussion on selected performance aspects of the new unit will also be presented. The thermal explosion of TNT is highly dependent on the material. Analysis of the time to explosion is complicated by historical and experimental factors such as material variability, sample preparation, temperature measurement and system errors. Many of these factors will be addressed. Finally, a kinetic model using a coupled thermal and heat transport code (chemical TOPAZ) was used to match the experimental data.

  8. Adsorption and thermal decomposition of 2-octylthieno[3,4-b]thiophene on Au(111).

    PubMed

    Park, Joon B; Zong, Kyukwan; Jeon, Il Chul; Hahn, Jae Ryang; Stacchiola, Dario; Starr, David; Müller, Kathrin; Noh, Jaegeun

    2012-10-15

    The adsorption and thermal stability of 2-octylthieno[3,4-b]thiophene (OTTP) on the Au(111) surfaces have been studied using scanning tunneling microscopy (STM), temperature programmed desorption (TPD), and X-ray photoelectron spectroscopy (XPS). UHV-STM studies revealed that the vapor-deposited OTTP on Au(111) generated disordered adlayers with monolayer thickness even at saturation coverage. XPS and TPD studies indicated that OTTP molecules on Au(111) are stable up to 450 K and further heating of the sample resulted in thermal decomposition to produce H(2) and H(2)S via C-S bond scission in the thieno-thiophene rings. Dehydrogenation continues to occur above 600 K and the molecules were ultimately transformed to carbon clusters at 900 K. Highly resolved air-STM images showed that OTTP adlayers on Au(111) prepared from solution are composed of a well-ordered and low-coverage phase where the molecules lie flat on the surface, which can be assigned as a (9×2√33)R5° structure. Finally, based on analysis of STM, TPD, and XPS results, we propose a thermal decomposition mechanism of OTTP on Au(111) as a function of annealing temperature. PMID:22818203

  9. Thermogravimetric and kinetic analysis of thermal decomposition characteristics of low-lipid microalgae.

    PubMed

    Gai, Chao; Zhang, Yuanhui; Chen, Wan-Ting; Zhang, Peng; Dong, Yuping

    2013-12-01

    The thermal decomposition behavior of two microalgae, Chlorella pyrenoidosa (CP) and Spirulina platensis (SP), were investigated on a thermogravimetric analyzer under non-isothermal conditions. Iso-conversional Vyazovkin approach was used to calculate the kinetic parameters, and the universal integral method was applied to evaluate the most probable mechanisms for thermal degradation of the two feedstocks. The differential equations deduced from the models were compared with experimental data. For the range of conversion fraction investigated (20-80%), the thermal decomposition process of CP could be described by the reaction order model (F3), which can be calculated by the integral equation of G(α) = [(1 - α)(-2) - 1]/2. And the apparent activation energy was in the range of 58.85-114.5 kJ/mol. As for SP, it can be described by the reaction order model (F2), which can be calculated by the integral equation of G(α) = (1 - α)(-1) - 1, and the range of apparent activation energy was 74.35-140.1 kJ/mol. PMID:24161552

  10. Thermal decomposition mechanisms of methylamine, ethylamine, and 1-propylamine on Si(100)-2 × 1 surface

    NASA Astrophysics Data System (ADS)

    Cho, Jieun; Choi, Cheol Ho

    2011-05-01

    The thermal decomposition reactions of methylamine, ethylamine, and 1-propylamine absorbed on Si(100)-2 × 1 surface were theoretically investigated. Eight decomposition channels were found leading to desorption products of imine, H2, alkyl cyanide, ammonia, aziridine, alkene, azetidine, and cyclopropane, which supports the experimental assignments. Our mechanistic studies strongly suggest that the alkyl cyanide (hydrogen cyanide in the case of methylamine) channel is coupled with the hydrogen desorption step. The β-hydrogen of ethylamine and 1-propylamine was found to undergo additional decomposition reactions producing aziridine and alkene, which were classified as γ- and β-eliminations, respectively. It was also found that the γ-hydrogen of 1-propylamine undergoes azetidine and cyclopropane producing decompositions, which were classified as δ- and γ-eliminations. In general, γ- and δ-hydrogen involved decomposition reactions are kinetically less favorable than β-hydrogen involved ones. Consequently, it is expected that the thermal decompositions of the primary alkyl amines with longer alkyl chains would not add additional favorable decomposition channels. Except alkyl cyanide and ammonia desorption channels, the decompositions occur in a concerted fashion.

  11. A metastable phase in thermal decomposition of Ca-deficient hydroxyapatite.

    PubMed

    Tamai, Masato; Nakamura, Mitsuhiro; Isshiki, Toshiyuki; Nishio, Koji; Endoh, Hisamitsu; Nakahira, Atsushi

    2003-07-01

    We investigated the microstructural changes on an atomic length scale during thermal decomposition process of Ca-deficient hydroxyapatite (Ca-def HAp) by high-resolution transmission electron microscopy (HRTEM). Ca-def HAp was prepared by hydrolysis of alpha-tricalcium phosphate. The Ca-def HAp had a whisker-like morphology 2-5 microm in length and 0.1 microm in diameter that was elongated along c-axis. Thicker planer defects parallel to the (100) plane of the HAp matrix were observed as precipitation in the sample annealed at 700 and 800 degrees C by HRTEM observation. Thickness of the precipitation was about 10 nm and the boundaries between the precipitation and HAp matrix was coincident. The periodicity in the precipitation was parallel to the (100) plane of the HAp matrix and measured to be 1.42 nm. Since the precipitation was observed only in the sample annealed at a narrow temperature range of 700-800 degrees C, it was regarded as a metastable phase formed on the thermal decomposition process. Absorption peaks in IR spectra of annealed Ca-def HAp containing the metastable phase appeared at 744 and 3538 cm(-1) due to non-stoichiometric HAp with high Ca/P molar ratio. Furthermore, the results of energy dispersive X-ray spectroscopy showed that the metastable phase had higher Ca/P molar ratio than that of the matrix and stoichiometric HAp. Therefore, the metastable phase could be identified as Ca-rich metastable phase. The presence of Ca-rich metastable phase was confirmed to be associated with the thermal decomposition process. PMID:15348424

  12. Thermal degradation kinetics and decomposition mechanism of PBSu nanocomposites with silica-nanotubes and strontium hydroxyapatite nanorods.

    PubMed

    Papageorgiou, D G; Roumeli, E; Chrissafis, K; Lioutas, Ch; Triantafyllidis, K; Bikiaris, D; Boccaccini, A R

    2014-03-14

    Novel poly(butylene succinate) (PBSu) nanocomposites containing 5 and 20 wt% mesoporous strontium hydroxyapatite nanorods (SrHNRs) and silica nanotubes (SiNTs) were prepared by melt-mixing. A systematic investigation of the thermal stability and decomposition kinetics of PBSu was performed using pyrolysis-gas chromatography-mass spectroscopy (Py-GC-MS) and thermogravimetry (TG). Thorough studies of evolving decomposition compounds along with the isoconversional and model-fitting analysis of mass loss data led to the proposal of a decomposition mechanism for PBSu. Moreover, the effects of SrHNRs and SiNTs on the thermal stability and decomposition kinetics of PBSu were also examined in detail. The complementary use of these techniques revealed that the incorporation of SiNTs in PBSu does not induce significant effects neither on its thermal stability nor on its decomposition mechanism. In contrast, the addition of SrHNRs resulted in the catalysis of the initial decomposition steps of PBSu and also in modified decomposition mechanisms and activation energies. The evolving gaseous products of PBSu and their evolution pattern in the SiNT nanocomposites were the same as in neat PBSu, while they were slightly modified for the SrHNR nanocomposites, confirming the findings from thermogravimetric analysis. PMID:24469599

  13. Non-chemically Pure Magnetites Produced from Thermal Decomposition of Ankerites

    NASA Astrophysics Data System (ADS)

    Jiménez López, C.; Romanek, C.; Rodríguez-Navarro, A.; Pérez-González, T.; Rodríguez Navarro, C.

    2008-12-01

    It has been claimed that chemically pure magnetites (Fe3O4) can be obtained from thermal decomposition of (Fe, Mg, Ca)CO3 (Golden et al., 2004). Such an observation is critical, since it opens the possibility of an inorganic way of formation of the magnetites found on Martian meteorite ALH84001. Such a chemical purity is one of the parameters used, so far, to recognize bacterial origin of natural magnetites (Thomas-Keptra et al., 2001), since it has been demonstrated that biologically-controlled magnetites are chemically pure (Bazylinski and Frankel, 2004) . However, while Golden et al. (2004) obtained pure magnetite from an almost pure precursor, the ankerite cores in ALH84001 in which magnetites are embedded are far from being chemically pure, since they contain considerable amounts of Ca and Mg (Kopp and Humayun, 2003). In this study we have performed several experiments to analyze the chemical purity of magnetites produced by thermal decomposition of four ankerite samples sinthetized in the laboratory, and containing different amounts of Ca, Fe and Mg. Such a thermal decomposition was achieved by two procedures: (1) by heating the samples at 470°C under CO2 pressure and (2) by decomposing the ankerite "in situ" under the TEM (Transmission electron Microscopy) electron beam. Magnetite produced by the first procedure was analyzed by XRD to determine whether or not the resulting solid was a mixture of oxides or rather a solid solution of (Ca, Fe and Mg)oxide. Magnetites formed by the two methods were studied by High Resolution TEM. The chemical composition of about 20 crystals of each experiment was analyzed by EDAX. Under our experimental conditions, ankerites decomposed in magnetite crystals of about 5 nanometers in size. Magentite crystals arranged to keep the morphology of the precursor. Our results confirm that any of these magnetites is chemically pure, but rather, each one of them is a solid solution of Ca and Mg. Therefore, chemically pure magnetites

  14. Application of subgroup decomposition in diffusion theory to gas cooled thermal reactor problem

    SciTech Connect

    Yasseri, S.; Rahnema, F.

    2013-07-01

    In this paper, the accuracy and computational efficiency of the subgroup decomposition (SGD) method in diffusion theory is assessed in a ID benchmark problem characteristic of gas cooled thermal systems. This method can be viewed as a significant improvement in accuracy of standard coarse-group calculations used for VHTR whole core analysis in which core environmental effect and energy angle coupling are pronounced. It is shown that a 2-group SGD calculation reproduces fine-group (47) results with 1.5 to 6 times faster computational speed depending on the stabilizing schemes while it is as efficient as single standard 6-group diffusion calculation. (authors)

  15. Optical and electrochemical properties of nanosized NiO via thermal decomposition of nickel oxalate nanofibres

    NASA Astrophysics Data System (ADS)

    Wang, Xiong; Song, Jimei; Gao, Lisheng; Jin, Jiayi; Zheng, Huagui; Zhang, Zude

    2005-01-01

    Nickel oxide nanoparticles with an average diameter of about 9 nm were synthesized via thermal decomposition of NiC2O4 precursor at 450 °C. The nanoparticles were investigated using XRD, TEM, TGA, and UV-vis spectrophotometry. The optical absorption spectrum indicates that the NiO nanoparticles have a direct band gap of 3.56 eV. The electrochemical tests show that the ultrafine NiO nanoparticles, as a promising electrode material, can deliver a large reversible discharge capacity of about 610 mA h g-1.

  16. The spectral properties of uranium hexafluoride and its thermal decomposition products

    NASA Technical Reports Server (NTRS)

    Krascella, N. L.

    1976-01-01

    This investigation was initiated to provide basic spectral data for gases of interest to the plasma core reactor concept. The attenuation of vacuum ultraviolet (VUV) radiation by helium at pressures up to 20 atm over path lengths of about 61 cm and in the approximate wavelength range between 80 and 300 nm was studied. Measurements were also conducted to provide basic VUV data with respect to UF6 and UF6/argon mixtures in the wavelength range between 80 and 120 nm. Finally, an investigation was initiated to provide basic spectral emission and absorption data for UF6 and possible thermal decomposition products of UF6 at elevated temperatures.

  17. Dynamic weakening and thermal decomposition during the Heart Mountain mega-landslide

    NASA Astrophysics Data System (ADS)

    Mitchell, T. M.; Smith, S. A.; Anders, M. H.; Di Toro, G.

    2012-12-01

    The 3400-km2 Heart Mountain landslide of northwestern Wyoming and southwestern Montana is the largest subaerial landslide known. This Eocene age slide slid ˜50 km on a carbonate rich basal layer ranging in thickness from a few tens of centimeters to several meters, along a shallow 2° slope, posing a long-standing question regarding its emplacement mechanism. It has recently been suggested that such large displacement was aided by strong dynamic weakening mechanism, thermal pressurization due to shear heating and thermal decomposition in the basal layer slip zone, with theoretical simulations suggesting slip velocities ranging between tens of meters per second to more than 100 ms-1. In this study, we present the results of a suite of high velocity friction experiments in a rotary shear configuration on initially intact carbonates collected from the Heart Mountain region, in attempt to reproduce conditions experienced in the slip zone of the basal section during emplacement of the landslide. Gouges were prepared from initially intact hostrocks of Madison limestone and Bighorn dolomite, and were sheared for a range of displacements up to 6 metres at normal stresses up to 25 MPa at slip rates up to 2 m/s. Mechanical results generally show strong dynamic weakening with peak friction dropping from 0.7 to a steady state friction as low as 0.1. Microstructural observations of the highly polished slip surfaces produced show localization of the principal slip surface to less than 100 microns thick. Thermal decomposition is evidenced by degassing bubbles in the rims of dolomite clasts, and the release of CO2 as measured by mass spectrometer during experiments, indicating that temperatures in the slip zone quickly reached the decomposition temperature of carbonates (at least 700 degrees) within just a few metres of slip. These results compare favorably with theoretical calculations and ample field evidence for carbonate decomposition during the emplacement. Independent

  18. A Review of Study on Thermal Energy Transport System by Synthesis and Decomposition Reactions of Methanol

    NASA Astrophysics Data System (ADS)

    Liu, Qiusheng; Yabe, Akira; Kajiyama, Shiro; Fukuda, Katsuya

    The study on thermal energy transport system by synthesis and decomposition reactions of methanol was reviewed. To promote energy conservation and global environment protection, a two-step liquid-phase methanol synthesis process, which starts with carbonylation of methanol to methyl formate, then followed by the hydrogenolysis of the formate, was studied to recover wasted or unused discharged heat from industrial sources for the thermal energy demands of residential and commercial areas by chemical reactions. The research and development of the system were focused on the following three points. (1) Development of low-temperature decomposition and synthetic catalysts, (2) Development of liquid phase reactor (heat exchanger accompanying chemical reaction), (3) Simulation of the energy transport efficiency of entire system which contains heat recovery and supply sections. As the result of the development of catalyst, promising catalysts which agree with the development purposes for the methyl formate decomposition reaction and the synthetic reaction are being developed though some studies remain for the methanol decomposition and synthetic reactions. In the fundamental development of liquid phase reactor, the solubilities of CO and H2 gases in methanol and methyl formate were measured by the method of total pressure decrease due to absorption under pressures up to 1500kPa and temperatures up to 140°C. The diffusivity of CO gas in methanol was determined by measuring the diameter and solution time of single CO bubbles in methanol. The chemical reaction rate of methanol synthesis by hydrogenolysis of methyl formate was measured using a plate-type of Raney copper catalyst in a reactor with rectangular channel and in an autoclave reactor. The reaction characteristics were investigated by carrying out the experiments at various temperatures, flow rates and at various catalyst development conditions. We focused on the effect of Raney copper catalyst thickness on the liquid

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

    NASA Astrophysics Data System (ADS)

    Cavaignac, A. L. O.; Lima, R. J. C.; Façanha Filho, P. F.; Moreno, A. J. D.; Freire, P. T. C.

    2016-03-01

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

  20. Study of the Thermal Decomposition of Some Components of Biomass by Desorption Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Palianytsia, Borys; Kulik, Tetiana; Dudik, Olesia; Cherniavska, Tetiana; Tonkha, Oksana

    The investigation of thermal transformations of lignin samples have been carried out using temperature programmed desorption mass spectrometry method (TPD-MS). Main stages and products of lignin pyrolysis have been identified. The first stages (Tmax = 230 °C and Tmax = 300 °C) are attributed to thermal transformations of lignin peripheral polysaccharide fragments such as hemicellulose and cellulose respectively. The second stage (Tmax = 335 °C) is associated with desorption of lignin structural elements in the molecular forms as a result of depolymerization processes of polymeric blocks of lignin. The third stage (Tmax = 370 °C) correspond to a deeper decomposition of lignin and characterized by desorption of smaller structural fragments in molecular forms (m/z = 110, pyrocatechol). Pressure-temperature curves of pyrolysis of lignin samples have been analyzed.

  1. The effect of cross-linking on the thermal decomposition of diphenylalkanes

    SciTech Connect

    Britt, P.F.; Buchanan, A.C. III

    1992-03-01

    In the early stages of the thermal depolymerization of coal, its cross-linked macromolecular structure may restrict the diffusion of reactive intermediates and alter the reaction pathways. In an effort to model the effects of restricted mass transport on the thermally induced free radical decomposition of polymethylene units bridging aromatic clusters in coal, a series of diphenylalkanes [Ph(CH{sub 2}){sub n}Ph] have been cross-linked to an inert silica surface by the condensation of the corresponding phenol, HOC{sub 6}H{sub 4}(CH{sub 2}){sub n}C{sub 6}H{sub 4}OH. Results from the thermolysis of the diattached substrates at 350--400 {degrees}C will be presented and compared to the thermolysis of fluid phase and mono-attached diphenylalkanes [{approx}Ph(CH{sub 2}){sub n}Ph] to highlight the impact that restricted diffusion has on the reaction mechanisms.

  2. The effect of cross-linking on the thermal decomposition of diphenylalkanes

    SciTech Connect

    Britt, P.F.; Buchanan, A.C. III.

    1992-01-01

    In the early stages of the thermal depolymerization of coal, its cross-linked macromolecular structure may restrict the diffusion of reactive intermediates and alter the reaction pathways. In an effort to model the effects of restricted mass transport on the thermally induced free radical decomposition of polymethylene units bridging aromatic clusters in coal, a series of diphenylalkanes (Ph(CH{sub 2}){sub n}Ph) have been cross-linked to an inert silica surface by the condensation of the corresponding phenol, HOC{sub 6}H{sub 4}(CH{sub 2}){sub n}C{sub 6}H{sub 4}OH. Results from the thermolysis of the diattached substrates at 350--400 {degrees}C will be presented and compared to the thermolysis of fluid phase and mono-attached diphenylalkanes ({approx}Ph(CH{sub 2}){sub n}Ph) to highlight the impact that restricted diffusion has on the reaction mechanisms.

  3. Pyrolytic and Kinetic Characteristics of the Thermal Decomposition of Perilla frutescens Polysaccharide

    PubMed Central

    Zhou, Quancheng; Sheng, Guihua

    2012-01-01

    The thermal decomposition of Perilla frutescens polysaccharide was examined by thermogravimetry, differential thermogravimetry, and differential thermal analysis. The results showed that the mass loss of the substance proceeded in three steps. The first stage can be attributed to the expulsion of the water from ambient temperature to 182°C. The second stage corresponded to devolatilization from 182°C to 439°C. The residue slowly degraded in the third stage. The weight loss in air is faster than that in nitrogen, because the oxygen in air accelerated the pyrolytic reaction speed reaction. The heating rate significantly affected the pyrolysis of the sample. Similar activation energies of the degradation process (210–211 kJ mol−1) were obtained by the FWO, KAS, and Popescu techniques. According to Popescu mechanism functions, the possible kinetic model was estimated to be Avrami–Erofeev 20 g(α) = [−ln(1–α)]4. PMID:23300715

  4. Thermal stability and decompositions kinetics under non-isothermal conditions of imatinib mesylate α form.

    PubMed

    Mucha, Igor; Baranowski, Przemysław; Owczarek, Artur; Gajda, Maciej; Pluta, Janusz; Górniak, Agata; Niklewicz, Paweł; Karolewicz, Bożena

    2016-09-10

    The thermal decomposition and kinetic parameters of synthetized imatinib mesylate α form α form were determined by thermogravimetry (TGA/DTG) under non-isothermal conditions. The experiments were performed at a 25-940°C temperature range at five different heating rates: 2.5Kmin(-1), 5Kmin(-1), 10Kmin(-1), 15Kmin(-1) and 20Kmin(-1) per minute in a nitrogen atmosphere. Imatinib mesylate α form presents one-step mass loss during the degradation process. The thermal stability of the examined material, the melting temperature (Tonset=220.6°C) and ΔH fusion=-95.74Jg(-1) at a heating rate of 10°Cmin(-1) was established. The values of activation energies have been estimated using Kissinger, Flynn-Wall-Ozawa (FWO) and Kissinger-Akahira-Sunose (KAS) methods. PMID:27392171

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

    SciTech Connect

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

    2014-09-01

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

  6. Production of films of uranium and americium compounds by thermal decomposition of volatile β-diketonates

    NASA Astrophysics Data System (ADS)

    Danilin, I. D.; Kartushin, V. D.; Pilipenko, N. V.; Abramycheva, I. D.; Vesnovskii, S. P.

    2002-03-01

    The production of films containing uranium and americium through thermal decomposition of diketonates and their adducts is described. It is demonstrated that for substrate temperatures in the range 300-400°C and at a residual reactor pressure of 1.3 Pa, stable uranium-containing layers up to several milligrams per square centimetre can be produced, with yields of up to 90%. A variety of metal backings were investigated, including aluminium and its alloys, stainless steel and titanium. Similar results were obtained for americium, but with a strong influence of backing material on the yield. X-ray diffraction identified the chemical form of the uranium deposits as dioxide, with crystal lattice parameters varying from 5.4338 to 5.4871 Å, while the density determined by X-rays lies within the range from 10920 to 11255 kg/m 3. In the case of Am (Cm) hexafluoroacetyl acetonate decomposition, the deposit is most probably AmF 3 (CmF 3). The gases released from the pyrolytic uranium dioxide layers heated in vacuum to 470°C were studied. The volume of gas released varied between 10 and 40 cm 3 per gram of UO 2 depending on the initial β-diketonate preparation and reagent purity. The released gases were mainly hydrogen, carbon monoxide, carbon dioxide, water and a small amount of methane. The films of uranium and americium obtained by thermal decomposition show good adhesion to backings and are suitable for use in a number of fields, for example in nuclear physics research and instrument engineering.

  7. Synthesis and thermal decomposition properties of hydrogen-rich phosphorus salts.

    SciTech Connect

    Cordaro, Joseph Gabriel

    2010-12-01

    Complex metal hydrides continue to be investigated as solid-materials for hydrogen storage. Traditional interstitial metal hydrides offer favorable thermodynamics and kinetics for hydrogen release but do not meet energy density requires. Anionic metal hydrides, and complex metal hydrides like magnesium borohydride have higher energy densities compared to interstitial metal hydrides, but poor kinetics and/or thermodynamically unfavorable side products limit their deployment as hydrogen storage materials in transportation applications. Main-group anionic materials such as the bis(borane)hypophosphite salt [PH2(BH3)2] have been known for decades, but only recently have we begun to explore their ability to release hydrogen. We have developed a new procedure for synthesizing the lithium and sodium hypophosphite salts. Routes for accessing other metal bis(borane)hypophosphite salts will be discussed. A significant advantage of this class of material is the air and water stability of the anion. Compared to metal borohydrides, which reactive violently with water, these phosphorus-based salts can be dissolved in protic solvents, including water, with little to no decomposition over the course of multiple days. The ability of these salts to release hydrogen upon heating has been assessed. While preliminary results indicate phosphine and boron-containing species are released, hydrogen is also a major component of the volatile species observed during the thermal decomposition. Additives such as NaH or KH mixed with the sodium salt Na[PH2(BH3)2] significantly perturb the decomposition reaction and greatly increase the mass loss as determined by thermal gravimetric analysis (TGA). This symbiotic behavior has the potential to affect the hydrogen storage ability of bis(borane)hypophosphite salts.

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

    PubMed

    Rueda-Ordóñez, Yesid Javier; Tannous, Katia

    2016-07-01

    The aim of this work was to analyze the thermal decomposition, kinetics and heat of reaction of sugarcane straw in synthetic air by thermogravimetry (TG) and differential scanning calorimetry (DSC). The TG and DSC experiments were carried out using heating rates of 2.5°C/min, 5°C/min, and 10°C/min, and particle diameter of 0.250mm. In the study of the smoldering reaction were identified three consecutive stages, drying, oxidative pyrolysis, and combustion. Thus, the kinetic pathway was composed by six independent parallel reactions, three for each stage after drying, in which the activation energies were 176, 313, 150, 80, 150, and 100kJ/mol. The heat of reaction in synthetic air was completely exothermic releasing 8MJ/kg. The modeled curves of thermal decomposition of sugarcane straw presented good agreement with experimental data. Then, the kinetic parameters obtained could be used to analyze different processes involving smoldering. PMID:27019126

  9. Mass-independent fractionation of oxygen isotopes during thermal decomposition of carbonates

    PubMed Central

    Miller, Martin F.; Franchi, Ian A.; Thiemens, Mark H.; Jackson, Teresa L.; Brack, André; Kurat, Gero; Pillinger, Colin T.

    2002-01-01

    Nearly all chemical processes fractionate 17O and 18O in a mass-dependent way relative to 16O, a major exception being the formation of ozone from diatomic oxygen in the presence of UV radiation or electrical discharge. Investigation of oxygen three-isotope behavior during thermal decomposition of naturally occurring carbonates of calcium and magnesium in vacuo has revealed that, surprisingly, anomalous isotopic compositions are also generated during this process. High-precision measurements of the attendant three-isotope fractionation line, and consequently the magnitude of the isotopic anomaly (Δ17O), demonstrate that the slope of the line is independent of the nature of the carbonate but is controlled by empirical factors relating to the decomposition procedure. For a slope identical to that describing terrestrial silicates and waters (0.5247 ± 0.0007 at the 95% confidence level), solid oxides formed during carbonate pyrolysis fit a parallel line offset by −0.241 ± 0.042‰. The corresponding CO2 is characterized by a positive offset of half this magnitude, confirming the mass-independent nature of the fractionation. Slow, protracted thermolysis produces a fractionation line of shallower slope (0.5198 ± 0.0007). These findings of a 17O anomaly being generated from a solid, and solely by thermal means, provide a further challenge to current understanding of the nature of mass-independent isotopic fractionation. PMID:12167677

  10. Recombination Reactions in the Thermal Decomposition of Anisole: An Investigation of Benzene and Naphthalene Formation

    NASA Astrophysics Data System (ADS)

    Scheer, Adam; Ellison, Barney; Mukarakate, Calvin; Robichaud, David; Nimlos, Mark

    2010-03-01

    Thermal decompositions of anisole (C6H5OCH3) and methyl-deuterated anisole (C6H5OCD3) are studied using a hyperthermal tubular reactor and photoionization reflectron time-of-flight mass spectrometer. Gas exiting the reactor is subject to a supersonic expansion after a residence time of 65 μs, allowing detection of highly chemically reactive radical species. Anisole decomposes through loss of a methyl group (CH3) to form phenoxy radical (C6H5O), followed by ejection of a CO to form cyclopentadienyl radical (c-C5H5; CPDR). Benzene is generated primarily by thermal decomposition of methylcyclopentadiene (C5H5CH3; MCPD). The MCPD results from methyl radical recombination with CPDR. The MCPD then undergoes two hydrogen atom losses and a ring expansion resulting in benzene. At Twall = 1200 C -- 1300 C a large amount of propargyl radical (CH2CCH) is observed. Propargyl radical recombination accounts for a small fraction of the observed benzene. Naphthalene and its precursor intermediates (C10H10, C10H9), resulting from CPDR recombination, are also observed. The presence of benzene and naphthalene is confirmed with resonance-enhanced multiphoton ionization (REMPI).

  11. Synthesis and Thermal Decomposition Mechanism of the Energetic Compound 3,5-Dinitro-4-nitroxypyrazole

    NASA Astrophysics Data System (ADS)

    Feng, Xiao-Qin; Cao, Duan-Lin; Cui, Jian-Lan

    2016-07-01

    A novel energetic material, 3,5-dinitro-4-nitroxypyrazole (DNNP), was synthesized via nitration and nucleophilic substitution reaction using 4-chloropyrazole as raw material. The structure of DNNP was characterized by Fourier transform infrared (FTIR), nuclear magnetic resonance (NMR), and elemental analysis. Its detonation properties were calculated and compared with those of other commonly used energetic compounds. The thermal decomposition mechanism of DNNP was studied by means of thermogravimetry and differential scanning calorimetry coupled with a mass spectrometry (DSC-MS). The results show that the detonation properties of DNNP were better than those of TNT and comparable to those of 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX). In addition, the thermal decomposition mechanism of DNNP was supposed. Initially, the O-NO2 bond was broken, thereby producing a nitropyrazole oxygen radical. Subsequently, the nitropyrazole oxygen radical was decomposed by free radical cleavage of nitro or isomerized to nitritepyrazole and subsequently decomposed by free radical cleavage of the nitroso group. Finally, pyrazole ring fission occurred and produced N2, NO, N2O, and CO2.

  12. Characterization and antimicrobial activity of silver nanoparticles prepared by a thermal decomposition technique

    NASA Astrophysics Data System (ADS)

    Tam, Le Thi; Phan, Vu Ngoc; Lan, Hoang; Thuy, Nguyen Thanh; Hien, Tran Minh; Huy, Tran Quang; Quy, Nguyen Van; Chinh, Huynh Dang; Tung, Le Minh; Tuan, Pham Anh; Lam, Vu Dinh; Le, Anh-Tuan

    2013-11-01

    Recently, there has been an increasing need of efficient synthetic protocols using eco-friendly conditions including low costs and green chemicals for production of metal nanoparticles. In this work, silver nanoparticles (silver NPs) with average particle size about 10 nm were synthesized by using a thermal decomposition technique. Unlike the colloidal chemistry method, the thermal decomposition method developed has advantages such as the high crystallinity, single-reaction synthesis, and easy dispersion ability of the synthesized NPs in organic solvents. In a modified synthesis process, we used sodium oleate as a capping agent to modify the surface of silver NPs because the oleate has a C18 tail with a double bond in the middle, therefore, forming a kink which is to be effective for aggregative stability. Importantly, the as-synthesized silver NPs have demonstrated strong antimicrobial effects against various bacteria and fungi strains. Electron microscopic studies reveal physical insights into the interaction and bactericidal mechanism between the prepared silver NPs and tested bacteria in question. The observed excellent antibacterial and antifungal activity of the silver NPs make them ideal for disinfection and biomedicine applications.

  13. Size dependence of the thermal decomposition kinetics of nano- CaC2O4: A theoretical and experimental study

    NASA Astrophysics Data System (ADS)

    Fu, Qingshan; Cui, Zixiang; Xue, Yongqiang

    2015-10-01

    In the processes of preparation and application of nanomaterials, the thermal decomposition of nanoparticles is often involved. An improved general theory of thermal decomposition kinetics of nanoparticles, developed over the past 10 years, was presented in this paper where the relations between reaction kinetic parameters and particle size were derived. Experimentally, the thermal decomposition kinetics of nano-sized calcium oxalate (nano- CaC2O4 with different sizes was studied by means of Thermogravimetry Analysis (TGA) at different heating rates. The values of the apparent activation energy and the logarithm of pre-exponential factor were calculated using the equation of Iterative Kissinger-Akahira-Sunose (IKAS) and its deformations. The influence regularities of particle size on the apparent activation energy and the pre-exponential factor were summarized, which are consistent with the thermal decomposition kinetics theory of nanoparticles. Based on the theory, the method of obtaining the surface thermodynamic properties by the determination of kinetic parameters was presented. Theoretical and experimental results show that the particle size, through the effect on the surface thermodynamic properties, has notable effect on the thermal decomposition kinetics. With the particle size decreasing, the partial molar surface enthalpy and the partial molar surface entropy increases, leading to the decrease of the apparent activation energy and the pre-exponential factor, respectively. Furthermore, the apparent activation energy, the pre-exponential factor, the partial molar surface enthalpy and the partial molar surface entropy are linearly related to the reciprocal of particle diameter, respectively.

  14. Comparison of CO2 and oxygen DC submerged thermal plasmas for decomposition of carboxylic acid in aqueous solution

    NASA Astrophysics Data System (ADS)

    Safa, S.; Hekmat-Ardakan, A.; Soucy, G.

    2014-11-01

    The feasibility of the carboxylic acid decomposition with two different direct current (DC) thermal plasma torches was investigated. An oxygen DC submerged thermal plasma torch and a newly designed submerged DC plasma torch operating with a mixture of carbon dioxide and methane (CO2/CH4) were used. Sebacic acid was selected as a representative of pollutants in the most wastewater produced by chemical process industries. The effect of different operational conditions including treatment time, the reactor pressure as well as the role of oxidizing agents such as (H2O2) were investigated on the decomposition rate of sebacic acid. Concentration of sebacic acid was quantified by Ion Chromatography/Mass Spectrometry (IC/MS). The oxygen plasma showed higher decomposition rate in basic medium. Adding H2O2 into aqueous solution enhanced the sebacic acid decomposition rate with the CO2/CH4 plasma up to the same decomposition rate of the oxygen plasma. Increasing the pressure also increased the decomposition rate for both plasmas with an increase twice higher for the CO2/CH4 plasma than that of the oxygen plasma. This work therefore presents the conditions in which these plasmas can provide the same decomposition rate for contaminants in aqueous solution.

  15. Proper orthogonal decomposition method for analysis of nonlinear panel flutter with thermal effects in supersonic flow

    NASA Astrophysics Data System (ADS)

    Xie, Dan; Xu, Min; Dai, Honghua; Dowell, Earl H.

    2015-02-01

    The proper orthogonal decomposition (POD) method for analysis of nonlinear panel flutter subjected to supersonic flow is presented. Optimal POD modes are extracted from a chaotic Galerkin mode responses. The aeroelastic equations of motion are constructed using von Karman plate theory, first-order piston theory and quasi-steady thermal stress theory. A simply-supported plate with thermal loads from a uniformly distributed temperature is considered. Many types of panel behaviors, including stable flat, dynamically stable buckled, limit cycle oscillation, nonharmonic periodic motion, quasi-periodic motion and chaotic motion are observed. Our primary focus is on chaos and the route to chaos. It is found that a sudden transition from the buckled state to chaos occurs. Time history, phase portrait, Poincaré map, bifurcation diagram and Lyapunov exponent are employed to study chaos. The POD chaotic results obtained are compared with the traditional Galerkin solutions. It is shown that the POD method can obtain accurate chaotic solutions, using fewer modes and less computational effort than the Galerkin mode approach; additionally, the POD method converges faster in the analysis of chaotic transients. Effects of length-to-width ratios and thermal loads are presented. It is found that a smaller width for fixed length will produce more stable flutter response, while the thermal loads degrade the flutter boundary and result in a more complex evolution of dynamic motions. The numerical simulations show that the robustness of the POD modes depends on the dynamic pressure but not on temperature.

  16. Thermal and electrochemical decomposition of lithium peroxide in non-catalyzed carbon cathodes for Li-air batteries.

    PubMed

    Beyer, H; Meini, S; Tsiouvaras, N; Piana, M; Gasteiger, H A

    2013-07-14

    The decomposition of lithium peroxide during the charging process of lithium-air batteries is investigated. A novel preparation method for electrodes in the discharged state, i.e., prefilled with Li2O2 using polyethylene oxide as a binder, is presented. The composition and reactivity of Li2O2-prefilled electrodes are examined by thermal analysis coupled with on-line mass spectrometry. Voltage profiles and gas evolution during the charging process of Li2O2-prefilled electrodes in battery cells are correlated with the thermal decomposition process of Li2O2 and its impact on other electrode compounds. It is found that both thermal Li2O2 decomposition and the electrochemical decomposition of Li2O2 during charging enhance the oxidation of the electrolyte, the binder, and/or carbon, which is suggested to be due to the formation of "nascent" oxygen during Li2O2 decomposition into O2 and Li2O (thermally) or into O2 and lithium ions (electrochemically). PMID:23715054

  17. Supersonic jet/multiphoton ionization spectrometry of chemical species resulting from thermal decomposition and laser ablation of polymers

    NASA Astrophysics Data System (ADS)

    Hozumi, Masami; Murata, Yoshiaki; Cheng-Huang Lin, Imasaka, Totaro

    1995-04-01

    The chemical species resulting from thermal decomposition and laser ablation of polymers are measured by excitation/fluorescence and multiphoton ionization/mass spectrometries after supersonic jet expansion for rotational cooling to simply the optical spectrum. The signal of minor chemical species occurred is strongly enhanced by resonant excitation and multiphoton ionization, and even the isomer can be clearly differentiated. For example, p-cresol occurred by thermal decomposition of polycarbonate is detected selectively by mass-selected resonant multiphoton ionization spectrometry. Various chemical species occurred by laser ablation of even a polystyrene foam are also measured by this technique.

  18. Fabrication of low-density GaN/AlN quantum dots via GaN thermal decomposition in MOCVD

    PubMed Central

    2014-01-01

    With an appropriate high anneal temperature under H2 atmosphere, GaN quantum dots (QDs) have been fabricated via GaN thermal decomposition in metal organic chemical vapor deposition (MOCVD). Based on the characterization of atomic force microscopy (AFM), the obtained GaN QDs show good size distribution and have a low density of 2.4 × 108 cm-2. X-ray photoelectron spectroscopy (XPS) analysis demonstrates that the GaN QDs were formed without Ga droplets by thermal decomposition of GaN. PMID:25136276

  19. Unimolecular thermal decomposition of phenol and d5-phenol: Direct observation of cyclopentadiene formation via cyclohexadienone

    NASA Astrophysics Data System (ADS)

    Scheer, Adam M.; Mukarakate, Calvin; Robichaud, David J.; Nimlos, Mark R.; Carstensen, Hans-Heinrich; Barney Ellison, G.

    2012-01-01

    The pyrolyses of phenol and d5-phenol (C6H5OH and C6D5OH) have been studied using a high temperature, microtubular (μtubular) SiC reactor. Product detection is via both photon ionization (10.487 eV) time-of-flight mass spectrometry and matrix isolation infrared spectroscopy. Gas exiting the heated reactor (375 K-1575 K) is subject to a free expansion after a residence time in the μtubular reactor of approximately 50-100 μs. The expansion from the reactor into vacuum rapidly cools the gas mixture and allows the detection of radicals and other highly reactive intermediates. We find that the initial decomposition steps at the onset of phenol pyrolysis are enol/keto tautomerization to form cyclohexadienone followed by decarbonylation to produce cyclopentadiene; C6H5OH → c-C6H6 = O → c-C5H6 + CO. The cyclopentadiene loses a H atom to generate the cyclopentadienyl radical which further decomposes to acetylene and propargyl radical; c-C5H6 → c-C5H5 + H → HC≡CH + HCCCH2. At higher temperatures, hydrogen loss from the PhO-H group to form phenoxy radical followed by CO ejection to generate the cyclopentadienyl radical likely contributes to the product distribution; C6H5O-H → C6H5O + H → c-C5H5 + CO. The direct decarbonylation reaction remains an important channel in the thermal decomposition mechanisms of the dihydroxybenzenes. Both catechol (o-HO-C6H4-OH) and hydroquinone (p-HO-C6H4-OH) are shown to undergo decarbonylation at the onset of pyrolysis to form hydroxycyclopentadiene. In the case of catechol, we observe that water loss is also an important decomposition channel at the onset of pyrolysis.

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

    PubMed

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

    2015-11-28

    Thermal decomposition of dolomite in the presence of CO2 in a calcination environment is investigated by means of in situ X-ray diffraction (XRD) and thermogravimetric analysis (TGA). The in situ XRD results suggest that dolomite decomposes directly at a temperature around 700 °C into MgO and CaO. Immediate carbonation of nascent CaO crystals leads to the formation of calcite as an intermediate product of decomposition. Subsequently, decarbonation of this poorly crystalline calcite occurs when the reaction is thermodynamically favorable and sufficiently fast at a temperature depending on the CO2 partial pressure in the calcination atmosphere. Decarbonation of this dolomitic calcite occurs at a lower temperature than limestone decarbonation due to the relatively low crystallinity of the former. Full decomposition of dolomite leads also to a relatively low crystalline CaO, which exhibits a high reactivity as compared to limestone derived CaO. Under CO2 capture conditions in the Calcium-Looping (CaL) process, MgO grains remain inert yet favor the carbonation reactivity of dolomitic CaO especially in the solid-state diffusion controlled phase. The fundamental mechanism that drives the crystallographic transformation of dolomite in the presence of CO2 is thus responsible for its fast calcination kinetics and the high carbonation reactivity of dolomitic CaO, which makes natural dolomite a potentially advantageous alternative to limestone for CO2 capture in the CaL technology as well as SO2in situ removal in oxy-combustion fluidized bed reactors. PMID:26506285

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

    PubMed

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

    2015-01-28

    The pyrolysis of the benzyl radical has been studied in a set of heated micro-reactors. A combination of photoionization mass spectrometry (PIMS) and matrix isolation infrared (IR) spectroscopy has been used to identify the decomposition products. Both benzyl bromide and ethyl benzene have been used as precursors of the parent species, C6H5CH2, as well as a set of isotopically labeled radicals: C6H5CD2, C6D5CH2, and C6H5 (13)CH2. The combination of PIMS and IR spectroscopy has been used to identify the earliest pyrolysis products from benzyl radical as: C5H4=C=CH2, H atom, C5H4-C ≡ CH, C5H5, HCCCH2, and HC ≡ CH. Pyrolysis of the C6H5CD2, C6D5CH2, and C6H5 (13)CH2 benzyl radicals produces a set of methyl radicals, cyclopentadienyl radicals, and benzynes that are not predicted by a fulvenallene pathway. Explicit PIMS searches for the cycloheptatrienyl radical were unsuccessful, there is no evidence for the isomerization of benzyl and cycloheptatrienyl radicals: C6H5CH2⇋C7H7. These labeling studies suggest that there must be other thermal decomposition routes for the C6H5CH2 radical that differ from the fulvenallene pathway. PMID:25637987

  2. Structural, optical and magnetic properties of gadolinium sesquioxide nanobars synthesized via thermal decomposition of gadolinium oxalate

    SciTech Connect

    Manigandan, R.; Giribabu, K.; Suresh, R.; Vijayalakshmi, L.; Stephen, A.; Narayanan, V.

    2013-10-15

    Graphical abstract: - Highlights: • The cubic Gd{sub 2}O{sub 3} nanobars are synthesized by decomposition of C{sub 6}H{sub 20}Gd{sub 2}O{sub 22}. • The nanoparticles are rectangular bar shape with high porous surface. • The combination of magnetic and optical properties within a single particle. • The Gd{sub 2}O{sub 3} nanobars have tailorable nanostructure, wide bandgap and are paramagnetic. - Abstract: Gadolinium oxide nanobars were obtained by thermal decomposition of gadolinium oxalate, which was synthesized by the chemical precipitation method along with glycerol. The functional group analysis and formation of gadolinium oxide from gadolinium oxalate were characterized by the Fourier transform infrared spectroscopy and thermo gravimetric analyzer. The crystal structure, average crystallite size, and lattice parameter were analyzed by X-ray diffraction technique. Moreover, Raman shifts, elemental composition and morphology of the gadolinium oxide was widely investigated by the laser Raman microscope, X-ray photoelectron spectroscopy, FE-SEM-EDAX and HR-TEM, respectively. Furthermore, the optical properties like band gap, absorbance measurement of the gadolinium oxide were extensively examined. In addition, the paramagnetic property of gadolinium oxide nanobars was explored by the vibrating sample magnetometer.

  3. Dynamic analysis of elemental mercury released from thermal decomposition of coal

    SciTech Connect

    Shaoqing Guo; Jianli Yang; Zhenyu Liu

    2009-09-15

    Mercury (Hg) is a toxic and ubiquitous trace element in coal. Monitoring its release behavior during coal processing is a challenging problem. This paper presents a method that is capable of online measurement of the dynamic release behavior of elemental Hg (Hg{sup 0}) from thermal decomposition of coal. The method couples a temperature-programmed decomposition unit with an atomic fluorescence spectrometry detector (TPD-AFS). The AFS signal can be converted to Hg content for quantitative analysis through calibration. The main advantage of the TPD-AFS system is that it can provide either real-time or accumulated data. It was confirmed that the amount of Hg{sup 0} determined by this method agreed well with that by the Ontario-Hydro method, and the results are reproducible with a high accuracy. The method can be used to characterize the release behavior of Hg in coals upon heating and may be used to identify the forms of occurrence of Hg in coals. 16 refs., 4 figs., 3 tabs.

  4. Thermal Decomposition of C7H7 Radicals; Benzyl, Tropyl, and Norbornadienyl

    NASA Astrophysics Data System (ADS)

    Buckingham, Grant; Ellison, Barney; Daily, John W.; Ahmed, Musahid

    2015-06-01

    Benzyl radical (C6H5CH2) and two other C7H7 radicals are commonly encountered in the combustion of substituted aromatic compounds found in biofuels and gasoline. High temperature pyrolysis of benzyl radical requires isomerization to other C7H7 radicals that may include cycloheptatrienyl (tropyl) radical (cyc-C7H7) and norbornadienyl radical. The thermal decomposition of all three radicals has now been investigated using a micro-reactor that heats dilute gas-phase samples up to 1600 K and has a residence time of about 100 μ-sec. The pyrolysis products exit the reactor into a supersonic expansion and are detected using synchrotron-based photoionization mass spectrometry and matrix-isolation IR spectroscopy. The products of the pyrolysis of benzyl radical (C6H5CH2) along with three isotopomers (C6H513CH2, C6D5CH2, and C6H5CD2) were detected and identified. The distribution of 13C atoms and D atoms indicate that multiple different decomposition pathways are active. Buckingham, G. T., Ormond, T. K., Porterfield, J. P., Hemberger, P., Kostko, O., Ahmed, M., Robichaud, D. J., Nimlos, M. R., Daily, J. W., Ellison, G. B. 2015, Journal of Chemical Physics 142 044307

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

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

  6. Theoretical Study of the Thermal Decomposition of Carboxylic Acids at Pyrolysis Temperature

    SciTech Connect

    Clark, J. M.; Robichaud, D. J.; Nimlos, M. R.

    2013-01-01

    Carboxylic acids are important in the processing of biomass into renewable fuels and chemicals. They are formed from the pretreatment and pyrolysis of hemicellulose biopolymers and are released from the decomposition of sugars. They result from the deconstruction of polyhydroxyalkanoates (bacterial carbon storage polymers) from fatty acids derived from algae, bacteria, and oil crops. The thermal deoxygenation of carboxylic acids is an important step in the conversion of biomass into aliphatic hydrocarbons suitable for use in renewable biofuels and as petrochemical replacements. Decarboxylation, a primary decomposition pathway under pyrolysis conditions, represents an ideal conversion process, because it eliminates two atoms of oxygen for every carbon atom removed. Problematically, additional deoxygenation processes exist (e.g. dehydration) that are in direct competition with decarboxylation and result in the formation of reactive and more fragmented end products. To better understand the competition between decarboxylation and other deoxygenation processes and to gain insight into possible catalysts that would favor decarboxylation, we have investigated the mechanisms and thermochemistry of the various unimolecular and bimolecular deoxygenation pathways for a family of C1-C4 organic acids using electronic structure calculations at the M06-2X/6-311++G(2df,p) level of theory.

  7. Study of condition-dependent decomposition reactions; Part I. The thermal behaviour and decomposition of 2-nitrobenzoyl chloride.

    PubMed

    Lever, Sarah D; Papadaki, Maria

    2004-11-11

    The risks associated with batch processing in the manufacture of chemicals and pharmaceuticals via highly exothermic reactions are of special interest due to the possibility of runaway reactions. o-Nitrated benzoyl chlorides are intermediates in the production of agrochemicals and are produced via the reaction of o-nitrated carboxylic acids with thionyl chloride in a solvent mixture. ortho-Nitrated acyl chlorides have exploded violently on attempted distillation on numerous occasions. An inadequate investigation of the process prior to large-scale operation is the most likely cause. Here we present preliminary results of studies on the decomposition of 2-nitrobenzoyl chloride. This study has revealed that the decomposition reaction is strongly condition dependent. The heating rate of the sample plays a preponderant role in the course of the decomposition reaction. That renders the interpretation of differential scanning calorimetry (DSC) or adiabatic calorimetry measurements, which are routinely used to assess the thermochemistry and safety of the large-scale reactions, problematic. Following this on-going study, we report here key features of the system that have been identified. PMID:15518968

  8. Thermal decomposition study of Mn doped Fe3O4 nanoparticles

    NASA Astrophysics Data System (ADS)

    Malek, Tasmira J.; Chaki, S. H.; Tailor, J. P.; Deshpande, M. P.

    2016-05-01

    Fe3O4 is an excellent magnetic material among iron oxides. It has a cubic inverse spinel structure exhibiting distinguished electric and magnetic properties. In this paper the authors report the synthesis of Mn doped Fe3O4 nanoparticles by wet chemical reduction technique at ambient temperature and its thermal characterization. Ferric chloride hexa-hydrate (FeCl3•6H2O), manganese chloride tetra-hydrate (MnCl2•4H2O) and sodium boro-hydrate (NaBH4) were used for synthesis of Fe3O4 nanoparticles at ambient temperature. The elemental composition of the as-synthesized Mn doped Fe3O4 nanoparticles were determined by energy dispersive analysis of X-rays (EDAX) technique. Thermogravimetric (TG) and differential thermal analysis (DTA) were carried out on the Mn doped Fe3O4 nanoparticles in the temperature range of ambient to 1124 K. The thermo-curves revealed that the particles decompose by four steps. The kinetic parameters were evaluated using non-mechanistic equations for the thermal decomposition.

  9. Development of Boundary Condition Independent Reduced Order Thermal Models using Proper Orthogonal Decomposition

    NASA Astrophysics Data System (ADS)

    Raghupathy, Arun; Ghia, Karman; Ghia, Urmila

    2008-11-01

    Compact Thermal Models (CTM) to represent IC packages has been traditionally developed using the DELPHI-based (DEvelopment of Libraries of PHysical models for an Integrated design) methodology. The drawbacks of this method are presented, and an alternative method is proposed. A reduced-order model that provides the complete thermal information accurately with less computational resources can be effectively used in system level simulations. Proper Orthogonal Decomposition (POD), a statistical method, can be used to reduce the order of the degree of freedom or variables of the computations for such a problem. POD along with the Galerkin projection allows us to create reduced-order models that reproduce the characteristics of the system with a considerable reduction in computational resources while maintaining a high level of accuracy. The goal of this work is to show that this method can be applied to obtain a boundary condition independent reduced-order thermal model for complex components. The methodology is applied to the 1D transient heat equation.

  10. Analysis of ZDDP Content and Thermal Decomposition in Motor Oils Using NAA and NMR

    NASA Astrophysics Data System (ADS)

    Ferguson, S.; Johnson, J.; Gonzales, D.; Hobbs, C.; Allen, C.; Williams, S.

    Zinc dialkyldithiophosphates (ZDDPs) are one of the most common anti-wear additives present in commercially-available motor oils. The ZDDP concentrations of motor oils are most commonly determined using inductively coupled plasma atomic emission spectroscopy (ICP-AES). As part of an undergraduate research project, we have determined the Zn concentrations of eight commercially-available motor oils and one oil additive using neutron activation analysis (NAA), which has potential for greater accuracy and less sensitivity to matrix effects as compared to ICP-AES. The 31P nuclear magnetic resonance (31P-NMR) spectra were also obtained for several oil additive samples which have been heated to various temperatures in order to study the thermal decomposition of ZDDPs.

  11. A DFT analysis of thermal decomposition reactions important to natural products.

    PubMed

    Setzer, William N

    2010-07-01

    The thermal decomposition reactions of several important natural flavor and fragrance chemicals have been investigated using density functional theory (DFT, B3LYP/6-31G*). Retro-aldol reactions of glucose, fructose, hernandulcin, epihernandulcin, [3]-gingerol, and [4]-isogingerol; retro-carbonyl-ene reactions of isopulegol, lavandulol, isolyratol, and indicumenone; and pyrolytic syn elimination reactions of linalyl acetate, alpha-terpinyl acetate, and bornyl acetate, have been carried out. The calculations indicate activation enthalpies of around 30 kcal/mol for the retro-aldol reactions and for retro-carbonyl-ene reactions, comparable to pericyclic reactions such as the Cope rearrangement and electrocyclic reactions, and therefore important reactions at elevated temperatures (e.g., boiling aqueous solutions, gas-chromatograph injection ports). Activation enthalpies for pyrolytic eliminations are around 40 kcal/mol and are unlikely to occur during extraction or GC analysis. PMID:20734926

  12. Fabrication of lotus-type porous copper through thermal decomposition of titanium hydride

    NASA Astrophysics Data System (ADS)

    Ide, T.; Nakajima, H.

    2009-05-01

    Lotus-type porous copper was fabricated by unidirectional solidification through thermal decomposition of titanium hydride. Effects of additive method and additive amount of titanium hydride on pore formation were investigated. The porosity of lotus copper depends on additive method and additive amount of titanium hydride. The pore formation effectively occurs in the method that titanium hydride decomposes in molten copper. For all the additive methods of titanium hydride, the porosity increases and pore diameter does not change with increasing additive amount of titanium hydride. While, for adding large amount of titanium hydride, the porosity became constant. This is because hydrogen solubility in liquid phase does not change owing to bubbling of hydrogen gas.

  13. Fabrication of Porous Copper with Directional Pores by Continuous Casting Technique Through Thermal Decomposition of Hydride

    NASA Astrophysics Data System (ADS)

    Ide, Takuya; Tsunemi, Akihiro; Nakajima, Hideo

    2014-08-01

    Lotus-type porous copper with aligned long cylindrical pores was fabricated by continuous casting technique through thermal decomposition method (TDM) in an argon atmosphere of 0.1 MPa. A pellet of titanium hydride was supplied into molten copper with adjusting the time interval to maintain the constant concentration of hydrogen to be dissolved in the melt, when the transfer velocity of the unidirectional solidification is changed. Long lotus-type porous copper slabs were fabricated with constant solidification velocity. The effect of the transfer velocity on the porosity and pore size was investigated. The average pore diameter was independent of the transfer velocity, but the porosity is slightly dependent on the velocity. It is apparent that the continuous casting technique can be applicable for production of lotus metals through TDM.

  14. A facile thermal decomposition route to synthesise CoFe2O4 nanostructures

    NASA Astrophysics Data System (ADS)

    Kalpanadevi, K.; Sinduja, C. R.; Manimekalai, R.

    2014-01-01

    The synthesis of CoFe2O4 nanoparticles has been achieved by a simple thermal decomposition method from an inorganic precursor, cobalt ferrous cinnamate hydrazinate (CoFe2(cin)3(N2H4)3) which was obtained by a novel precipitation method from the corresponding metal salts, cinnamic acid and hydrazine hydrate. The precursor was characterized by hydrazine and metal analyses, infrared spectral analysis and thermo gravimetric analysis. Under appropriate annealing, CoFe2(cin)3(N2H4)3 yielded CoFe2O4 nanoparticles, which were characterized for their size and structure using X-Ray diffraction (XRD), high resolution transmission electron microscopic (HRTEM), selected area electron diffraction (SAED) and scanning electron microscopic (SEM) techniques.

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

    NASA Astrophysics Data System (ADS)

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

    2009-04-01

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

  16. Thermodynamic data for the modeling of the thermal decomposition of biodiesel. 1. Saturated and monounsaturated FAMEs.

    PubMed

    Osmont, Antoine; Catoire, Laurent; Dagaut, Philippe

    2010-03-25

    Thermochemical data were computed for numerous species needed for performing detailed chemical kinetic modeling of biodiesel thermal decomposition and combustion. Most of these data concerning large species had not been experimentally determined. A B3LYP/6-31G(d,p) method using the atomization approach derived earlier was used to provide these data. The presently computed thermochemical data are provided in the CHEMKIN-NASA format as Supporting Information. Species considered are fatty acid methyl esters (FAMEs), various oxygenated radicals formed from FAMEs by C-H, C-C, and C-O bond breakings and subsequent chemistries, 1-, 2-, 3-, and 5-saturated alkyl radicals, monounsaturated 1-alkyl radicals, among others. PMID:19694476

  17. Experimental and modeling study of the thermal decomposition of methyl decanoate

    PubMed Central

    Herbinet, Olivier; Glaude, Pierre-Alexandre; Warth, Valérie; Battin-Leclerc, Frédérique

    2013-01-01

    The experimental study of the thermal decomposition of methyl decanoate was performed in a jet-stirred reactor at temperatures ranging from 773 to 1123 K, at residence times between 1 and 4 s, at a pressure of 800 Torr (106.6 kPa) and at high dilution in helium (fuel inlet mole fraction of 0.0218). Species leaving the reactor were analyzed by gas chromatography. Main reaction products were hydrogen, carbon oxides, small hydrocarbons from C1 to C3, large 1-olefins from 1-butene to 1-nonene, and unsaturated esters with one double bond at the end of the alkyl chain from methyl-2-propenoate to methyl-8-nonenoate. At the highest temperatures, the formation of polyunsaturated species was observed: 1,3-butadiene, 1,3-cyclopentadiene, benzene, toluene, indene, and naphthalene. These results were compared with previous ones about the pyrolysis of n-dodecane, an n-alkane of similar size. The reactivity of both molecules was found to be very close. The alkane produces more olefins while the ester yields unsaturated oxygenated compounds. A detailed kinetic model for the thermal decomposition of methyl decanoate has been generated using the version of software EXGAS which was updated to take into account the specific chemistry involved in the oxidation of methyl esters. This model contains 324 species and 3231 reactions. It provided a very good prediction of the experimental data obtained in jet-stirred reactor. The formation of the major products was analyzed. The kinetic analysis showed that the retro-ene reactions of intermediate unsaturated methyl esters are of importance in low reactivity systems. PMID:23710078

  18. Parallel computation for reservoir thermal simulation: An overlapping domain decomposition approach

    NASA Astrophysics Data System (ADS)

    Wang, Zhongxiao

    2005-11-01

    In this dissertation, we are involved in parallel computing for the thermal simulation of multicomponent, multiphase fluid flow in petroleum reservoirs. We report the development and applications of such a simulator. Unlike many efforts made to parallelize locally the solver of a linear equations system which affects the performance the most, this research takes a global parallelization strategy by decomposing the computational domain into smaller subdomains. This dissertation addresses the domain decomposition techniques and, based on the comparison, adopts an overlapping domain decomposition method. This global parallelization method hands over each subdomain to a single processor of the parallel computer to process. Communication is required when handling overlapping regions between subdomains. For this purpose, MPI (message passing interface) is used for data communication and communication control. A physical and mathematical model is introduced for the reservoir thermal simulation. Numerical tests on two sets of industrial data of practical oilfields indicate that this model and the parallel implementation match the history data accurately. Therefore, we expect to use both the model and the parallel code to predict oil production and guide the design, implementation and real-time fine tuning of new well operating schemes. A new adaptive mechanism to synchronize processes on different processors has been introduced, which not only ensures the computational accuracy but also improves the time performance. To accelerate the convergence rate of iterative solution of the large linear equations systems derived from the discretization of governing equations of our physical and mathematical model in space and time, we adopt the ORTHOMIN method in conjunction with an incomplete LU factorization preconditioning technique. Important improvements have been made in both ORTHOMIN method and incomplete LU factorization in order to enhance time performance without affecting

  19. Magnetite Formation from Thermal Decomposition of Siderite: Implications for Inorganic Magnetite Formation in Martian Meteorite ALH84001

    NASA Technical Reports Server (NTRS)

    Morris, RIchard V.

    2002-01-01

    A biogenic mechanism for formation of a subpopulation magnetite in Martian meteorite ALH84001 has been suggested [McKay et al., 1996; Thomas-Keprta, et al., 2000]. We are developing experimental evidence for an alternating working hypothesis, that the subpopulation was produced inorganically by the thermal decomposition of siderite [Golden et al., 2000].

  20. Effect of thermal shock on the decomposition of rocks under controlled laboratory conditions

    NASA Astrophysics Data System (ADS)

    Kasanin-Grubin, Milica; Vezmar, Tijuana; Kuhn, Nikolaus J.

    2013-04-01

    The major factor determining the rate of weathering of a given rock are the climatic conditions of the surrounding environment, most notably type and amount of precipitation and temperature. For the latter, average annual temperature and where applicable, the frequency of freezing and thawing are often considered to be relevant for weathering. The rate of temperature change is mostly ignored. However, a rapid change in temperature, referred to as thermal shock could have more severe consequences of rock deterioration then gradual heating and cooling of rocks is gradual. Thermal shock induces a stress of such a magnitude that the material is unable to adjust fast enough and so it breaks down. The aim of this study is to examine the importance of mechanical decomposition of rocks when treated with thermal shock by freezing. The rate of decomposition of rocks of various sizes was measured based on their weight loss. In addition, they were immersed in water after freezing and the electrical conductivity and pH of the water were measured as an index for thermal-shock induced micro-fracturing. Samples of three rock types were chosen for the experiment: limestone, tuffaceous rock and basalt. Samples were examined in two separate cycles: (i) 24h immersion in ultra-clean water followed by 24h drying at 30o and (ii) 24h immersion, 24h temperature shock by freezing at -20˚C and 6h thawing. Each cycle was repeated approximately 20 times. In each cycle three different sizes of rock were examined: <16mm, 16-8mm and 8-5mm. Limestone mass decreased for both cycles, although more distinctly after repeated thermal shocks. Furthermore, the rate of decay decreased with increasing rock size. Tuffaceous rock exposed to cycle (i) also showed a significant weight loss. Somewhat surprisingly, the mass of the tuffaceous rock exposed to thermal shock increased by about 13% in all sample size groups. It is possible that pore volume increased during experiment and that the rocks became

  1. Analysis of polyethylene microplastics in environmental samples, using a thermal decomposition method.

    PubMed

    Dümichen, Erik; Barthel, Anne-Kathrin; Braun, Ulrike; Bannick, Claus G; Brand, Kathrin; Jekel, Martin; Senz, Rainer

    2015-11-15

    Small polymer particles with a diameter of less than 5 mm called microplastics find their way into the environment from polymer debris and industrial production. Therefore a method is needed to identify and quantify microplastics in various environmental samples to generate reliable concentration values. Such concentration values, i.e. quantitative results, are necessary for an assessment of microplastic in environmental media. This was achieved by thermal extraction in thermogravimetric analysis (TGA), connected to a solid-phase adsorber. These adsorbers were subsequently analysed by thermal desorption gas chromatography mass spectrometry (TDS-GC-MS). In comparison to other chromatographic methods, like pyrolyse gas chromatography mass spectrometry (Py-GC-MS), the relatively high sample masses in TGA (about 200 times higher than used in Py-GC-MS) analysed here enable the measurement of complex matrices that are not homogenous on a small scale. Through the characteristic decomposition products known for every kind of polymer it is possible to identify and even to quantify polymer particles in various matrices. Polyethylene (PE), one of the most important representatives for microplastics, was chosen as an example for identification and quantification. PMID:26376022

  2. Size dependence of the magnetic properties of Ni nanoparticles prepared by thermal decomposition method

    PubMed Central

    2013-01-01

    By means of thermal decomposition, we prepared single-phase spherical Ni nanoparticles (23 to 114 nm in diameter) that are face-centered cubic in structure. The magnetic properties of the Ni nanoparticles were experimentally as well as theoretically investigated as a function of particle size. By means of thermogravimetric/differential thermal analysis, the Curie temperature TC of the 23-, 45-, 80-, and 114-nm Ni particles was found to be 335°C, 346°C, 351°C, and 354°C, respectively. Based on the size-and-shape dependence model of cohesive energy, a theoretical model is proposed to explain the size dependence of TC. The measurement of magnetic hysteresis loop reveals that the saturation magnetization MS and remanent magnetization increase and the coercivity decreases monotonously with increasing particle size, indicating a distinct size effect. By adopting a simplified theoretical model, we obtained MS values that are in good agreement with the experimental ones. Furthermore, with increase of surface-to-volume ratio of Ni nanoparticles due to decrease of particle size, there is increase of the percentage of magnetically inactive layer. PMID:24164907

  3. Perchlorate induced low temperature carbonate decomposition in the Mars Phoenix Thermal and Evolved Gas Analyzer (TEGA)

    NASA Astrophysics Data System (ADS)

    Cannon, K. M.; Sutter, B.; Ming, D. W.; Boynton, W. V.; Quinn, R.

    2012-07-01

    Simulated Thermal Evolved Gas Analyzer (TEGA) analyses have shown that a CO2 release detected between 400°C and 680°C by the Phoenix Lander's TEGA instrument may have been caused by a reaction between calcium carbonate and hydrated magnesium perchlorate. In our experiments a CO2 release beginning at 385 ± 12°C was attributed to calcite reacting with water vapor and HCl gas from the dehydration and thermal decomposition of Mg-perchlorate. The release of CO2 is consistent with the TEGA detection of CO2 released between 400 and 680°C, with the amount of CO2 increasing linearly with added perchlorate. X-ray diffraction (XRD) experiments confirmed CaCl2 formation from the reaction between calcite and HCl. These results have important implications for the Mars Science Laboratory (MSL) Curiosity rover. Heating soils may cause inorganic release of CO2; therefore, detection of organic fragments, not CO2 alone, should be used as definitive evidence for organics in Martian soils.

  4. Thermal decomposition of HMX: Low temperature reaction kinetics and their use for assessing response in abnormal thermal environments and implications for long-term aging

    SciTech Connect

    Behrens, R.; Bulusu, S.

    1995-12-01

    The thermal decomposition of HMX between 175 and 200{degree}C has been studied using the simultaneous thermogravimetric modulated beam mass spectrometer (STMBMS) apparatus with a focus on the initial stages of the decomposition. The identity of thermal decomposition products is the same as that measured in previous higher temperature experiments. The initial stages of the decomposition are characterized by an induction period followed by two acceleratory periods. The Arrhenius parameters for the induction and two acceleratory periods are (Log(A) = 18.2 {plus_minus} 0.8, Ea = 48.2 {plus_minus} 1.8 kcal/mole), (Log(A) = 17.15 {plus_minus} 1.5 and Ea = 48.9 {plus_minus} 3.2 kcal/mole), (Log A) = 19.1 {plus_minus} 3.0 and Ea = 52.1 {plus_minus} 6.3 kcal/mole), respectively. This data can be used to calculate the time and temperature required to decompose a desired fraction of a sample that is being prepared to test the effect of thermal degradation on its sensitivity or burn rates. It can also be used to estimate the extent of decomposition that may be expected under normal storage conditions for munitions containing HMX. This data, along with previous mechanistic studies conducted at higher temperatures, suggest that the process that controls the early stages of decomposition of HMX in the solid phase is scission of the N-NO{sub 2} bond, reaction of the N0{sub 2} within a ``lattice cage`` to form the mononitroso analogue of HMX and decomposition of the mononitroso HMX within the HMX lattice to form gaseous products that are retained in bubbles or diffuse into the surrounding lattice.

  5. Condensed-phase thermal decomposition of TATB investigated by atomic force microscopy (AFM) and simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS)

    SciTech Connect

    Land, T.A.; Siekhaus, W.J.; Foltz, M.F.; Behrens, R. Jr.

    1993-05-01

    A combination of techniques has been used to investigate the condensed-phase thermal decomposition of TATB. STMBMS has been used to identify the thermal decomposition products and their temporal correlation`s. These experiments have shown that the condensed-phase decomposition proceeds through several autocatalytic pathways. Both low and high molecular weight decomposition products have been identified. Mono-, di- and tri-furazans products have been identified and, their temporal behaviors are consistent with a stepwise loss of water. AFM has been used to correlate the decomposition chemistry with morphological changes occurring as a function of heating. Patches of small 25-140 nm round holes were observed throughout the lattice of TATB crystals that were heated briefly to 300C. It is likely that these holes show where decomposition reactions have started. Evidence of decomposition products have been seen in TATB that has been held at 250C for one hour.

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

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

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

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

    SciTech Connect

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

    2015-01-28

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

  8. Unimolecular Thermal Decomposition of Phenol and d5-Phenol: Direct Observation of Cyclopentadiene Formation via Cyclohexadienone

    SciTech Connect

    Scheer, A. M.; Mukarakate, C.; Robichaud, D. J.; Nimlos, M. R.; Carstensen, H. H.; Barney, E. G.

    2012-01-28

    The pyrolyses of phenol and d{sub 5}-phenol (C{sub 6}H{sub 5}OH and C{sub 6}D{sub 5}OH) have been studied using a high temperature, microtubular ({mu}tubular) SiC reactor. Product detection is via both photon ionization (10.487 eV) time-of-flight mass spectrometry and matrix isolation infrared spectroscopy. Gas exiting the heated reactor (375 K-1575 K) is subject to a free expansion after a residence time in the {mu}tubular reactor of approximately 50-100 {micro}s. The expansion from the reactor into vacuum rapidly cools the gas mixture and allows the detection of radicals and other highly reactive intermediates. We find that the initial decomposition steps at the onset of phenol pyrolysis are enol/keto tautomerization to form cyclohexadienone followed by decarbonylation to produce cyclopentadiene; C{sub 6}H{sub 5}OH {yields} c-C{sub 6}H{sub 6} = O {yields} c-C{sub 5}H{sub 6} + CO. The cyclopentadiene loses a H atom to generate the cyclopentadienyl radical which further decomposes to acetylene and propargyl radical; c-C{sub 5}H{sub 6} {yields} c-C{sub 5}H{sub 5} + H {yields} HC {triple_bond} CH + HCCCH{sub 2}. At higher temperatures, hydrogen loss from the PhO-H group to form phenoxy radical followed by CO ejection to generate the cyclopentadienyl radical likely contributes to the product distribution; C{sub 6}H{sub 5}O-H {yields} C{sub 6}H{sub 5}O + H {yields} c-C{sub 5}H{sub 5} + CO. The direct decarbonylation reaction remains an important channel in the thermal decomposition mechanisms of the dihydroxybenzenes. Both catechol (o-HO-C{sub 6}H{sub 4}-OH) and hydroquinone (p-HO-C{sub 6}H{sub 4}-OH) are shown to undergo decarbonylation at the onset of pyrolysis to form hydroxycyclopentadiene. In the case of catechol, we observe that water loss is also an important decomposition channel at the onset of pyrolysis.

  9. A flexible and stable numerical method for simulating the thermal decomposition of wood particles.

    PubMed

    Peters, B; Bruch, C

    2001-01-01

    The objective of this paper is to present a flexible and stable simulation method to predict the thermal conversion of wood particles. A combination of several subprocesses such as heating-up, drying, pyrolysis, gasification and combustion of fuel particles of different properties and sizes represents the global process of thermal conversion. This approach allows for simultaneous processes e.g. reactions in time and covers the entire range between transport-limited (shrinking core) and kinetically limited (reacting core) reaction regimes. Thus, the model is applicable to simulate sufficiently accurate the thermal decomposition of each particle in a packed bed, of which the entire conversion is regarded as the sum of all particle processes. Effects such as fragmentation, swelling, homogeneous reactions e.g. ignition outside a particle are excluded as a tradeoff between complexity and calculation time. However, a description of the particle processes by one-dimensional and transient differential conservation equations for mass and energy is feasible to represent the above mentioned subprocesses. The particles are coupled to the gas phase by heat and mass transfer taking into account the Stefan correction due to the gas outflow during conversion. A general formulation of the conservation equations allows the geometry of a fuel particle to be treated as a plate, cylinder or sphere. In order to achieve a high degree of flexibility, the method distinguishes between data, such as kinetics or material properties and the conversion process, for which relevant data are stored in a data base for easy access and extension. The resulting modules of this subdivision are encapsulated into separate software units cast in a hierarchy of well-defined classes in Tools of Object-oriented Software for Continuum-Mechanics Applications (TOSCA) by object-oriented techniques. PMID:11219672

  10. Effect of water vapor on the thermal decomposition process of zinc hydroxide chloride and crystal growth of zinc oxide

    SciTech Connect

    Kozawa, Takahiro; Onda, Ayumu; Yanagisawa, Kazumichi; Kishi, Akira; Masuda, Yasuaki

    2011-03-15

    Thermal decomposition process of zinc hydroxide chloride (ZHC), Zn{sub 5}(OH){sub 8}Cl{sub 2}.H{sub 2}O, prepared by a hydrothermal slow-cooling method has been investigated by simultaneous X-ray diffractometry and differential scanning calorimetry (XRD-DSC) and thermogravimetric-differential thermal analysis (TG-DTA) in a humidity-controlled atmosphere. ZHC was decomposed to ZnO through {beta}-Zn(OH)Cl as the intermediate phase, leaving amorphous hydrated ZnCl{sub 2}. In humid N{sub 2} with P{sub H{sub 2O}}=4.5 and 10 kPa, the hydrolysis of residual ZnCl{sub 2} was accelerated and the theoretical amount of ZnO was obtained at lower temperatures than in dry N{sub 2}, whereas significant weight loss was caused by vaporization of residual ZnCl{sub 2} in dry N{sub 2}. ZnO formed by calcinations in a stagnant air atmosphere had the same morphology of the original ZHC crystals and consisted of the c-axis oriented column-like particle arrays. On the other hand, preferred orientation of ZnO was inhibited in the case of calcinations in 100% water vapor. A detailed thermal decomposition process of ZHC and the effect of water vapor on the crystal growth of ZnO are discussed. -- Graphical abstract: Thermal decomposition process of zinc hydroxide chloride (ZHC), Zn{sub 5}(OH){sub 8}Cl{sub 2}.H{sub 2}O, has been investigated by novel thermal analyses with three different water vapor partial pressures. In the water vapor atmosphere, the formation of ZnO was completed at lower temperatures than in dry. Display Omitted highlights: > We examine the thermal decomposition of zinc hydroxide chloride in water vapor. > Water vapor had no effects on its thermal decomposition up to 230 {sup o}C. > Water vapor accelerated the decomposition of the residual ZnCl{sub 2} in ZnO. > Without water vapor, a large amount of ZnCl{sub 2} evaporated to form the c-axis oriented ZnO.

  11. Thermal decomposition of ammonium perchlorate in the presence of Al(OH)(3)·Cr(OH)(3) nanoparticles.

    PubMed

    Zhang, WenJing; Li, Ping; Xu, HongBin; Sun, Randi; Qing, Penghui; Zhang, Yi

    2014-03-15

    An Al(OH)(3)·Cr(OH)(3) nanoparticle preparation procedure and its catalytic effect and mechanism on thermal decomposition of ammonium perchlorate (AP) were investigated using transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric analysis and differential scanning calorimetry (TG-DSC), X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis and mass spectroscopy (TG-MS). In the preparation procedure, TEM, SAED, and FT-IR showed that the Al(OH)(3)·Cr(OH)(3) particles were amorphous particles with dimensions in the nanometer size regime containing a large amount of surface hydroxyl under the controllable preparation conditions. When the Al(OH)(3)·Cr(OH)(3) nanoparticles were used as additives for the thermal decomposition of AP, the TG-DSC results showed that the addition of Al(OH)(3)·Cr(OH)(3) nanoparticles to AP remarkably decreased the onset temperature of AP decomposition from approximately 450°C to 245°C. The FT-IR, RS and XPS results confirmed that the surface hydroxyl content of the Al(OH)(3)·Cr(OH)(3) nanoparticles decreased from 67.94% to 63.65%, and Al(OH)3·Cr(OH)3 nanoparticles were limitedly transformed from amorphous to crystalline after used as additives for the thermal decomposition of AP. Such behavior of Al(OH)(3)·Cr(OH)(3) nanoparticles promoted the oxidation of NH3 of AP to decompose to N2O first, as indicated by the TG-MS results, accelerating the AP thermal decomposition. PMID:24530852

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

    NASA Astrophysics Data System (ADS)

    Scheer, Adam Michael

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

  13. Rapid thermal decomposition for YBa2Cu3O7-δ films derived by DEA-modified TFA-MOD

    NASA Astrophysics Data System (ADS)

    Zhang, Q. Q.; Zhao, S. C.; Liu, Z. Y.; Rui, R. S.; Qiu, W. B.; Guo, Y. Q.; Li, M. J.; Yang, W. T.; Cai, C. B.

    2014-05-01

    Thermal decomposition of YBa2Cu3O7-δ (YBCO) films derived by diethanolamine (DEA)-modified trifluoroacetic acid-metal organic deposition (TFA-MOD) was investigated with respect to the understanding of the correlation between the stress releasing and rapid decomposition. It is revealed that the evaporation of DEA and the decomposition of precursor films occur simultaneously. A pyrolysis time as 20 seconds is optimal to keep the proper amount of DEA which prevents the films from severe stress during the pyrolysis. Then smooth surface of resultant films appears. In case of a pyrolysis time longer than 40 s, cracks emerge in the films accompanied with complete evaporation of DEA and appearance of Cu-rich particles, while films with pyrolysis time shorter than 10s is excessively soft, with large amount of DEA and TFA remaining in the film, implying insufficient pyrolysis.

  14. Sulfur speciation in hard coal by means of a thermal decomposition method.

    PubMed

    Spiewok, W; Ciba, J; Trojanowska, J

    2002-02-01

    A new method for the determination of organic and pyritic sulfur in hard coal is presented. The method is based on controlled thermal decomposition of coal sample in oxygen-free and oxygen atmospheres. The results for sulfur liberated in an argon atmosphere at temperatures up to 773 K were close to organic sulfur contents (Sorg), although owing to the definition of 'organic sulfur' the values were not directly comparable. Sorg contents are calculated from the difference between total sulfur content in coal and contents of this element in the form of sulfides, sulfates and pyrites. Sulfur contents, found in the second stage of analysis, were close to pyritic sulfur contents. The difference between total sulfur content and the sum of sulfur values obtained in stages I and II corresponded to sulfur contents in those samples which were neither decomposed nor oxidized at temperatures up to 1173 K. Although not comparable with such conventional concepts for industrial purposes these data are attractive due to the ease and rapidity of the new method for the control of sulfur streams in industrial processes. PMID:11939541

  15. Synthesis, Crystal Structure, and Thermal Decomposition of the Cobalt(II) Complex with 2-Picolinic Acid

    PubMed Central

    Li, Di

    2014-01-01

    The cobalt(II) complex of 2-picolinic acid (Hpic), namely, [Co(pic)2(H2O)2] · 2H2O, was synthesized with the reaction of cobalt acetate and 2-picolinic acid as the reactants by solid-solid reaction at room temperature. The composition and structure of the complex were characterized by elemental analysis, infrared spectroscopy, single crystal X-ray diffraction, and thermogravimetry-differential scanning calorimetry (TG-DSC). The crystal structure of the complex belongs to monoclinic system and space group P2(1)/n, with cell parameters of a = 9.8468(7) Å, b = 5.2013(4) Å, c = 14.6041(15) Å, β = 111.745(6)°, V = 747.96(11) Å3, Z = 2, Dc = 1.666 g cm−3, R1 = 0.0297, and wR2 = 0.0831. In the title complex, the Co(II) ion is six-coordinated by two pyridine N atoms and two carboxyl O atoms from two 2-picolinic acid anions, and two O atoms from two H2O molecules, and forming a slightly distorted octahedral geometry. The thermal decomposition processes of the complex under nitrogen include dehydration and pyrolysis of the ligand, and the final residue is cobalt oxalate at about 450°C. PMID:24578654

  16. Thermodynamics and thermal decomposition for shape memory effects with crystallization based on dissipation and logarithmic strain

    NASA Astrophysics Data System (ADS)

    Hall, R. B.; Rao, I. J.; Qi, H. J.

    2014-05-01

    The present effort provides a 3-D thermodynamic framework generalizing the 1-D modeling of 2-way shape memory materials described by Westbrook et al. (J. Eng. Mater. Technol. 312:041010, 2010) and Chung et al. (Macromolecules 41:184-192, 2008), while extending the strain-induced crystallization and shape memory approaches of Rao and Rajagopal (Interfaces Free Bound. 2:73-94, 2000; Int. J. Solids Struct. 38:1149-1167, 2001), Barot and Rao (Z. Angew. Math. Phys. 57:652-681, 2006), and Barot et al. (Int. J. Eng. Sci. 46:325-351, 2008) to include finite thermal expansion within a logarithmic strain basis. The free energy of newly-formed orthotropic crystallites is assumed additive, with no strains in their respective configurations of formation. A multiplicative decomposition is assumed for the assumed thermoelastic orthotropic expansional strains of the respective crystallites. The properties of the crystallites are allowed to depend both on current temperature and their respective temperatures of formation. The entropy production rate relation is written in the frame rotating with the logarithmic spin and produces stress and entropy relations incorporating the integrated configurational free energies, and a driving term for the crystallization analogous to that obtained by the previous studies of Rao et al. The salient attributes of the 1-D modeling of Westbrook et al. are recovered, and applications are discussed.

  17. Thermochemical cycles for energy storage: Thermal decomposition of ZnCO sub 4 systems

    SciTech Connect

    Wentworth, W.E. )

    1992-04-01

    The overall objective of our research has been to develop thermochemical cycles that can be used for energy storage. A specific cycle involving ammonium hydrogen sulfate (NH{sub 4}HSO{sub 4}) has been proposed. Each reaction in the proposed cycle has been examined experimentally. Emphasis has been placed on the basic chemistry of these reactions. In the concluding phase of this research, reported herein, we have shown that when NH{sub 4}HSO{sub 4} is mixed with ZnO and decomposed, the resulting products can be released stepwise (H{sub 2}A{sub (g)} at {approximately}163{degrees}C, NH{sub 3(g)} at 365--418{degrees}C, and a mixture of SO{sub 2(g)} and SO{sub 3(g)} at {approximately}900{degrees}C) and separated by controlling the reaction temperature. Side reactions do not appear to be significant and the respective yields are high as would be required for the successful use of this energy storage reaction in the proposed cycle. Thermodynamic, kinetic, and other reaction parameters have been measured for the various steps of the reaction. Finally we have completed a detailed investigation of one particular reaction: the thermal decomposition of zinc sulfate (ZnSO{sub 4}). We have demonstrated that this reaction can be accelerated and the temperature required reduced by the addition of excess ZnO, V{sub 2}A{sub 5} and possibly other metal oxides.

  18. Adsorption and thermal decomposition of n-azopropane on Pt(111)

    NASA Astrophysics Data System (ADS)

    Gleason, N. R.; Jenks, C. J.; French, C. R.; Bent, B. E.; Zaera, F.

    1998-05-01

    The adsorption and thermal decomposition of n-azopropane on Pt(111) were studied by using temperature-programmed desorption (TPD) and reflection-absorption infra-red spectroscopy (RAIRS). At low temperatures, n-azopropane chemisorbs molecularly on Pt(111), but it isomerizes into a cis configuration upon bonding to the surface and changes its adsorption orientation as a function coverage. Multilayer and monolayer molecular desorption occur about 130 and 170 K, respectively, and a new surface species - probably dipropyl hydrazine - forms upon annealing the remaining chemisorbed molecules above 175 K. Further heating of the sample leads to the desorption of small amounts of propylene and ethylene, at 240 and 275 K, respectively. Another surface transformation is identified by RAIRS around 275 K, possibly the conversion to an imine-type species, and propionitrile and small amounts of propyl and methyl amines are produced soon after that; they desorb at 320 and 330 K, respectively. Finally, a more extensive dehydrogenation of the remaining surface species takes place, and HCN desorbs in two stages around 525 and 600 K. The chemistry of propionitrile and propyl amine was also explored briefly by RAIRS and TPD for reference.

  19. Wavelet subspace decomposition of thermal infrared images for defect detection in artworks

    NASA Astrophysics Data System (ADS)

    Ahmad, M. Z.; Khan, A. A.; Mezghani, S.; Perrin, E.; Mouhoubi, K.; Bodnar, J. L.; Vrabie, V.

    2016-07-01

    Health of ancient artworks must be routinely monitored for their adequate preservation. Faults in these artworks may develop over time and must be identified as precisely as possible. The classical acoustic testing techniques, being invasive, risk causing permanent damage during periodic inspections. Infrared thermometry offers a promising solution to map faults in artworks. It involves heating the artwork and recording its thermal response using infrared camera. A novel strategy based on pseudo-random binary excitation principle is used in this work to suppress the risks associated with prolonged heating. The objective of this work is to develop an automatic scheme for detecting faults in the captured images. An efficient scheme based on wavelet based subspace decomposition is developed which favors identification of, the otherwise invisible, weaker faults. Two major problems addressed in this work are the selection of the optimal wavelet basis and the subspace level selection. A novel criterion based on regional mutual information is proposed for the latter. The approach is successfully tested on a laboratory based sample as well as real artworks. A new contrast enhancement metric is developed to demonstrate the quantitative efficiency of the algorithm. The algorithm is successfully deployed for both laboratory based and real artworks.

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

    SciTech Connect

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

    2015-06-03

    We present a comprehensive template for the design and synthesis of iron oxide nanoparticles with control over size, size distribution, phase, and resulting properties. Monodisperse superparamagnetic iron oxide nanoparticles were synthesized by thermal decomposition of three different iron containing precursors (iron oleate, iron pentacarbonyl, and iron oxyhydroxide) in organic solvents under a variety of synthetic conditions. We compare the suitability of these three kinetically controlled synthesis protocols, which have in common the use of iron oleate as a starting precursor or reaction intermediate, for producing nanoparticles with specific size and magnetic properties. Monodisperse particles were produced over a tunable range of sizes from approximately 2-30 nm. Reaction parameters such as precursor concentration, addition of surfactant, temperature, ramp rate, and time were adjusted to kinetically control size and size-distribution. In particular, large quantities of excess surfactant (up to 25:1 molar ratio) alter reaction kinetics and result in larger particles with uniform size; however, there is often a trade-off between large particles and a narrow size distribution. Iron oxide phase is also critical for establishing magnetic properties. As an example, we show the importance of obtaining the required iron oxide phase for application to Magnetic Particle Imaging (MPI), and describe how phase purity can be controlled.

  1. Growth of Single-Layer Graphene on Pt(111) by Thermal Decomposition of Propylene

    NASA Astrophysics Data System (ADS)

    Hodges, Gregory; Geisler, Heike; Ventrice, Carl

    2009-10-01

    Graphene, which is a one-atom-thick layer of sp^2-bonded carbon, has sparked keen interest within the scientific community because it is predicted to have a wide range of unique properties. In particular, it has one of the highest known mobilities of all the semiconducting materials. Since its discovery in 2004, there have been several studies of the growth of graphene by various techniques. We have performed studies on the growth of graphene on the catalytically active Pt(111) surface by thermal decomposition of propylene in an ultra-high vacuum (UHV) chamber. Two methods have been used: deposition of a monolayer of propylene followed by annealing in UHV and growth of graphene in an atmosphere of 10-6 Torr of propylene at 500 ^oC. The crystal structure of the graphene films was monitored using low energy electron diffraction (LEED). In addition, we are currently performing high resolution electron energy loss spectroscopy (HREELS) measurements of the electronic structure of the graphene films.

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

    SciTech Connect

    Dowding, Kevin J.; Leslie, Ian H.; Hobbs, Michael L.; Rutherford, Brian Milne; Hills, Richard Guy; Pilch, Martin M.

    2004-10-01

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

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

    PubMed Central

    2013-01-01

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

  4. Competing channels in the thermal decomposition of azidoacetone studied by pyrolysis in combination with molecular beam mass spectrometric techniques.

    PubMed

    O'Keeffe, Patrick; Scotti, Giorgio; Stranges, Domenico; Rodrigues, Paula; Barros, M Teresa; Costa, Maria L

    2008-04-10

    The thermal decomposition of azidoacetone (CH3COCH2N3) was studied using a combined experimental and computational approach. Flash pyrolysis at a range of temperatures (296-1250 K) was used to induce thermal decomposition, and the resulting products were expanded into a molecular beam and subsequently analyzed using electron bombardment ionization coupled to a quadrupole mass spectrometer. The advantages of this technique are that the parent molecules spend a very short time in the pyrolysis zone (20-30 mus) and that the subsequent expansion permits the stabilization of thermal products that are not observable using conventional pyrolysis methods. A detailed analysis of the mass spectra as a function of pyrolysis temperature revealed the participation of five thermal decomposition channels. Ab initio calculations on the stable structures and transition states of the azidoacetone system in combination with an analysis of the dissociative ionization pattern of each channel allowed the identity and mechanism of each channel to be elucidated. At low temperatures (296-800 K) the azide decomposes principally by the loss of N2 to yield the imine (CH3COCHNH), which can further decompose to CH3CO and CHNH. At low and intermediate temperatures a process involving the loss of N2 to yield CH3CHO and HCN is also open. Finally, at high temperatures (800-1250 K) a channel in which the azide decomposes to a stable cyclic amine (CO(CH2)2NH) (after loss of N2) is active. The last channel involves subsequent thermal decomposition of this cyclic amine to ketene (H2CCO) and methanimine (H2CNH). PMID:18341306

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

    SciTech Connect

    Huba, ZJ; Carpenter, EE

    2014-06-06

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

  6. An experimental and modeling study of the thermal decomposition of siloxanes on alumina

    NASA Astrophysics Data System (ADS)

    Sonoc, Alexandru Catalin

    Siloxanes are contaminants in biogas produced at wastewater treatment plants and landfills. Siloxanes need to be removed to below 0.01 ppm (vol/vol) Si equivalent before biogas can be used as a fuel in solid oxide fuel cells without damaging them. In engines, the tolerance is no higher than 9.1 ppm (vol/vol) Si equivalent. Thermal decomposition in a packed bed of gamma alumina is a method that can remove siloxanes to the requisite tolerances. The kinetics of the decomposition reaction have not been previously studied and a kinetic model is necessary to design adsorption beds. Experiments with synthetic biogas and packed beds of activated gamma alumina were conducted to provide data to which kinetic models were fitted. The synthetic biogas used was a mixture of carbon dioxide and methane contaminated with octamethylcyclotetrasiloxane (D4) at concentrations between 32.3 and 72.7 ppm (vol/vol) Si equivalent. The alumina mass, contact times, and temperatures investigated were 0.0700 g, 5.0 to 8.0 ms, and 307 to 384 °C, respectively. The experiments consisted of exposing a heated bed of alumina, initially free of siloxanes, to a stream of synthetic biogas of constant D4 concentration and monitoring the bed exit D4 concentration. Eleven out of the twelve breakthrough curves obtained were adequately predicted by a model that assumed a first order surface reaction, shrinking core particle kinetics, and plug flow in the bed. There were no statistically significant correlations between quality of fit (sum of weighted squares residuals) and concentration, contact time, or temperature in these eleven experiments. The model was not adequate in predicting the breakthrough curve from the experiment at 307 °C and thus should only be used to predict breakthrough curves at temperatures between 333 and 384 °C. The estimated model parameters were 2.10 for intraparticle tortuosity, 406,000 m3˙m -2˙s-1 for Arrhenius pre-exponential factor, and 81.4 kJ˙mor-1 for activation energy.

  7. Differential Scanning Calorimetry of Volatile-Bearing Iron Minerals Under Mars-Like Pressures: New Insights Into Energetics and Mechanisms of Thermal Decomposition

    NASA Technical Reports Server (NTRS)

    Lin, I.-C.; Lauer, H. V., Jr.; Golden, D. C.; Ming, D. W.

    2000-01-01

    In this study, we have examined the thermal decomposition of two volatile-bearing iron minerals, in particular, lepidocrocite (gamma-FeOOH) and siderite (FeCO3), under Mars-like pressures. Both minerals exhibit different enthalpic events during their decomposition at reduced atmospheric pressures when compared to those at ambient pressure. These differences in energetics are related to the mechanisms of thermal decomposition at Mars-like pressures. Such knowledge regarding the thermal stability of volatile-bearing minerals on Mars will provide useful information for planetary surface processes.

  8. Development of a ReaxFF reactive force field for ammonium nitrate and application to shock compression and thermal decomposition.

    PubMed

    Shan, Tzu-Ray; van Duin, Adri C T; Thompson, Aidan P

    2014-02-27

    We have developed a new ReaxFF reactive force field parametrization for ammonium nitrate. Starting with an existing nitramine/TATB ReaxFF parametrization, we optimized it to reproduce electronic structure calculations for dissociation barriers, heats of formation, and crystal structure properties of ammonium nitrate phases. We have used it to predict the isothermal pressure-volume curve and the unreacted principal Hugoniot states. The predicted isothermal pressure-volume curve for phase IV solid ammonium nitrate agreed with electronic structure calculations and experimental data within 10% error for the considered range of compression. The predicted unreacted principal Hugoniot states were approximately 17% stiffer than experimental measurements. We then simulated thermal decomposition during heating to 2500 K. Thermal decomposition pathways agreed with experimental findings. PMID:24479769

  9. Effect of fast neutron, gamma-ray and combined radiations on the thermal decomposition of ammonium perchlorate single crystals

    NASA Technical Reports Server (NTRS)

    Herley, P. J.; Wang, C. S.; Varsi, G.; Levy, P. W.

    1974-01-01

    The thermal decomposition kinetics have been determined for ammonium perchlorate crystals subjected to a fast neutron irradiation or to a fast neutron irradiation followed by a gamma-ray irradiation. Qualitatively, the radiation induced changes are similar to those obtained in this and in previous studies, with samples exposed only to gamma rays. The induction period is shortened and the rate constants, obtained from an Avrami-Erofeyev kinetic analysis, are modified. The acceleratory period constant increases and the decay period constant decreases. When compared on an equal deposited energy basis, the fast neutron induced changes are appreciably larger than the gamma-ray induced changes. Some, or all, of the fast neutron induced effects might be attributable to the introduction of localized regions of concentrated radiation damage ('spikes') by lattice atom recoils which become thermal decomposition sites when the crystals are heated.

  10. An integrated methodology for the assessment of environmental health implications during thermal decomposition of nano-enabled products

    PubMed Central

    Sotiriou, Georgios A.; Singh, Dilpreet; Zhang, Fang; Wohlleben, Wendel; Chalbot, Marie-Cecile G.; Kavouras, Ilias G.; Demokritou, Philip

    2015-01-01

    The proliferation of nano-enabled products (NEPs) renders human exposure to engineered nanomaterials (ENMs) inevitable. Over the last decade, the risk assessment paradigm for nanomaterials focused primarily on potential adverse effect of pristine, as-prepared ENMs. However, the physicochemical properties of ENMs may be drastically altered across their life-cycle (LC), especially when they are embedded in various NEP matrices. Of a particular interest is the end-of-life scenario by thermal decomposition. The main objective of the current study is to develop a standardized, versatile and reproducible methodology that allows for the systematic physicochemical and toxicological characterization of the NEP thermal decomposition. The developed methodology was tested for an industry-relevant NEP in order to verify its versatility for such LC investigations. Results are indicative of potential environmental health risks associated with waste from specific NEP families and prompt for the development of safer-by-design approaches and exposure control strategies. PMID:26200119

  11. Mathematical modeling of frontal process in thermal decomposition of a substance with allowance for the finite velocity of heat propagation

    SciTech Connect

    Shlenskii, O.F.; Murashov, G.G.

    1982-05-01

    In describing frontal processes of thermal decomposition of high-energy condensed substances, for example detonation, it is common practice to write the equation for the conservation of energy without any limitations on the heat propagation velocity (HPV). At the same time, it is known that in calculating fast processes of heat conduction, the assumption of an infinitely high HPV is not always justified. In order to evaluate the influence of the HPV on the results from calculations of heat conduction process under conditions of a short-term exothermic decomposition of a condensed substance, the solution of the problem of heating a semiinfinite, thermally unstable solid body with boundary conditions of the third kind on the surface has been examined.

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

    SciTech Connect

    Henson, Bryan F

    2010-01-01

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

  13. Study of the solid-phase thermal decomposition of NTO using Simultaneous Thermogravimetric Modulated Beam Mass Spectrometry (STMBMS)

    NASA Technical Reports Server (NTRS)

    Minier, L.; Behrens, R.; Burkey, T. J.

    1997-01-01

    The solid phase thermal reaction chemistry of NTO between 190 and 250 C is presently being evaluated by utilizing STMBMS, a technique that enables the authors to measure the vapor pressure of NTO and to explore the reaction mechanisms and chemical kinetics associated with the NTO thermal decomposition process. The vapor pressure of NTO is expressed as Log(sub 10) p(torr) = 12.5137 + 6,296.553(1/t(k)) and the Delta-H(sub subl) = 28.71 +/- 0.07 kcal/mol (120.01 +/- 0.29 kJ/mol). The pyrolysis of NTO results in the formation of gaseous products and a condensed-phase residue. The identity of the major gaseous products and their origin from within the NTO molecules are determined based on the results from pyrolysis of NTO, NTO-3-C-13, NTO-1,2- (15)N2 and NTO-(2)H2. Identification of the products show the major gaseous products to be N2, CO2, NO, HNCO, H2O and some N2O, CO, HCN and NH3. The N2 is mostly derived from the N-1 and N-2 positions with some being from the N-4 and N-1 or N-2 positions. The CO2 is derived from both carbons in the NTO molecule in comparable amounts. The residue has an elemental formula of C(2.1)H(.26)N(2.9)O and FTIR analysis suggests that the residue is polyurea- and polycarbamate- like in nature. The temporal behaviors of the rates of formation of the gaseous products indicate that the overall thermal decomposition of NTO in the temperature range evaluated involves four major processes: (1) NTO sublimation; (2) an apparent solid-solid phase transition between 190 and 195 C; (3) a decomposition regime induced by the presence of exogenous H2O at the onset of decomposition; and (4) a decomposition regime that occurs at the onset of decomposition and continues until the depletion of NTO. Decomposition pathways that are consistent with the data are presented.

  14. A study of the solid-phase thermal decomposition of NTO using simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS)

    SciTech Connect

    Minier, L.; Behrens, R.; Burkey, T.J.

    1997-01-01

    The solid phase thermal reaction chemistry of NTO between 190 and 250 C is presently being evaluated by utilizing STMBMS, a technique that enables the authors to measure the vapor pressure of NTO and to explore the reaction mechanisms and chemical kinetics associated with the NTO thermal decomposition process. The vapor pressure of NTO is expressed as Log{sub 10} p(torr) = 12.5137 + 6,296.553(1/t{sub k}) and the {Delta}H{sub subl} = 28.71 {+-} 0.07 kcal/mol (120.01 {+-} 0.29 kJ/mol). The pyrolysis of NTO results in the formation of gaseous products and a condensed-phase residue. The identity of the major gaseous products and their origin from within the NTO molecules are determined based on the results from pyrolysis of NTO, NTO-3-{sup 13}C, NTO-1,2-{sup 15}N{sub 2} and NTO-{sup 2}H{sub 2}. Identification of the products show the major gaseous products to be N{sub 2}, CO{sub 2}, NO, HNCO, H{sub 2}O and some N{sub 2}O, CO, HCN and NH{sub 3}. The N{sub 2} is mostly derived from the N-1 and N-2 positions with some being from the N-4 and N-1 or N-2 positions. The CO{sub 2} is derived from both carbons in the NTO molecule in comparable amounts. The residue has an elemental formula of C{sub 2.1}H{sub .26}N{sub 2.9}O and FTIR analysis suggests that the residue is polyurea- and polycarbamate-like in nature. The temporal behaviors of the rates of formation of the gaseous products indicate that the overall thermal decomposition of NTO in the temperature range evaluated involves four major processes: (1) NTO sublimation; (2) an apparent solid-solid phase transition between 190 and 195 C; (3) a decomposition regime induced by the presence of exogenous H{sub 2}O at the onset of decomposition; and (4) a decomposition regime that occurs at the onset of decomposition and continues until the depletion of NTO. Decomposition pathways that are consistent with the data are presented.

  15. Multistep Kinetic Behavior of the Thermal Decomposition of Granular Sodium Percarbonate: Hindrance Effect of the Outer Surface Layer.

    PubMed

    Wada, Takeshi; Nakano, Masayoshi; Koga, Nobuyoshi

    2015-09-24

    The kinetics and mechanism of the thermal decomposition of granular sodium percarbonate (SPC), which is used as a household oxygen bleach, were studied by thermoanalytical measurements under systematically changing conditions and morphological observation of the reactant solids at different reaction stages. A physico-geometrical kinetic behavior of the reaction that occurs in a core-shell structure composed of an outer surface layer and internal aggregates of SPC crystalline particles was illustrated through detailed kinetic analyses using the kinetic deconvolution method. Simultaneously, the hazardous nature of SPC as a combustion improver was evaluated on the basis of the kinetic behavior of the thermal decomposition. It was found that the outer surface layers of the SPC granules hinder the diffusional removal of product gases generated by the thermal decomposition of the internal SPC crystalline particles. The reaction rate decelerates because of an increase in the internal gaseous pressure as the reaction advances. However, the reaction rate accelerates once crack formation occurs in the outer surface layer at the midpoint of the reaction. Therefore, the overall reaction was empirically demonstrated to consist of two overlapping reaction steps owing to the changes in the self-generated reaction conditions in the interior of the SPC granules. PMID:26372469

  16. The role of petrography on the thermal decomposition and burnability of limestones used in industrial cement clinker

    NASA Astrophysics Data System (ADS)

    Marinoni, Nicoletta; Bernasconi, Andrea; Della Porta, Giovanna; Marchi, Maurizio; Pavese, Alessandro

    2015-12-01

    The present research examines the influence of the petrographic features on the thermal decomposition and burnability of three limestones, the main raw materials for Portland cement-making. A detailed characterisation of the limestones has been performed by means of optical microscopy and X-Ray Powder Diffraction. The carbonate thermal decomposition was conducted under isothermal conditions by means of in situ High Temperature X-Ray Powder Diffraction and the heated samples were further investigated by Scanning Electron Microscopy. Three kiln feeds were then prepared and submitted to burning trials and the temperature of occurrence of the main clinker phases was investigated as well as the content of the uncombined CaO in the heated samples was determined by using the Franke method. The results attest that the microfabric, a combination of depositional and diagenetic features, drives the kinetics of the thermal decomposition of the selected limestones as well as it appears to influence the temperature of crystallisation of the main clinker phases and the uncombined CaO content in the final clinker. In particular, the limestone with the lowest micrite to sparite ratio (1) exhibits the lowest Apparent Activation Energy ( E a ) value and the highest rate of calcination and (2) requires a lower temperature for observing the clinker phases crystallisation and has the lowest content of uncombined CaO in the final clinker, thus reflecting a high burnability of the limestone.

  17. Thermal decomposition of CH{sub 2}Cl{sub 2}

    SciTech Connect

    Lim, K.P.; Michael, J.V.

    1994-06-01

    The thermal decomposition of CH{sub 2}Cl{sub 2} has been investigated in reflected shock waves experiments at temperatures between 1400--2300 K and at three different loading pressures with various initial CH{sub 2}Cl{sub 2} concentrations. The resulting product Cl-atoms are monitored by the atomic resonance absorption spectrometer (ARAS) technique. A reaction mechanism is used to numerically simulate the measured Cl-atom profiles in order to obtain rate constants for the two primary dissociation reactions: (1) CH{sub 2}Cl{sub 2} {yields} CHCl + HCl and (2) CH{sub 2}Cl{sub 2} {yields} CH{sub 2}Cl + Cl. The experimental second-order Arrhenius expressions for the two reactions are k{sub 1}/[Kr] = 2.26 {times} 10{sup {minus}8} exp(-29007 K/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1} and k{sub 2}/[Kr] = 6.64 {times} 10{sup {minus}9} exp(-28404 K/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}, with standard deviations of {plus_minus}43% and 40%, respectively. Results are compared to theoretical calculations using the semi-empirical Tore formalism. The best fits to the experimental data obtained with threshold energy and collisional energy transfer parameters of E{sub 10}{sup o} = 73.0 kcal mole{sup {minus}1} and {Delta}E{sub 1down} = 630 cm{sup {minus}1}. Similar values for reaction (2) are E{sub 20}{sup o} = {Delta}H{sub 20}{sup o} = 78.25 kcal mole{sup {minus}1} and {delta}E{sub 2down} = 394 cm{sup {minus}1}.

  18. Direct observation of roaming radicals in the thermal decomposition of acetaldehyde.

    SciTech Connect

    Sivaramakrishnan, R.; Michael, J. V.; Klippenstein, S. J.; Chemical Sciences and Engineering Division

    2010-01-21

    The thermal dissociation of acetaldehyde has been studied with the reflected shock tube technique using H(D)-atom atomic resonance absorption spectrometry detection. The use of an unreversed light source yields extraordinarily sensitive H atom detection. As a result, we are able to measure both the total decomposition rate and the branching to radical versus molecular channels. This branching provides a direct measure of the contribution from the roaming radical mechanism since the contributions from the usual tight transition states are predicted by theory to be negligible. The experimental observations also provide a measure of the rate coefficient for H + CH{sub 3}CHO. Another set of experiments employing C{sub 2}H{sub 5}I as an H-atom source provides additional data for this rate coefficient that extends to lower temperature. An evaluation of the available experimental results for H + CH{sub 3}CHO can be expressed by a three-parameter Arrhenius expression as k = 7.66 x 10{sup -20}T{sup 2.75} exp((-486 K)/T) cm{sup 3} molecule{sup -1} s{sup -1} (298-1415 K). Analogous experiments employing C{sub 2}D{sub 5}I as a D-atom source allow for the study of the isotopically substituted reaction. The present experiments are the only direct measure for this reaction rate constant, and the results can be expressed by an Arrhenius expression as k = 5.20 x 10{sup -10} exp((-4430 K)/T) cm{sup 3} molecule{sup -1} s{sup -1} (1151-1354 K). The H/D + CH{sub 3}CHO reactions are also studied with ab initio transition-state theory, and the results are in remarkably good agreement with the current experimental data.

  19. The thermal decomposition of C{sub 2}H{sub 5}I

    SciTech Connect

    Kumaran, S.S.; Su, M.C.; Lim, K.P.; Michael, J.V.

    1996-06-01

    The high temperature thermal dissociation of C{sub 2}H{sub 5}I has been characterized in this study. Kinetics and overall yield experiments were performed over the temperature range, 946--2,046 K, using the atomic resonance absorption spectrometric technique (ARAS) for the temporal detection of both product H- and I-atoms behind reflected shock waves. The C{sub 2}H{sub 5}I decomposition proceeds by both C-I fission and HI elimination. Rate constants for the C-I fission process, measured over the temperature and density ranges, 946--1,303 K and 0.82--4.4 {times} 10{sup 18} cm{sup {minus}3}, respectively, can be well represented to within {+-}37% by the first-order expression: k = 6.34 {times} 10{sup 9} exp({minus}15,894 K/T) s{sup {minus}1}. Overall yield data for atomic product gave a branching ratio for C-I fission of (0.87 {+-} 0.11) suggesting that 13% of the reaction proceeds through molecular HI elimination. This conclusion is consistent with earlier studies that showed C-I fission to be the dominant dissociation channel. The temperature and pressure dependences of the dissociation rate constants and the yield data have been theoretically described using three formulations of unimolecular rate theory. The best description was obtained with a full Master`s equation analysis. However, all three calculations confirm that the HI elimination pathway is lower lying than the C-I fission process by {approximately} 3 kcal/mole.

  20. Thermal Decomposition of NCN: Shock-Tube Study, Quantum Chemical Calculations, and Master-Equation Modeling.

    PubMed

    Busch, Anna; González-García, Núria; Lendvay, György; Olzmann, Matthias

    2015-07-16

    The thermal decomposition of cyanonitrene, NCN, was studied behind reflected shock waves in the temperature range 1790-2960 K at pressures near 1 and 4 bar. Highly diluted mixtures of NCN3 in argon were shock-heated to produce NCN, and concentration-time profiles of C atoms as reaction product were monitored with atomic resonance absorption spectroscopy at 156.1 nm. Calibration was performed with methane pyrolysis experiments. Rate coefficients for the reaction (3)NCN + M → (3)C + N2 + M (R1) were determined from the initial slopes of the C atom concentration-time profiles. Reaction R1 was found to be in the low-pressure regime at the conditions of the experiments. The temperature dependence of the bimolecular rate coefficient can be expressed with the following Arrhenius equation: k1(bim) = (4.2 ± 2.1) × 10(14) exp[-242.3 kJ mol(-1)/(RT)] cm(3) mol(-1) s(-1). The rate coefficients were analyzed by using a master equation with specific rate coefficients from RRKM theory. The necessary molecular data and energies were calculated with quantum chemical methods up to the CCSD(T)/CBS//CCSD/cc-pVTZ level of theory. From the topography of the potential energy surface, it follows that reaction R1 proceeds via isomerization of NCN to CNN and subsequent C-N bond fission along a collinear reaction coordinate without a tight transition state. The calculations reproduce the magnitude and temperature dependence of the rate coefficient and confirm that reaction R1 is in the low-pressure regime under our experimental conditions. PMID:25853321

  1. Fabrication of Powder Metallurgy Pure Ti Material by Using Thermal Decomposition of TiH2

    NASA Astrophysics Data System (ADS)

    Mimoto, Takanori; Nakanishi, Nozomi; Umeda, Junko; Kondoh, Katsuyoshi

    Titanium (Ti) and titanium alloys have been interested as an engineering material because they are widely used across various industrial applications, for example, motorcycle, automotive and aerospace industries, due to their light weight, high specific strength and superior corrosion resistance. Ti materials are particularly significant for the aircraft using carbon/carbon (C/C) composites, for example, carbon fiber reinforced plastics (CFRP), because Ti materials are free from the problem of contact corrosion between C/C composites. However, the applications of Ti materials are limited because of their high cost. From a viewpoint of cost reduction, cost effective process to fabricate Ti materials is strongly required. In the present study, the direct consolidation of titanium hydride (TiH2) raw powders in solid-state was employed to fabricate pure Ti bulk materials by using thermal decomposition of TiH2. In general, the production cost of Ti components is expensive due to using commercially pure (CP) Ti powders after dehydrogenation. On the other hand, the novel process using TiH2 powders as starting materials is a promising low cost approach for powder metallurgy (P/M) Ti products. Furthermore, this new process is also attractive from a viewpoint of energy saving because the dehydrogenation is integrated into the sintering process. In this study, TiH2 raw powders were directly consolidated by conventional press technique at 600 MPa to prepare TiH2 powder compacted billets. To thermally decompose TiH2 and obtain sintered pure Ti billets, the TiH2 powder billets were heated in the integrated sintering process including dehydrogenation. The hot-extruded pure Ti material, which was heat treated at 1273 K for 180 min in argon gas atmosphere, showed tensile strength of 701.8 MPa and elongation of 27.1%. These tensile properties satisfied the requirements for JIS Ti Grade 4. The relationship between microstructures, mechanical properties response and heat treatment

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

    SciTech Connect

    Flament, T.A.

    1998-02-26

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

  3. Moessbauer spectroscopy evidence of a spinodal mechanism for the thermal decomposition of fcc FeCu

    SciTech Connect

    Crespo, P. |; Barro, M.J.; Hernando, A.; Escorial, A.G.; Menendez, N.; Tornero, J.D.; Barandiaran, J.M.

    1998-07-24

    Moessbauer spectroscopy shows the existence of compositional fluctuations, where different Fe environments coexist, during decomposition upon heat treatment of metastable f.c.c. FeCu solid solution. The presence of isolated Fe atoms in the Cu matrix, f.c.c. Fe{sub rich}Cu, f.c.c. FeCu{sub rich} and b.c.c. Fe has been detected in early decomposition stages. At later decomposition stages, low temperature Moessbauer spectroscopy indicates the presence of a broad distribution of Curie temperatures, coexisting with isolated Fe atoms in the Cu matrix, f.c.c. Fe and b.c.c. Fe.

  4. Kinetic analysis of the thermal decomposition of gamma-irradiated nickel oxalate

    NASA Astrophysics Data System (ADS)

    Mahfouz, R. M.; Abd-El-Wahab, M. M. M.

    1994-03-01

    The isothermal decomposition of un-irradiated and pre-γ-irradiated dehydrated nickel oxalate has been studied in the temperature range 250-365°C. Irradiation appears to increase the number of potential nuclei-forming sites without modification of the mechanism both for un-irradiated and has been shown to proceed by a nucleation and growth mechanism both for un-irradiated and pre-γ-irradiated samples of nickel oxalate. Application of Vand-Primak method for analysis of the decomposition data and calculation of activation energies of the decomposition process gives a good fit with that calculated using Arrhenious equation.

  5. Thermal Decomposition of an Impure (Roxbury) Siderite: Relevance to the Presence of Chemically Pure Magnetite Crystals in ALH84001 Carbonate Disks

    NASA Astrophysics Data System (ADS)

    Thomas-Keprta, K. L.; Clemett, S. J.; McKay, D. S.; Gibson, E. K.; Wentworth, S. J.

    2009-03-01

    Thermal decomposition of Roxbury siderite resulted in the formation of impure (Mg,Mn)-ferrites. These findings, which are supported by kinetic and thermodynamic equilibrium modeling studies, are in stark contrast to the chemically pure ALH 84001 magnetite.

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

    NASA Technical Reports Server (NTRS)

    Walker, R. D., Jr.

    1973-01-01

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

  7. Mathematical modeling and investigations of the processes of heat conduction of ammonium perchlorate with phase transitions in thermal decomposition and gasification

    NASA Astrophysics Data System (ADS)

    Mikhailov, A. V.; Lagun, I. M.; Polyakov, E. P.

    2013-01-01

    Transient heat-conduction processes occurring in the period of thermal decomposition and gasification of a crystalline oxidant — ammonium perchlorate — have been investigated and analyzed on the basis of the developed mathematical model.

  8. Effect of nanoclay loading on the thermal decomposition of nanoclay polyurethane elastomers obtained by bulk polymerization

    NASA Astrophysics Data System (ADS)

    Quagliano, Javier; Bocchio, Javier

    2014-08-01

    Thermoplastic urethane (TPU) nanocomposite was prepared successfully by dispersion at high shear stress of the nanoclay in polyol and further bulk polymerization. Our results from DSC studies showed an increase in decomposition temperature when nanoclay was loaded at 3,5% on elastomeric PU made from TDI, PTMEG and BDO, while not when nanoclay content was lower (1,5%). The exotherms at 370-375°C could be adscribed to the decomposition of the hard segments according to previous work.

  9. A fluorescence detection scheme for capillary electrophoresis of N-methylcarbamates with on-column thermal decomposition and derivatization

    PubMed

    Wu; Lee; Li

    2000-04-01

    This paper describes a fluorescence detection method for N-methylcarbamate (NMC) pesticides in micellar electrokinetic chromatography (MEKC) separation. Fulfillment of the fluorescence detection hinged on the discovery that quaternary ammonium surfactants (particularly cetyltrimethylammonium bromide, CTAB), besides serving as hydrophobic pseudophases in MEKC, are also capable of catalyzing the thermal decomposition of NMCs to liberate methylamine. Thus, a multifunctional MEKC medium consisting of borate buffer, CTAB, and derivatizing components (o-phthaldialdehyde/2-mercaptoethanol) was formulated, which allowed first normal MEKC separation, subsequent thermal decomposition, and finally in situ derivatization of NMCs. With careful optimization of the operation conditions, fluorescence detection of 10 NMC compounds was achieved, with column efficiencies typically higher than 50,000 and detection limits better than 0.5 ppm. The present work represents an unprecedented effort in capillary electrophoresis (CE), in which an intact capillary was consecutively utilized as chambers for separation, decomposition, derivatization, and detection, without involving any interfacing features. The success in the implementation of such a detection system resulted in strikingly simple instrumentation as compared with the traditional postcolumn fluorescence determination of NMCs by reversed-phase HPLC. Similar protocols should be workable in the determination of a wide range of pesticides and pharmaceuticals in CE formats. PMID:10763238

  10. Structural investigation of oxovanadium(IV) Schiff base complexes: X-ray crystallography, electrochemistry and kinetic of thermal decomposition

    NASA Astrophysics Data System (ADS)

    Asadi, Mozaffar; Asadi, Zahra; Savaripoor, Nooshin; Dusek, Michal; Eigner, Vaclav; Shorkaei, Mohammad Ranjkesh; Sedaghat, Moslem

    2015-02-01

    A series of new VO(IV) complexes of tetradentate N2O2 Schiff base ligands (L1-L4), were synthesized and characterized by FT-IR, UV-vis and elemental analysis. The structure of the complex VOL1ṡDMF was also investigated by X-ray crystallography which revealed a vanadyl center with distorted octahedral coordination where the 2-aza and 2-oxo coordinating sites of the ligand were perpendicular to the "-yl" oxygen. The electrochemical properties of the vanadyl complexes were investigated by cyclic voltammetry. A good correlation was observed between the oxidation potentials and the electron withdrawing character of the substituents on the Schiff base ligands, showing the following trend: MeO < H < Br < Cl. We also studied the thermodynamics of formation of the complexes and kinetic aspects of their thermal decomposition. The formation constants with various substituents on the aldehyde ring follow the trend 5-OMe > 5-H > 5-Br > 5-Cl. Furthermore, the kinetic parameters of thermal decomposition were calculated by using the Coats-Redfern equation. According to the Coats-Redfern plots the kinetics of thermal decomposition of studied complexes is of the first-order in all stages, the free energy of activation for each following stage is larger than the previous one and the complexes have good thermal stability. The preparation of VOL1ṡDMF yielded also another compound, one kind of vanadium oxide [VO]X, with different habitus of crystals, (platelet instead of prisma) and without L1 ligand, consisting of a V10O28 cage, diaminium moiety and dimethylamonium as a counter ions. Because its crystal structure was also new, we reported it along with the targeted complex.

  11. In situ formation of a MoS2 -based inorganic-organic nanocomposite by directed thermal decomposition.

    PubMed

    Djamil, John; Segler, Stefan A W; Bensch, Wolfgang; Schürmann, Ulrich; Deng, Mao; Kienle, Lorenz; Hansen, Sven; Beweries, Torsten; von Wüllen, Leo; Rosenfeldt, Sabine; Förster, Stephan; Reinsch, Helge

    2015-06-01

    Nanocomposites based on molybdenum disulfide (MoS2 ) and different carbon modifications are intensively investigated in several areas of applications due to their intriguing optical and electrical properties. Addition of a third element may enhance the functionality and application areas of such nanocomposites. Herein, we present a facile synthetic approach based on directed thermal decomposition of (Ph4 P)2 MoS4 generating MoS2 nanocomposites containing carbon and phosphorous. Decomposition at 250 °C yields a composite material with significantly enlarged MoS2 interlayer distances caused by in situ formation of Ph3 PS bonded to the MoS2 slabs through MoS bonds and (Ph4 P)2 S molecules in the van der Waals gap, as was evidenced by (31) P solid-state NMR spectroscopy. Visible-light-driven hydrogen generation demonstrates a high catalytic performance of the materials. PMID:25925691

  12. A STUDY OF THE PROPERTIES OF CP: COEFFICIENT OF THERMAL EXPANSION, DECOMPOSITION KINETICS AND REACTION TO SPARK, FRICTION AND IMPACT

    SciTech Connect

    Weese, R K; Burnham, A K; Fontes, A T

    2005-03-30

    The properties of pentaamine (5-cyano-2H-tetrazolato-N2) cobalt (III) perchlorate (CP), which was first synthesized in 1968, continues to be of interest for predicting behavior in handling, shipping, aging, and thermal cook-off situations. We report coefficient of thermal expansion (CTE) values over four specific temperature ranges, decomposition kinetics using linear heating rates, and the reaction to three different types of stimuli: impact, spark, and friction. The CTE was measured using a Thermal Mechanical Analyzer (TMA) for samples that were uniaxially compressed at 10,000 psi and analyzed over a dynamic temperature range of -20 C to 70 C. Using differential scanning calorimetry, DSC, CP was decomposed at linear heating rates of 1, 3, and 7 C/min and the kinetic triplet calculated using the LLNL code Kinetics05. Values are also reported for spark, friction, and impact sensitivity.

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

    SciTech Connect

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

    1999-10-25

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

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

    NASA Astrophysics Data System (ADS)

    Chai, Ming

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

  15. Thermal decomposition of 1,1-dimethylhydrazine on Si(100)-2 × 1

    NASA Astrophysics Data System (ADS)

    Armstrong, J. L.; Sun, Y.-M.; White, J. M.

    1997-12-01

    The surface reaction of 1,1-dimethylhydrazine (DMH) with Si(100) has been studied with temperature programmed desorption spectroscopy (TPD), temperature programmed static secondary ion mass spectrometry (TPSSIMS), X-ray photoelectron spectroscopy (XPS), and Auger electron spectroscopy (AES). Adsorption of DMH on Si(100) at 170 K followed by annealing to 1100 K results in significant decomposition to form surface carbide and nitride. TPD results show that the only gas phase desoprtion products are hydrogen and dimethylamine. Furthermore, decomposition occurs over a broad temperature range; XPS and TPSIMS results indicate C sbnd N bond cleavage beginning at 400 K and by 600 K, all the C sbnd N bonds have dissociated. We propose a molecular level mechanism that involves partial decomposition upon adsorption followed by extensive bond cleavage to form surface carbide and nitride.

  16. Syntheses and characterizations of two new energetic copper-amine-DNANT complexes and their effects on thermal decomposition of RDX

    NASA Astrophysics Data System (ADS)

    Qiu, Qianqian; Xu, Kangzhen; Yang, Shihe; Gao, Zhe; Zhang, Hang; Song, Jirong; Zhao, Fengqi

    2013-09-01

    Two novel copper complexes of dinitroacetonitrile (DNANT), Cu(NH3)4(DNANT)2 (1) and Cu(en)2(DNATN)2 (2), have been synthesized for the first time through an unique reaction, and structurally characterized. The single-crystal X-ray structural analysis shows that the Cu2+ cations in the two complexes share a similar four-coordinated structure, which however does not directly involve the main energetic DNANT- anion. The differential scanning calorimetry (DSC) study reveals that the two complexes have higher thermal stability and lower sensitivity than the analogous FOX-7 complexes, and exhibit good catalytic action to the decomposition of RDX.

  17. Thermal decomposition of sodium bicarbonate and its effect on the reaction of sodium bicarbonate and sulfur dioxide in a simulated flue gas

    SciTech Connect

    Keener, T.C.

    1982-01-01

    The effect of thermally decomposing sodium bicarbonate while simultaneously reacting with SO/sub 2/, was studied. The study was performed by quantitatively determining the rate of thermal decomposition as a function of particle size in an SO/sub 2/ free gas stream. The rate of reaction of sodium carbonate (product of the thermal decomposition) with SO/sub 2/ was then studied, and the data applied to a pore-plugging model which accounts for the loss in reactivity with increased reaction time. The reaction of sodium bicarbonate with SO/sub 2/ was then studied and the results compared to that for sodium carbonate. From the analysis of the data, the activation energy for the thermal decomposition reaction, the SO/sub 2/ sodium carbonate and SO/sub 2/ sodium bicarbonate reaction were derived. The thermal decomposition reaction of sodium biocarbonate was found to be similar to that of calcium carbonate below the point where heat transfer is rate limiting. The degree of conversion of sodium bicarbonate was found to be 12-17 times greater (depending on particle size) than that of sodium carbonate in the temperature range 250/sup 0/-350/sup 0/F (120/sup 0/-177/sup 0/C). This greater conversion was qualitatively explained by hypothesizing the formation of an activated species during thermal decomposition which would be more chemically reactive.

  18. Infrared spectroscopic study on the thermal decomposition of external and internal gelation products of simulated mixed oxide nuclear fuel.

    PubMed

    Kumar, K Suresh; Bhat, N P

    2004-02-01

    The thermal decomposition of urania-ceria gel corresponding to the composition U(0.7)Ce(0.3)O(2+x) obtained through external and internal gelation routes were studied using infrared spectroscopy (IR). In the case of externally gelated compound, the gel decomposes with the release of H2O and NH3 below 500 degrees C. A part of the NH3 released is entrapped in the solid and above 500 degrees C self reduction occurs in which U(VI) in the gel is reduced to U3O8. The decomposition products were identified to be U3O8 and CeO2. In the case of internally gelated compound, decomposition similar to the one for externally gelated compound occurred below 500 degrees C. Above 500 degrees C the carbon present in the gel reduced U(VI) to UO2 which formed solid solution with CeO2 around 650 degrees C. PMID:14747073

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

    PubMed

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

    2013-12-15

    The effects of ferrous iron, heating temperature and different additives on the decomposition of trimethylamine oxide (TMAO) to formaldehyde (FA) and dimethylamine (DMA) and generation of free radicals in jumbo squid (Dosidicus gigas) extract during heating were evaluated by electron spin resonance (ESR). The thermal decomposition of TMAO to TMA, DMA and FA and free radical signals was observed in squid extract, whereas no DMA, FA and free radical signals were detected in cod extract or in aqueous TMAO solution in vitro at high temperatures. Significant increase in levels of DMA, FA and radicals intensity were observed in squid extract and TMAO solution in the presence of ferrous iron with increasing temperature. Hydrogen peroxide stimulated the production of DMA, FA and ESR signals in squid extract, while citric acid, trisodium citrate, calcium chloride, tea polyphenols and resveratrol had the opposite effect. Similar ESR spectra of six peaks regarded as amminium radical were detected in the squid extract and TMAO-iron(II) solution, suggesting that the amminium radical was involved in the decomposition of TMAO. PMID:23993561

  20. Shock wave and modeling study of the thermal decomposition reactions of pentafluoroethane and 2-H-heptafluoropropane.

    PubMed

    Cobos, C J; Sölter, L; Tellbach, E; Troe, J

    2014-06-01

    The thermal decomposition reactions of CF3CF2H and CF3CFHCF3 have been studied in shock waves by monitoring the appearance of CF2 radicals. Temperatures in the range 1400-2000 K and Ar bath gas concentrations in the range (2-10) × 10(-5) mol cm(-3) were employed. It is shown that the reactions are initiated by C-C bond fission and not by HF elimination. Differing conclusions in the literature about the primary decomposition products, such as deduced from experiments at very low pressures, are attributed to unimolecular falloff effects. By increasing the initial reactant concentrations in Ar from 60 to 1000 ppm, a retardation of CF2 formation was observed while the final CF2 yields remained close to two CF2 per C2F5H or three CF2 per C3F7H decomposed. This is explained by secondary bimolecular reactions which lead to comparably stable transient species like CF3H, releasing CF2 at a slower rate. Quantum-chemical calculations and kinetic modeling help to identify the reaction pathways and provide estimates of rate constants for a series of primary and secondary reactions in the decomposition mechanism. PMID:24352693

  1. Kinetics and Mechanism of the CIO + CIO Reaction: Pressure and Temperature Dependences of the Bimolecular and Termolecular Channels andThermal Decomposition of Chlorine Peroxide, CIOOCI

    NASA Technical Reports Server (NTRS)

    Nickolaisen, Scott L.; Friedl, Randall R.; Sander, Stanley P.

    1993-01-01

    The kinetics and mechanism of the CIO + CIO reaction and the thermal decomposition of CIOOCI were studied using the flash photolysis/long path ultraviolet absorption technique. Pressure and temperature dependences were determined for the rate coefficients for the bimolecular and termolecular reaction channels, and for the thermal decompositon of CIOOCI.

  2. Y2O3-MgO Nano-Composite Synthesized by Plasma Spraying and Thermal Decomposition of Solution Precursors

    NASA Astrophysics Data System (ADS)

    Muoto, Chigozie Kenechukwu

    This research aims to identify the key feedstock characteristics and processing conditions to produce Y2O3-MgO composite coatings with high density and hardness using solution precursor plasma spray (SPPS) and suspension plasma spray (SPS) processes, and also, to explore the phenomena involved in the production of homogenized nano-composite powders of this material system by thermal decomposition of solution precursor mixtures. The material system would find potential application in the fabrication of components for optical applications such as transparent windows. It was shown that a lack of major endothermic events during precursor decomposition and the resultant formation of highly dense particles upon pyrolysis are critical precursor characteristics for the deposition of dense and hard Y2O3-MgO coatings by SPPS. Using these principles, a new Y2O3-MgO precursor solution was developed, which yielded a coating with Vickers hardness of 560 Hv. This was a considerable improvement over the hardness of the coatings obtained using conventional solution precursors, which was as low as 110 Hv. In the thermal decomposition synthesis process, binary solution precursor mixtures of: yttrium nitrate (Y[n]) or yttrium acetate (Y[a]), with magnesium nitrate (Mg[n]) or magnesium acetate (Mg[a]) were used in order to study the effects of precursor chemistry on the structural characteristics of the resultant Y2O3-MgO powders. The phase domains were coarse and distributed rather inhomogeneously in the materials obtained from the Y[n]Mg[n] and Y[a]Mg[a] mixtures; finer and more homogeneously-distributed phase domains were obtained for ceramics produced from the Y[a]Mg[n] and Y[n]Mg[a] mixtures. It was established that these phenomena were related to the thermal characteristics for the decomposition of the precursors and their effect on phase separation during oxide crystallization. Addition of ammonium acetate to the Y[n[Mg[n] mixture changed the endothermic process to exothermic

  3. Effect of aluminum chloride on formation of a polyconjugated bond system in the initial stage of polyvinyl alcohol thermal decomposition

    NASA Astrophysics Data System (ADS)

    Kulak, A. I.; Bondareva, G. V.; Shchurevich, O. A.

    2013-03-01

    Fine-structure bands have been located in electronic absorption spectra of polyvinyl alcohol (PVA) films decomposed thermally in air at 80-150°C. Doping of the PVA film with aluminum chloride (thermolysis catalyst) was found both to enhance the degree of thermal decomposition and to reduce the starting temperature for formation of poly-π-conjugated chains although it had no effect on the spectral positions of the polyene-unit absorption bands. Values of the band gap of heat-treated PVA films were determined to be in the range 1.65-1.78 eV based on an analysis of the electronic spectra long-wavelength edge.

  4. Artificial Neural Network Prediction for Thermal Decomposition of Potassium Nitrate (KNO3) and Benzoic Acid (C6H5COOH)

    NASA Astrophysics Data System (ADS)

    Beken, Murat

    The aim of this work is to correlate the results of experimental data by using the differential thermal analysis (DTA) method and predictions of artificial neural networks (ANNs). Thermal decomposition of potassium nitrate (KNO3) and benzoic acid (C6H5COOH) have been analyzed by the simultaneous DTA method. Kinetic parameters (critical points, the change of enthalpy) have been investigated. A computer model, based on multilayer feed-forwarding back-propagation is used for the prediction of critical points, phase transitions of potassium nitrate (KNO3) and benzoic acid (C6H5COOH). As a result of our study, we conclude that the ANN model shows a considerably good result about the prediction of experimental data.

  5. Thermodynamic studies of studtite thermal decomposition pathways via amorphous intermediates UO3, U2O7, and UO4

    DOE PAGESBeta

    Guo, Xiaofeng; Wu, Di; Xu, Hongwu; Burns, Peter C.; Navrotsky, Alexandra

    2016-06-08

    The thermal decomposition of studtite (UO2)O2(H2O)2·2H2O results in a series of intermediate X-ray amorphous materials with general composition UO3+x (x = 0, 0.5, 1). As an extension of a structural study on U2O7, this work provides detailed calorimetric data on these amorphous oxygen-rich materials since their energetics and thermal stability are unknown. These were characterized in situ by thermogravimetry, and mass spectrometry. Ex situ X-ray diffraction and infrared spectroscopy characterized their chemical bonding and local structures. This detailed characterization formed the basis for obtaining formation enthalpies by high temperature oxide melt solution calorimetry. The thermodynamic data demonstrate the metastability ofmore » the amorphous UO3+x materials, and explain their irreversible and spontaneous reactions to generate oxygen and form metaschoepite. Thus, formation of studtite in the nuclear fuel cycle, followed by heat treatment, can produce metastable amorphous UO3+x materials that pose the risk of significant O2 gas. Quantitative knowledge of the energy landscape of amorphous UO3+x was provided for stability analysis and assessment of conditions for decomposition.« less

  6. Thermal Decomposition of Bulk K-CoMoSx Mixed Alcohol Catalyst Precursors and Effects on Catalyst Morphology and Performance

    SciTech Connect

    Menart, M. J.; Hensley, J. E.; Costelow, K. E.

    2012-09-26

    Cobalt molybdenum sulfide-type mixed alcohol catalysts were synthesized via calcination of precipitated bulk sulfides and studied with temperature programmed decomposition analysis. Precursors containing aqueous potassium were also considered. Precipitates thermally decomposed in unique events which released ammonia, carbon dioxide, and sulfur. Higher temperature treatments led to more crystalline and less active catalysts in general with ethanol productivity falling from 203 to 97 g (kg cat){sup -1} h{sup -1} when the calcination temperature was increased from 375 to 500 C. The addition of potassium to the precursor led to materials with crystalline potassium sulfides and good catalytic performance. In general, less potassium was required to promote alcohol selectivity when added before calcination. At calcination temperatures above 350 C, segregated cobalt sulfides were observed, suggesting that thermally decomposed sulfide precursors may contain a mixture of molybdenum and cobalt sulfides instead of a dispersed CoMoS type of material. When dimethyl disulfide was fed to the precursor during calcination, crystalline cobalt sulfides were not detected, suggesting an important role of free sulfur during decomposition.

  7. Thermodynamic studies of studtite thermal decomposition pathways via amorphous intermediates UO3, U2O7, and UO4

    NASA Astrophysics Data System (ADS)

    Guo, Xiaofeng; Wu, Di; Xu, Hongwu; Burns, Peter C.; Navrotsky, Alexandra

    2016-09-01

    The thermal decomposition of studtite (UO2)O2(H2O)2·2H2O results in a series of intermediate X-ray amorphous materials with general composition UO3+x (x = 0, 0.5, 1). As an extension of a structural study on U2O7, this work provides detailed calorimetric data on these amorphous oxygen-rich materials since their energetics and thermal stability are unknown. These were characterized in situ by thermogravimetry, and mass spectrometry. Ex situ X-ray diffraction and infrared spectroscopy characterized their chemical bonding and local structures. This detailed characterization formed the basis for obtaining formation enthalpies by high temperature oxide melt solution calorimetry. The thermodynamic data demonstrate the metastability of the amorphous UO3+x materials, and explain their irreversible and spontaneous reactions to generate oxygen and form metaschoepite. Thus, formation of studtite in the nuclear fuel cycle, followed by heat treatment, can produce metastable amorphous UO3+x materials that pose the risk of significant O2 gas. Quantitative knowledge of the energy landscape of amorphous UO3+x was provided for stability analysis and assessment of conditions for decomposition.

  8. Thermal decomposition behaviors and kinetic properties of 1,8-naphthalic anhydride loaded dense nano-silica hybrids

    NASA Astrophysics Data System (ADS)

    Wang, Jinpeng; Sun, Jihong; Wang, Feng; Ren, Bo

    2013-06-01

    A certain amount of (3-aminopropyl)triethoxysilane (APTES) and various capacity of 1,8-naphthalic anhydride (NA) were employed to modify and then graft onto the surface of the dense nano-silica spheres (DNSS) via a post-grafting method, and thereby, a novel luminescent density nano-silica hybrid materials have been successfully synthesized. Meanwhile, the structures and properties of obtained hybrid DNSS were characterized by XRD, TEM, N2 sorption, FT-IR, and TG analysis. Furthermore, the thermal stability of before and after modification were demonstrated by using both Kissinger methods and Ozawa-Flynn-Wall methods. Particularly, the thermal decomposition behaviors of amino-modified groups and NA-grafted organic molecules were emphasized based on the TG and DTG analysis and then the related mechanism was put forward according to Coats and Redfern methods. Finally, as a comparison, the obtained results and the proposed decomposition mechanism of hybrid DNSS with non-pores were discussed with that of mesopores silicas in details.

  9. Thermal decomposition of HfCl{sub 4} as a function of its hydration state

    SciTech Connect

    Barraud, E.; Begin-Colin, S. . E-mail: begin@ipcms.u-strasbg.fr; Le Caer, G.; Villieras, F.; Barres, O.

    2006-06-15

    The thermogravimetric behavior of HfCl{sub 4} powders with different hydration states has been compared. Strongly hydrated powders consist of HfOCl{sub 2}.nH{sub 2}O with n>4. Partially hydrated powders consist of particles with a HfCl{sub 4} core and a hydrated outerlayer of HfOCl{sub 2}.nH{sub 2}O with n in the range of 0-8. Hydrated powders decomposed at temperature lower than 200 deg. C whereas the decomposition of partially hydrated powders was completed at a temperature of around 450 deg. C. The observed differences in decomposition temperature is related to the structure of HfOCl{sub 2}.nH{sub 2}O, which is different if n is higher or smaller than 4 and leads to intermediate compounds, which decompose at different temperatures.

  10. An ab initio study of possible pathways in the thermal decomposition of NaAlH{sub 4}

    SciTech Connect

    Ojwang, J.G.O. Santen, Rutger van; Jan Kramer, Gert; Ke Xuezhi

    2008-11-15

    Density functional theory (DFT) has been used to study the structural stability of possible intermediate alanate structures, Na{sub 5}Al{sub 3}H{sub 14} and Na{sub 2}AlH{sub 5}, in the thermal decomposition of NaAlH{sub 4}. Na{sub 5}Al{sub 3}H{sub 14} crystallizes in the space group P4/mnc with lattice constants a=6.769A, c=10.289A and c/a=1.52. It is shown that both Na{sub 5}Al{sub 3}H{sub 14} and Na{sub 2}AlH{sub 5} have the right thermodynamics and can fit in as an intermediate state during the thermal decomposition process of NaAlH{sub 4}. The heat of formation of Na{sub 5}Al{sub 3}H{sub 14} is -60 kJ/mol H{sub 2}, which is intermediate between that of NaAlH{sub 4} (-51 kJ/mol H{sub 2}) and Na{sub 3}AlH{sub 6} (-69.7 kJ/mol H{sub 2}). An alternative decomposition pathway based on Na{sub 2}AlH{sub 5} has also been discussed. Frequency analysis showed that the least energetic Na{sub 2}AlH{sub 5} structure has imaginary frequencies, implying that it is unstable. The presence of soft phonon modes also shows that Na{sub 5}Al{sub 3}H{sub 14} is mechanically metastable. These results are consistent with the notion that they are the intermediate states that lead to the formation of AlH{sub 3}. This facilitates the mass transport of aluminum atoms in the decomposition pathway of NaAlH{sub 4}. - Projections of the Na{sub 5}Al{sub 3}H{sub 14} structure. Na atoms are represented by small spheres. The polyhedra represents the AlH{sub 6} moiety.

  11. Thermal decomposition of iron(VI) oxides, K{sub 2}FeO{sub 4} and BaFeO{sub 4}, in an inert atmosphere

    SciTech Connect

    Madarasz, Janos; Zboril, Radek; Homonnay, Zoltan . E-mail: vsharma@fit.edu; Pokol, Gyoergy

    2006-05-15

    The thermal decomposition of solid samples of iron(VI) oxides, K{sub 2}FeO{sub 4}.0.088 H{sub 2}O (1) and BaFeO{sub 4}.0.25H{sub 2}O (2) in inert atmosphere has been examined using simultaneous thermogravimetry and differential thermal analysis (TG/DTA), in combination with in situ analysis of the evolved gases by online coupled mass spectrometer (EGA-MS). The final decomposition products were characterized by {sup 57}Fe Moessbauer spectroscopy. Water molecules were released first, followed by a distinct decomposition step with endothermic DTA peak of 1 and 2 at 273 and 248 deg. C, respectively, corresponding to the evolution of molecular oxygen as confirmed by EGA-MS. The released amounts of O{sub 2} were determined as 0.42 and 0.52 mol pro formula of 1 and 2, respectively. The decomposition product of K{sub 2}FeO{sub 4} at 250 deg. C was determined as Fe(III) species in the form of KFeO{sub 2}. Formation of an amorphous mixture of superoxide, peroxide, and oxide of potassium may be other products of the thermal conversion of iron(VI) oxide 1 to account for less than expected released oxygen. The thermogravimetric and Moessbauer data suggest that barium iron perovskite with the intermediate valence state of iron (between III and IV) was the product of thermal decomposition of iron(VI) oxide 2.

  12. Thermal decomposition of iron(VI) oxides, K 2FeO 4 and BaFeO 4, in an inert atmosphere

    NASA Astrophysics Data System (ADS)

    Madarász, János; Zbořil, Radek; Homonnay, Zoltán; Sharma, Virender K.; Pokol, György

    2006-05-01

    The thermal decomposition of solid samples of iron(VI) oxides, K 2FeO 4·0.088 H 2O ( 1) and BaFeO 4·0.25H 2O ( 2) in inert atmosphere has been examined using simultaneous thermogravimetry and differential thermal analysis (TG/DTA), in combination with in situ analysis of the evolved gases by online coupled mass spectrometer (EGA-MS). The final decomposition products were characterized by 57Fe Mössbauer spectroscopy. Water molecules were released first, followed by a distinct decomposition step with endothermic DTA peak of 1 and 2 at 273 and 248 °C, respectively, corresponding to the evolution of molecular oxygen as confirmed by EGA-MS. The released amounts of O 2 were determined as 0.42 and 0.52 mol pro formula of 1 and 2, respectively. The decomposition product of K 2FeO 4 at 250 °C was determined as Fe(III) species in the form of KFeO 2. Formation of an amorphous mixture of superoxide, peroxide, and oxide of potassium may be other products of the thermal conversion of iron(VI) oxide 1 to account for less than expected released oxygen. The thermogravimetric and Mössbauer data suggest that barium iron perovskite with the intermediate valence state of iron (between III and IV) was the product of thermal decomposition of iron(VI) oxide 2.

  13. Thermal decomposition studies of energetic materials using confined rapid thermolysis/FTIR spectroscopy

    SciTech Connect

    Kim, E.S.; Lee, H.S.; Mallery, C.F.; Thynell, S.T.

    1997-07-01

    An experimental setup for performing rapid thermolysis studies of small samples of energetic materials is described. In this setup, about 8 {micro}L of a liquid sample or about 2 mg of a solid sample is heated at rates exceeding 1,500 K/s to a set temperature where decomposition occurs. The rapid heating is achieved as a result of confining the sample between two closely spaced isothermal surfaces. The gaseous decomposition products depart from the confined space through a rectangular slit into the region of detection. The evolved gases are quantified using FTIR absorption spectroscopy by accounting for the instrument line shape. To illustrate the use of this setup, the thermolysis behaviors of three different energetic materials are examined. These materials include HMX, RDX, and HAN, all of which are considered as highly energetic propellant ingredients. The results obtained in this study of the temporal evolution of species concentrations from these ingredients are in reasonably close agreement with results available in the literature.

  14. Dielectric properties of the collagen-glycosaminoglycans scaffolds in the temperature range of thermal decomposition.

    PubMed

    Pietrucha, K; Marzec, E

    2005-10-22

    Dielectric spectroscopy has been applied to study the decomposition process of unmodified collagen and chondroitin sulfate (CS)- and hyaluronic acid (HA)-modified collagen. Measurements were performed over the frequency range from 10 Hz to 100 kHz and at temperatures from 22 to 260 degrees C. According to the Kramers-Kronig relationship a dispersion is apparent in both epsilon' and epsilon'' for the three materials below 140 degrees C and at higher temperatures as a broad peak around 220-230 degrees C, respectively. The values of epsilon' and epsilon'' at the same temperature for constant frequency are higher in HA-modified collagen than in the unmodified collagen. However, small differences are shown in these parameters between CS-modified collagen and unmodified collagen. The observed dispersion around 220-230 degrees C corresponds to the decomposition of unmodified and CS- and HA-modified collagen. Power-low responses are observed for the frequency dependence of ac conductivity for unmodified and modified collagen. The behaviour observed for temperature dependencies of the exponent n for the three materials is considered to be related to the proton polarization and conduction processes. PMID:16099587

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

    NASA Astrophysics Data System (ADS)

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

    2012-06-01

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

  16. Coal thermolysis modeling: The effect of cross-linking on the thermal decomposition of 1,3-diphenylpropane

    SciTech Connect

    Britt, P.F.; Buchanan, A.C. III.; Hagaman, E.W.; Biggs, C.A. )

    1990-08-01

    In an effort to model the effects of restricted diffusion and cross-linking on the thermal decomposition of polymethylene units linking aromatic moieties in coal, a surface-attached, cross-linked 1,3-diphenylpropane has been synthesized through the condensation of p, p{prime}-HOPh(CH{sub 2}){sub 3}PhOH with a silica surface. Thermolysis of DPP at 375 C has been studied at a variety of surface coverages in which the fraction of diattached DPP varies from ca. 24 to 86% with complete diattachment not yet achieved. The influence of cross-linking and free phenolic functionality (Ph(CH{sub 2}){sub 3}PhOH) on the rate of decomposition and product distribution will be discussed and compared to the thermolysis of Ph(CH{sub 2}){sub 3}Ph as well as fluid phase DPP. Solid state CP/MAS {sup 13}C NMR will be used to prove the chemical composition and motional behavior of the substrate on the surface and their potential mechanistic impact.

  17. Coupling experimental data and a prototype model to probe the physical and chemical processes of 2,4-dinitroimidazole solid-phase thermal decomposition

    SciTech Connect

    Behrens, R.; Minier, L.; Bulusu, S.

    1998-12-31

    The time-dependent, solid-phase thermal decomposition behavior of 2,4-dinitroimidazole (2,4-DNI) has been measured utilizing simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS) methods. The decomposition products consist of gaseous and non-volatile polymeric products. The temporal behavior of the gas formation rates of the identified products indicate that the overall thermal decomposition process is complex. In isothermal experiments with 2,4-DNI in the solid phase, four distinguishing features are observed: (1) elevated rates of gas formation are observed during the early stages of the decomposition, which appear to be correlated to the presence of exogenous water in the sample; (2) this is followed by a period of relatively constant rates of gas formation; (3) next, the rates of gas formation accelerate, characteristic of an autocatalytic reaction; (4) finally, the 2,4-DNI is depleted and gaseous decomposition products continue to evolve at a decreasing rate. A physicochemical and mathematical model of the decomposition of 2,4-DNI has been developed and applied to the experimental results. The first generation of this model is described in this paper. Differences between the first generation of the model and the experimental data collected under different conditions suggest refinements for the next generation of the model.

  18. Comparison of the thermal decompositions of HMX and 2,4-DNI for evaluation of slow cookoff response and long-term stability

    SciTech Connect

    Minier, L.; Behrens, R.; Bulusu, S.

    1995-12-01

    Thermal decomposition of HMX between 175C and 200C was studied using the simultaneous thermogravimetric modulated beam mass spectrometer with focus on initial stages of the decomposition. Thermal decomposition products are the same as in previous higher temperature experiments. The initial stages of the decomposition have an induction period followed by two acceleratory periods. Arrhenius parameters for the induction and two acceleratory periods are (Log(A)= 18.2 {plus_minus} 0.8, Ea = 48.2 {plus_minus} 1.8 kcal/mole), (Log (A) = 17.15 {plus_minus} 1.5 and Ea = 48.9 {plus_minus} 3.2 kcal/mole), (Log (A) = 19.1 {plus_minus} 3.0 and Ea = 52.1 {plus_minus} 6.3 kcal/mole). This data can be used to calculate the time and temperature required to decompose a desired fraction of a test sample testing the effect of thermal degradation on sensitivity or bum rates. It can also be used to estimate the extent of decomposition expected under normal storage conditions for munitions containing HMX. This data, along with previous mechanistic studies conducted at higher temperatures, suggest that the process that controls the early stages of decomposition of HMX in the solid phase is scission of the N-NO{sub 2} bond, reaction of the N0{sub 2} within a lattice cage to form the mononitroso analogue of HMX and decomposition of the mononitroso HMX within the HMX lattice to form gaseous products that are retained in bubbles or diffuse into the surrounding lattice. These methods evaluating HMX can be used to evaluate new energetic materials such as 2,4-DNI. The early 2,4-DNI thermal decomposition is characterized by an initial decomposition, an apparent induction period, then an initial acceleratory period. The main gaseous products are NO, C0{sub 2}, HNCO, H{sub 2}0, N{sub 2}, CO, HCN and C{sub 2}N{sub 2}. The presence of adsorbed and occluded H{sub 2}0 is the major cause of the early decomposition.

  19. Preparation and sonocatalytic activity of monodisperse porous bread-like CuO via thermal decomposition of copper oxalate precursors

    NASA Astrophysics Data System (ADS)

    Zhang, Lihui; Liu, Rong; Yang, Heqing

    2012-04-01

    Porous bread-like CuO have been obtained via the thermal decomposition of copper oxalate precursor synthesized by the room temperature reaction of Cu(NO3)2 with Na2C2O4 in water. These bread-like CuO with the monoclinic structure are well dispersed with good monodispersity, their diameters are about 1.5 μm. The sonocatalytic activity of porous CuO for the degradation of acid scarlet dye was studied. It was found that the as-prepared porous CuO nanostructures exhibit efficient sonocatalytic ability for the degradation of acid scarlet dye in the presence of H2O2, which are expected to be useful in the treatment of non- or low-transparent wastewaters.

  20. Structural and magnetic properties of Fe1-x Co x Se1.09 nanoparticles obtained by thermal decomposition

    NASA Astrophysics Data System (ADS)

    Li, Oksana A.; Lin, Chun-Rong; Chen, Hung-Yi; Hsu, Hua-Shu; Wu, Kai-Wun; Tseng, Yaw-Teng; Bayukov, Oleg A.; Edelman, Irina S.; Ovchinnikov, Sergey G.; Shih, Kun-Yauh

    2015-12-01

    A series of Fe1-x CoxSe1.09 (x = 0 to 1) nanoparticles were synthesized by thermal decomposition method. Particles in composition range Fe0.5Co0.5Se1.09 to CoSe1.09 crystallized in monoclinic structure of Co6.8Se8, while FeSe1.09 crystallized in hexagonal structure of FeSe achavalite. Magnetization dependences on temperature and external magnetic field reveal complicated magnetic behavior and correspond to the sum of paramagnetic and superparamagnetic response. Mössbauer spectra contain several paramagnetic doublets with parameters corresponding to nonequivalent positions of divalent and trivalent iron cations with low spin. The nonequivalent positions appeared due to inhomogeneous distribution of Co ions or metal vacancies in iron surrounding.

  1. Fabrication of chain-like Mn 2O 3 nanostructures via thermal decomposition of manganese phthalate coordination polymers

    NASA Astrophysics Data System (ADS)

    Salavati-Niasari, Masoud; Mohandes, Fatemeh; Davar, Fatemeh; Saberyan, Kamal

    2009-12-01

    A novel manganese coordination polymer [Mn(Pht)(H 2O)] n as a precursor was obtained by chemical precipitation involving an aqueous solution of anhydrous manganese acetate and phthalate anion as a potential O-banded ligand. Fourier transform infrared (FT-IR) results proved that phthalate anions coordinate to metal cations as a chelating bidentate ligand, making polymeric structure. The Mn 2O 3 nanostructures have been prepared via thermal decomposition of as-prepared manganese phthalate polymers as precursor in the presence of oleic acid (OA) and triphenylphosphine (TPP) as a stabilizer and capping. Different approaches such as FT-IR, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were applied to characterize the products. TEM images and XRD analysis indicated that the as-synthesized chain-like Mn 2O 3 has a crystal phase of cubic syngony with a mean size of ˜40 nm.

  2. Boron nitride encapsulated copper nanoparticles: a facile one-step synthesis and their effect on thermal decomposition of ammonium perchlorate

    NASA Astrophysics Data System (ADS)

    Huang, Caijin; Liu, Qiuwen; Fan, Wenjie; Qiu, Xiaoqing

    2015-11-01

    Reactivity is of great importance for metal nanoparticles used as catalysts, biomaterials and advanced sensors, but seeking for high reactivity seems to be conflict with high chemical stability required for metal nanoparticles. There is a subtle balance between reactivity and stability. This could be reached for colloidal metal nanoparticles using organic capping reagents, whereas it is challenging for powder metal nanoparticles. Here, we developed an alternative approach to encapsulate copper nanoparticles with a chemical inertness material—hexagonal boron nitride. The wrapped copper nanoparticles not only exhibit high oxidation resistance under air atmosphere, but also keep excellent promoting effect on thermal decomposition of ammonium perchlorate. This approach opens the way to design metal nanoparticles with both high stability and reactivity for nanocatalysts and their technological application.

  3. Pt deposited TiO2 catalyst fabricated by thermal decomposition of titanium complex for solar hydrogen production

    NASA Astrophysics Data System (ADS)

    Truong, Quang Duc; Le, Thanh Son; Ling, Yong-Chien

    2014-12-01

    C, N codoped TiO2 catalyst has been synthesized by thermal decomposition of a novel water-soluble titanium complex. The structure, morphology, and optical properties of the synthesized TiO2 catalyst were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and UV-vis diffuse reflectance spectroscopy. The photocatalytic activity of the Pt deposited TiO2 catalysts synthesized at different temperatures was evaluated by means of hydrogen evolution reaction under both UV-vis and visible light irradiation. The investigation results reveal that the photocatalytic H2 evolution rate strongly depended on the crystalline grain size as well as specific surface area of the synthesized catalyst. Our studies successfully demonstrate a simple method for the synthesis of visible-light responsive Pt deposited TiO2 catalyst for solar hydrogen production.

  4. Boron nitride encapsulated copper nanoparticles: a facile one-step synthesis and their effect on thermal decomposition of ammonium perchlorate

    PubMed Central

    Huang, Caijin; liu, Qiuwen; Fan, Wenjie; Qiu, Xiaoqing

    2015-01-01

    Reactivity is of great importance for metal nanoparticles used as catalysts, biomaterials and advanced sensors, but seeking for high reactivity seems to be conflict with high chemical stability required for metal nanoparticles. There is a subtle balance between reactivity and stability. This could be reached for colloidal metal nanoparticles using organic capping reagents, whereas it is challenging for powder metal nanoparticles. Here, we developed an alternative approach to encapsulate copper nanoparticles with a chemical inertness material—hexagonal boron nitride. The wrapped copper nanoparticles not only exhibit high oxidation resistance under air atmosphere, but also keep excellent promoting effect on thermal decomposition of ammonium perchlorate. This approach opens the way to design metal nanoparticles with both high stability and reactivity for nanocatalysts and their technological application. PMID:26567862

  5. Compact Ag@Fe3O4 Core-shell Nanoparticles by Means of Single-step Thermal Decomposition Reaction

    PubMed Central

    Brollo, Maria Eugênia F.; López-Ruiz, Román; Muraca, Diego; Figueroa, Santiago J. A.; Pirota, Kleber R.; Knobel, Marcelo

    2014-01-01

    A temperature pause introduced in a simple single-step thermal decomposition of iron, with the presence of silver seeds formed in the same reaction mixture, gives rise to novel compact heterostructures: brick-like Ag@Fe3O4 core-shell nanoparticles. This novel method is relatively easy to implement, and could contribute to overcome the challenge of obtaining a multifunctional heteroparticle in which a noble metal is surrounded by magnetite. Structural analyses of the samples show 4 nm silver nanoparticles wrapped within compact cubic external structures of Fe oxide, with curious rectangular shape. The magnetic properties indicate a near superparamagnetic like behavior with a weak hysteresis at room temperature. The value of the anisotropy involved makes these particles candidates to potential applications in nanomedicine. PMID:25354532

  6. Probing the thermal decomposition behaviors of ultrathin HfO2 films by an in situ high temperature scanning tunneling microscope.

    PubMed

    Xue, Kun; Wang, Lei; An, Jin; Xu, Jianbin

    2011-05-13

    The thermal decomposition of ultrathin HfO(2) films (∼0.6-1.2 nm) on Si by ultrahigh vacuum annealing (25-800 °C) is investigated in situ in real time by scanning tunneling microscopy. Two distinct thickness-dependent decomposition behaviors are observed. When the HfO(2) thickness is ∼ 0.6 nm, no discernible morphological changes are found below ∼ 700 °C. Then an abrupt reaction occurs at 750 °C with crystalline hafnium silicide nanostructures formed instantaneously. However, when the thickness is about 1.2 nm, the decomposition proceeds gradually with the creation and growth of two-dimensional voids at 800 °C. The observed thickness-dependent behavior is closely related to the SiO desorption, which is believed to be the rate-limiting step of the decomposition process. PMID:21430314

  7. Pyrolysis of aseptic packages (tetrapak) in a laboratory screw type reactor and secondary thermal/catalytic tar decomposition

    SciTech Connect

    Haydary, J.; Susa, D.; Dudáš, J.

    2013-05-15

    Highlights: ► Pyrolysis of aseptic packages was carried out in a laboratory flow reactor. ► Distribution of tetrapak into the product yields was obtained. ► Composition of the pyrolysis products was estimated. ► Secondary thermal and catalytic decomposition of tars was studied. ► Two types of catalysts (dolomite and red clay marked AFRC) were used. - Abstract: Pyrolysis of aseptic packages (tetrapak cartons) in a laboratory apparatus using a flow screw type reactor and a secondary catalytic reactor for tar cracking was studied. The pyrolysis experiments were realized at temperatures ranging from 650 °C to 850 °C aimed at maximizing of the amount of the gas product and reducing its tar content. Distribution of tetrapak into the product yields at different conditions was obtained. The presence of H{sub 2}, CO, CH{sub 4}, CO{sub 2} and light hydrocarbons, HCx, in the gas product was observed. The Aluminum foil was easily separated from the solid product. The rest part of char was characterized by proximate and elemental analysis and calorimetric measurements. The total organic carbon in the tar product was estimated by elemental analysis of tars. Two types of catalysts (dolomite and red clay marked AFRC) were used for catalytic thermal tar decomposition. Three series of experiments (without catalyst in a secondary cracking reactor, with dolomite and with AFRC) at temperatures of 650, 700, 750, 800 and 850 °C were carried out. Both types of catalysts have significantly affected the content of tars and other components in pyrolytic gases. The effect of catalyst on the tetrapack distribution into the product yield on the composition of gas and on the total organic carbon in the tar product is presented in this work.

  8. Abiotic formation of hydrocarbons and oxygenated compounds during thermal decomposition of iron oxalate

    NASA Technical Reports Server (NTRS)

    McCollom, T. M.; Simoneit, B. R.

    1999-01-01

    The formation of organic compounds during the decomposition of iron oxalate dihydrate (IOD) was investigated as a possible analog for abiotic organic synthesis in geological systems. After heating at 330 degrees C for 2-4 days, IOD decomposed to a mixture of the minerals siderite and magnetite plus gas and non-volatile organic compounds. The organic products included an extremely large variety of compounds, making identification of individual reaction products difficult. However, the non-volatile products were dominated by several homologous series of alkylated cyclic compounds mostly containing a single aromatic ring, including alkylphenols, alkylbenzenes, alkyltetrahydronaphthols, and alkyltetrahydronaphthalenes. Traces of n-alkanols, n-alkanoic acids, n-alkanones, and n-alkanes were also identified. Carbon in the gas phase was predominantly CO2 (+CO?), with lesser amounts of light hydrocarbons to > C6 including all possible branched and normal isomers of the alkanes and alkenes. The organic products were apparently the result of two concurrent reaction processes: (1) condensation of the two-carbon units present in the initial oxalate moiety, and (2) Fischer-Tropsch-type synthesis from CO2 or CO generated during the experiment. Compounds produced by the former process may not be characteristic of synthesis from the single-carbon precursors which predominate in geologic systems, suggesting iron oxalate decomposition may not provide a particularly suitable analog for investigation of abiotic organic synthesis. When water was included in the reaction vessels, CO2 and traces of methane and light hydrocarbon gases were the only carbon products observed (other than siderite), suggesting that the presence of water allowed the system to proceed rapidly towards equilibrium and precluded the formation of metastable organic intermediates.

  9. Thermal decomposition study of Mo0.6W0.4Se2 single crystals

    NASA Astrophysics Data System (ADS)

    Chaki, Sunil H.; Deshpande, M. P.; Tailor, Jiten P.

    2013-06-01

    The Mo0.6W0.4Se2 single crystals were grown by direct vapour transport (DVT) technique. The thermogravimetric analysis (TGA), differential thermal analysis (DTA) and differential thermogravimetric (DTG) analysis were carried out on the as-grown Mo0.6W0.4Se2 single crystals in inert nitrogen atmosphere. All these thermal analysis were done from ambient temperature to 1223 K. The activation energy, enthalpy, entropy and Gibbs free energy of Mo0.6W0.4Se2 single crystals were determined from the thermal curves using Broido, Horowitz-Metzger (H-M), Piloyan-Novikova (P-N) and Coats-Redfern (C-R) relations. The results are reported in this paper.

  10. Thermal decomposition behavior of potassium and sodium jarosite synthesized in the presence of methylamine and alanine

    SciTech Connect

    J. Michelle Kotler; Nancy W. Hinman; C. Doc Richardson; Jill R. Scott

    2010-10-01

    Biomolecules, methylamine and alanine, found associated with natural jarosite samples peaked the interest of astrobiologists and planetary geologists. How the biomolecules are associated with jarosite remains unclear although the mechanism could be important for detecting biosignatures in the rock record on Earth and other planets. A series of thermal gravimetric experiments using synthetic K-jarosite and Na-jarosite were conducted to determine if thermal analysis could differentiate physical mixtures of alanine and methylamine with jarosite from samples where the methylamine or alanine was incorporated into the synthesis procedure. Physical mixtures and synthetic experiments with methylamine and alanine could be differentiated from one another and from the standards by thermal analysis for both the K-jarosite and Na-jarosite end-member suites. Changes included shifts in on-set temperatures, total temperature changes from on-set to final, and the presence of indicator peaks for methylamine and alanine in the physical mixture experiments.

  11. Thermal decomposition of t-butylamine borane studied by in situ solid state NMR

    SciTech Connect

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

    2010-03-18

    Development of suitable materials to store hydrogen for automotive use has received pointed attention over the past decade. Significant progress has been made with the discovery of novel chemical hydrides, complex metal hydrides, and adsorption substrates which continue to optimize both thermodynamics and kinetics of hydrogen sorption. Chemical hydrides typically offer the largest theoretical gravimetric capacities. Autrey et al. have recently shown that mechanical milling of alkali metal hydrides with ammonia borane can further lower the decomposition temperature. In all cases, however, many challenges remain in order to meet the current US DOE performance targets. Amine boranes are being considered for hydrogen storage materials since they contain significant quantities of hydrogen which potentially can be released at low temperatures (80-150 C) via chemical reactions. Ammonia borane, NH{sub 3}BH{sub 3}, is one of the most promising in this class as it decomposes to release greater than two moles of pure hydrogen gas (14 wt%) below 160 C. Although isoelectronic to ethane, NH{sub 3}BH{sub 3} is a solid at room temperature due to the di-hydrogen bonding network formed between the amine protons and boron hydrides in the solid state lattice. Further, it has been shown that the hydrogen release mechanism involves transformation and isomerization to an ionic dimer where a hydride migrates from one boron to the adjacent boron in the dimer. The greatest challenge to the use of ammonia borane as a hydrogen fuel is the regeneration path from spent fuel to ammonia borane again. The proposed chemical synthesis involves complicated organometallic reactions to form boron hydrogen bonds from the thermodynamically stable polyimidoborane products (BNH){sub n}. Recent theoretical calculations suggested that incorporation of carbon atoms into the (BNH)n product would be less thermodynamically stable. These (CBNH)n compounds are potentially less energy intensive making regeneration

  12. Corrosion-resistant coating prepared by the thermal decomposition of lithium permanganate

    SciTech Connect

    Ferrando, W.A.

    1999-09-01

    A ceramic, metal, or metal alloy surface is covered with lithium permanganate which is then thermally decomposed to produce a corrosion resistant coating on the surface. This coating serves as a primer coating which is preferably covered with an overcoat of a sealing paint.

  13. High resistance to thermal decomposition in brown cotton is linked to tannis and sodium content

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Brown cotton (Gossypium hirsutum L.) fibers (SA-1 and MC-BL) studied were inferior to white cotton fiber Sure-Grow 747 (SG747) in fiber quality, i.e., shorter length, fewer twists, and lower crystallinity, but exhibited superior thermal properties in thermogravimetry (TG), differential thermogravime...

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

    NASA Astrophysics Data System (ADS)

    Perovic, M.; Kusigerski, V.; Mrakovic, A.; Spasojevic, V.; Blanusa, J.; Nikolic, V.; Schneeweiss, O.; David, B.; Pizúrová, N.

    2015-03-01

    Nanorod ferrous oxalate dihydrate (FeC2O4 × 2H2O) which had been synthesized by the microemulsion method, was used as a precursor in the thermal decomposition process performed in air atmosphere. The formation of nanocrystalline hematite as the final product was preceded by the appearence of an intermediate product. Comprehensive study comprising several complementary techniques (x-ray diffraction, transmission electron microscopy, selected area electron diffraction, thermogravimetric/differential thermal analyses and SQUID magnetometry) confirmed that the intermediate product corresponds to the poorly crystalline Fe2O3. Due to the specific nanorod shape and poorly crystalline structure, the investigated Fe2O3 showed high coercive field value of ∼ 0.5 T at 5 K. Special attention in this study was devoted to the peculiar magnetic properties of poorly crystalline Fe2O3, which were thoroughly investigated by employing sophisticated experimental procedures such as relaxation of thermoremanent magnetization for different cooling fields, zero field and field cooled memory effects as well as aging experiments for different waiting times. At low temperatures and weak applied magnetic fields, the investigated system behaves similarly to spin glasses, manifesting slow, collective relaxation dynamics of magnetic moments through memory, rejuvenation and aging effects.

  15. Evaluation of shipboard formation of a neurotoxicant (trimethylolpropane phosphate) from thermal decomposition of synthetic aircraft engine lubricant.

    PubMed

    Wyman, J; Pitzer, E; Williams, F; Rivera, J; Durkin, A; Gehringer, J; Servé, P; von Minden, D; Macys, D

    1993-10-01

    MIL-L-23699 lubricants that are composed principally of trimethylolpropane triheptanoate (TMP) and tricresyl phosphate (TCP) have been shown to form a neurotoxicant, trimethylolpropane phosphate (TMPP), during pyrolysis and/or combustion. Mechanistically, TMPP is thought to irreversibly inhibit the GABA-mediated inhibitory response and thereby produce epileptiform clonic/tonic seizures with convulsions followed by death. Thermal decomposition of MIL-L-23699 lubricant produces TMPP under laboratory conditions, but this product has not been detected in the workplace following actual fires. This study has examined whether TMPP is produced during an actual shipboard fire by placing the synthetic lubricant in a fire environment aboard the ex-U.S.S. Shadwell, Mobile, Alabama. Both biological and chemical analyses were performed on the thermally decomposed lubricant to ensure detection of the neurotoxic material. Under the conditions of this study, the formation of TMPP during a shipboard fire was confirmed. The implications of this finding for safe management of post-fire cleanup are discussed. PMID:8237791

  16. Analysis of thermal radiation from laser-heated nanoparticles formed by laser-induced decomposition of ferrocene

    NASA Astrophysics Data System (ADS)

    Landström, L.; Elihn, K.; Boman, M.; Granqvist, C. G.; Heszler, P.

    2005-09-01

    Thermal radiation, originating from laser-heated gas-phase nanoparticles, was detected in the 400 700 nm wavelength range by means of optical emission spectroscopy. The particles were formed upon laser-induced photolytic decomposition of ferrocene (Fe(C5H5)2) and consisted of an iron core surrounded by a carbon shell. The laser-induced excitation was performed as the particles were still within the reactor zone, and the temperature of the particles could be determined from thermal emission. Both the temperature of the nanoparticles and the relative intensity changes of the emission were monitored as a function of time (with respect to the laser pulse), laser fluence and Ar ambient pressure. At high laser fluences, the particles reached high temperatures, and evidence was found for boiling of iron. Modeling of possible energy-releasing mechanisms such as black-body radiation, thermionic electron emission, evaporation and heat transfer by the ambient gas was also performed. The dominant cooling mechanisms at different ranges of temperature were clarified, together with a determination of the accommodation factor for the Ar nanoparticle collisions. The strong evaporation at elevated temperatures also led to significant iron loss from the produced particles.

  17. Thermal decomposition studies of 1,3,3-trinitroazetidine (TNAZ) and 1-nitroso-3,3-dinitroazetidine (NDNAZ) by simultaneous thermogravimetric modulated beam mass spectroscopy

    SciTech Connect

    Behrens, R. Jr.; Bulusu, S.

    1995-12-01

    The initial results from a study of the thermal decomposition of TNAZ, TNAZ-1-{sup 15}NO{sub 2} and NDNAZ using the simultaneous thermogravimetric modulated beam mass spectrometer (STMBMS) are presented. The major products formed in the decomposition of TNAZ are NO{sub 2} and NO with slightly lesser amounts of H{sub 2}O, HCN, CO/N{sub 2}, CO{sub 2}/N{sub 2}O and NDNAZ. The major product formed in the decomposition of NDNAZ is NO with lesser amounts of H{sub 2}O, HCN, CO/N{sub 2}O. The lower molecular weight products are similar to those observed in RSFTIR and IRMPD studies conducted previously by others. However, this study has shown that the mononitroso analogue of TNAZ, NDNAZ, is an important intermediate formed during the decomposition of TNAZ. It plays an important role in determining the identity of the products formed in the decomposition of TNAZ. The temporal behaviors Of the ion signals associated with the various thermal decomposition products from TNAZ, TNAZ-1-{sup 15}NO{sub 2} and NDNAZ are also presented. The illustrate the evolution sequence of the various products that are associated with the different reaction pathways that control the decomposition of these materials. In particular, the study of the {sup 15}N-labeled sample revealed that NO{sub 2} originates from both the likely sites in the TNAZ molecule and that the cleavage of the nitramine-NO{sub 2} group precedes that of the C-NO{sub 2} cleavage, resulting in similar sequences in the formation of NO and NDNAZ also.

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

    NASA Technical Reports Server (NTRS)

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

    1982-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1982-11-01

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

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

    PubMed

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

    2011-01-26

    High performance liquid chromatography (HPLC) on a calcium form cation exchange column with refractive index and photodiode array detection was used to investigate thermal decomposition as the cause of the loss of crystalline structure in sucrose. Crystalline sucrose structure was removed using a standard differential scanning calorimetry (SDSC) method (fast heating method) and a quasi-isothermal modulated differential scanning calorimetry (MDSC) method (slow heating method). In the fast heating method, initial decomposition components, glucose (0.365%) and 5-HMF (0.003%), were found in the sucrose sample coincident with the onset temperature of the first endothermic peak. In the slow heating method, glucose (0.411%) and 5-HMF (0.003%) were found in the sucrose sample coincident with the holding time (50 min) at which the reversing heat capacity began to increase. In both methods, even before the crystalline structure in sucrose was completely removed, unidentified thermal decomposition components were formed. These results prove not only that the loss of crystalline structure in sucrose is caused by thermal decomposition, but also that it is achieved via a time-temperature combination process. This knowledge is important for quality assurance purposes and for developing new sugar based food and pharmaceutical products. In addition, this research provides new insights into the caramelization process, showing that caramelization can occur under low temperature (significantly below the literature reported melting temperature), albeit longer time, conditions. PMID:21175200

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

    SciTech Connect

    Xu, Hongwu; Zhao, Yusheng; Vogel, Sven C; Hickmott, Donald D; Daemen, Luke L; Hartl, Monika A

    2009-01-01

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

  2. Thermal decomposition of electronic wastes: Mobile phone case and other parts

    SciTech Connect

    Molto, Julia; Egea, Silvia; Conesa, Juan Antonio; Font, Rafael

    2011-12-15

    Highlights: > Pyrolysis and combustion of different parts of mobile phones produce important quantities of CO and CO{sub 2}. > Naphthalene is the most abundant PAH obtained in the thermal treatment of mobile phones. > Higher combustion temperature increases the chlorinated species evolved. - Abstract: Pyrolysis and combustion runs at 850 {sup o}C in a horizontal laboratory furnace were carried out on different parts of a mobile phone (printed circuit board, mobile case and a mixture of both materials). The analyses of the carbon oxides, light hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), polychlorodibenzo-p-dioxin, polychlorodibenzofurans (PCDD/Fs), and dioxin-like PCBs are shown. Regarding semivolatile compounds, phenol, styrene, and its derivatives had the highest yields. In nearly all the runs the same PAHs were identified, naphthalene being the most common component obtained. Combustion of the printed circuit board produced the highest emission factor of PCDD/Fs, possibly due to the high copper content.

  3. Channel specific rate constants relevant to the thermal decomposition of disilane.

    SciTech Connect

    Matsumoto, Keiji; Klippenstein, Stephen J.; Koshi, Mitsuo; Tonokura, Kenichi

    2005-01-01

    Rate constants for the thermal dissociation of Si{sub 2}H{sub 6} are predicted with a novel transition state model. The saddle points for dissociation on the Si{sub 2}H{sub 6} potential energy surface are lower in energy than the corresponding separated products, as confirmed by high level ab initio quantum mechanical calculations. Thus, the dissociations of Si{sub 2}H{sub 6} to produce SiH{sub 2} + SiH{sub 4} (R1) and H{sub 3}SiSiH + H{sub 2} (R2) both proceed through tight inner transition states followed by loose outer transition states. The present 'dual' transition state model couples variational phase space theory treatments of the outer transition states with ab initio based fixed harmonic vibrator treatments of the inner transition states to obtain effective numbers of states for the two transition states acting in series. It is found that, at least near room temperature, such a dual transition state model is generally required for the proper description of each of the dissociations. Only at quite high temperatures, i.e., above 2000 K for (R1) and 600 K for (R2), does a single fixed inner transition state provide an adequate description. Similarly, only at quite low temperatures (below 100 and 10 K for (R1) and (R2), respectively) does a single outer transition state provide an adequate description. Pressure dependent rate constants are obtained from solutions to the multichannel master equation. These calculations confirm that dissociation channel (R2) is negligible under conditions relevant to the thermal chemical vapor deposition (CVD) processes. Rate constants for the chemical activation reactions, SiH{sub 2} + SiH{sub 4} {yields} Si{sub 2}H{sub 6} (R-1) and SiH{sub 2} + SiH{sub 4} {yields} H{sub 3}SiSiH + H{sub 2} (R3), are also evaluated within the dual transition state model. It is found that reaction R3 is the dominant channel for low pressures and high temperatures, i.e., below 100 Torr for temperatures above 1100 K.

  4. Channel specific rate constants relevant to the thermal decomposition of disilane.

    PubMed

    Matsumoto, Keiji; Klippenstein, Stephen J; Tonokura, Kenichi; Koshi, Mitsuo

    2005-06-01

    Rate constants for the thermal dissociation of Si2H6 are predicted with a novel transition state model. The saddle points for dissociation on the Si2H6 potential energy surface are lower in energy than the corresponding separated products, as confirmed by high level ab initio quantum mechanical calculations. Thus, the dissociations of Si2H6 to produce SiH2 + SiH4 (R1) and H3SiSiH + H2 (R2) both proceed through tight inner transition states followed by loose outer transition states. The present "dual" transition state model couples variational phase space theory treatments of the outer transition states with ab initio based fixed harmonic vibrator treatments of the inner transition states to obtain effective numbers of states for the two transition states acting in series. It is found that, at least near room temperature, such a dual transition state model is generally required for the proper description of each of the dissociations. Only at quite high temperatures, i.e., above 2000 K for (R1) and 600 K for (R2), does a single fixed inner transition state provide an adequate description. Similarly, only at quite low temperatures (below 100 and 10 K for (R1) and (R2), respectively) does a single outer transition state provide an adequate description. Pressure dependent rate constants are obtained from solutions to the multichannel master equation. These calculations confirm that dissociation channel (R2) is negligible under conditions relevant to the thermal chemical vapor deposition (CVD) processes. Rate constants for the chemical activation reactions, SiH2 + SiH4 --> Si2H6 (R-1) and SiH2 + SiH4 --> H3SiSiH + H2 (R3), are also evaluated within the dual transition state model. It is found that reaction R3 is the dominant channel for low pressures and high temperatures, i.e., below 100 Torr for temperatures above 1100 K. PMID:16833838

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

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

  6. A Signature of Roaming Dynamics in the Thermal Decomposition of Ethyl Nitrite: Chirped-Pulse Rotational Spectroscopy and Kinetic Modeling.

    PubMed

    Prozument, Kirill; Suleimanov, Yury V; Buesser, Beat; Oldham, James M; Green, William H; Suits, Arthur G; Field, Robert W

    2014-11-01

    Chirped-pulse (CP) Fourier transform rotational spectroscopy is uniquely suited for near-universal quantitative detection and structural characterization of mixtures that contain multiple molecular and radical species. In this work, we employ CP spectroscopy to measure product branching and extract information about the reaction mechanism, guided by kinetic modeling. Pyrolysis of ethyl nitrite, CH3CH2ONO, is studied in a Chen type flash pyrolysis reactor at temperatures of 1000-1800 K. The branching between HNO, CH2O, and CH3CHO products is measured and compared to the kinetic models generated by the Reaction Mechanism Generator software. We find that roaming CH3CH2ONO → CH3CHO + HNO plays an important role in the thermal decomposition of ethyl nitrite, with its rate, at 1000 K, comparable to that of the radical elimination channel CH3CH2ONO → CH3CH2O + NO. HNO is a signature of roaming in this system. PMID:26278732

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

    SciTech Connect

    Cui, BZ; Marinescu, M; Liu, JF

    2013-12-14

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

  8. Hexagonal ZnO porous plates prepared from microwave synthesized layered zinc hydroxide sulphate via thermal decomposition

    SciTech Connect

    Machovsky, Michal; Kuritka, Ivo; Sedlak, Jakub; Pastorek, Miroslav

    2013-10-15

    Graphical abstract: - Highlights: • Zinc hydroxy sulphate was synthesized in 3 min via microwave hydrothermal route. • Zinc hydroxy sulphate was converted into mesh like porous ZnO by calcining at 900°. • The process of transformation is topotactic. - Abstract: Layered zinc hydroxide sulphate (ZHS) was prepared by microwave-assisted hydrothermal precipitation of zinc sulphate monohydrate with hexamethylenetetramine. Under ambient conditions, the structure of ZHS determined by X-ray diffraction (XRD) was found to be a mixture of zinc hydroxide sulphate pentahydrate Zn{sub 4}SO{sub 4}(OH){sub 6}·5H{sub 2}O and tetrahydrate Zn{sub 4}SO{sub 4}(OH){sub 6}·4H{sub 2}O. Fourier transform infrared (FTIR) spectroscopy was used for characterization of the prepared materials. Based on the interpretation of ZHS's thermal decomposition profile obtained by thermogravimetric analysis, ZnO of high purity was prepared by calcination at 900 °C for 2 h. The structure of the resulting ZnO was confirmed by the XRD. The morphology examination by scanning electron microscopy revealed a porous mesh-like ZnO structure developed from the ZHS precursor at the expense of mass removal due to the release of water and sulphate during the calcination.

  9. Structural insights into the thermal decomposition sequence of barium tetrahydrogenorthotellurate(VI), Ba[H4TeO6

    NASA Astrophysics Data System (ADS)

    Weil, Matthias; Stöger, Berthold; Gierl-Mayer, Christian; Libowitzky, Eugen

    2016-09-01

    The compounds Ba[H4TeO6] (I), Ba[H2TeO5] (II), Ba[Te2O6(OH)2] (III) and Ba[TeO4] (IV) were prepared by application of a diffusion method (I), under hydrothermal conditions (II and III) and from solid state reactions (IV), respectively. Structure analysis on the basis of single crystal X-ray diffraction data revealed novel structure types for (I), (II) and (III) and isotypism of (IV) with PrSbO4 and LaSbO4. Common feature of the four oxotellurate(VI) structures are [TeO6] octahedra. Whereas in the crystal structure of (I) the octahedral units are isolated, they are condensed into chains via corner-sharing in (II) and via edge-sharing in (III) and (IV). The coordination numbers of the barium cations in the four structures range from seven to ten. Although hydrogen atom positions could not be located for the structures of (I) and (II), short interpolyhedral O···O contacts are evident for strong hydrogen bonding. The temperature behaviour of (I), (II) and (IV) was monitored by simultaneous thermal analysis (STA) measurements and in situ powder X-ray diffraction, revealing the decomposition sequence Ba[H4TeO6] → Ba[H2TeO5] → Ba[TeO4]→ Ba[TeO3] upon heating to temperatures up to 900 °C.

  10. Kinetics of thermal decomposition of styrene-butadiene rubber at low heating rates in nitrogen and oxygen

    SciTech Connect

    Chen, K.S.; Yeh, R.Z.; Chang, Y.R.

    1997-03-01

    The kinetics of thermal decomposition of styrene-butadiene rubber have been investigated thermogravimetrically under various heating rates either in nitrogen or mixed with 5--25% oxygen in nitrogen. The results show that in pure nitrogen the reaction involves only one stage, with an initial reaction temperature of 622--661 K and an apparent activation energy at 211 {+-} 15 kJ/mol. The initial reaction temperature decreases, but the reaction rate and its temperature range increase when the heating rate is increased. When oxygen is present, the reaction involves two parallel steps. The fractional conversion at the end of the first reaction is 0.83--0.87, depending on the oxygen concentration. Although the presence of oxygen somewhat delays the start of the initial reaction, the activation energy is reduced significantly, so that its rate becomes faster once reaction commences. The complete rate equation for both stages of reaction was obtained by summing the individual weighted rate equations; the weighting factors were determined from the fractional conversion at the end of the first reaction.

  11. RuO2/Activated Carbon Composite Electrode Prepared by Modified Colloidal Procedure and Thermal Decomposition Method

    NASA Astrophysics Data System (ADS)

    Li, Xiang; Zheng, Feng; Gan, Weiping; Luo, Xun

    2016-01-01

    RuO2/activated carbon (AC) composite electrode was prepared by a modified colloidal procedure and a thermal decomposition method. The precursor for RuO2/AC was coated on tantalum sheet and annealed at 150°C to 190°C for 3 h to develop thin-film electrode. The microstructure and morphology of the RuO2/AC film were characterized by thermogravimetric analysis (TGA), x-ray diffraction (XRD) analysis, and scanning electron microscopy (SEM). The TGA results showed the maximum loss of RuO2/AC composite film at 410°C, with residual RuO2 of 23.17 wt.%. The amorphous phase structure of the composite was verified by XRD analysis. SEM analysis revealed that fine RuO2 particles were dispersed in an activated carbon matrix after annealing. The electrochemical properties of RuO2/AC electrode were examined by cycling voltammetry, galvanostatic charge-discharge, and cyclic behavior measurements. The specific capacitance of RuO2/AC electrode reached 245 F g-1. The cyclic behavior of RuO2/AC electrode was stable. Optimal annealing was achieved at 170°C for 3 h.

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

    PubMed

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

    2015-11-01

    Tricalcium phosphate (TCP) is a bioceramic that is widely used in orthopedic and dental applications. TCP structures show excellent biocompatibility as well as biodegradability. In this study, porous β-TCP scaffolds were prepared by thermal decomposition of naphthalene. Scaffolds with 57.64% ± 3.54% density and a maximum pore size around 100 μm were fabricated via removing 30% naphthalene at 1150°C. The compressive strength for these scaffolds was 32.85 ± 1.41 MPa. Furthermore, by mixing 1 wt % SrO and 0.5 wt % SiO2 , pore interconnectivity improved, but the compressive strength decreased to 22.40 ± 2.70 MPa. However, after addition of polycaprolactone coating layers, the compressive strength of doped scaffolds increased to 29.57 ± 3.77 MPa. Porous scaffolds were implanted in rabbit femur defects to evaluate their biological property. The addition of dopants triggered osteoinduction by enhancing osteoid formation, osteocalcin expression, and bone regeneration, especially at the interface of the scaffold and host bone. This study showed processing flexibility to make interconnected porous scaffolds with different pore size and volume fraction porosity, while maintaining high compressive mechanical strength and excellent bioactivity. Results show that SrO/SiO2 -doped porous TCP scaffolds have excellent potential to be used in bone tissue engineering applications. PMID:25504889

  13. Studies of magnetite nanoparticles synthesized by thermal decomposition of iron (III) acetylacetonate in tri(ethylene glycol)

    NASA Astrophysics Data System (ADS)

    Maity, Dipak; Kale, S. N.; Kaul-Ghanekar, Ruchika; Xue, Jun-Min; Ding, Jun

    2009-10-01

    In this paper, water-soluble magnetite nanoparticles have been directly synthesized by thermal decomposition of iron (III) acetylacetonate, Fe(acac) 3 in tri(ethyleneglycol). Size and morphology of the nanoparticles are determined by transmission electron microscopy (TEM) and dynamic light scattering (DLS) measurements while the crystal structure is identified using X-ray diffraction (XRD). Surface charge and surface coating of the nanoparticles are recognized using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectra (XPS) and zeta potential measurements. Magnetic properties are determined using vibrating sample magnetometer (VSM) and superconducting quantum interference device (SQUID) measurements. The results show that as-prepared magnetite nanoparticles are relatively monodisperse, single crystalline and superparamagnetic in nature with the blocking temperature at around 100 K. The magnetite nanoparticles are found to be highly soluble in water due to steric and electrostatic interactions between the particles arising by the surface adsorbed tri(ethyleneglycol) molecules and associated positive charges, respectively. Cytotoxicity studies on human cervical (SiHa), mouse melanoma (B16F10) and mouse primary fibroblast cells demonstrate that up to a dose of 80 μg/ml, the magnetic nanoparticles are nontoxic to the cells. Specific absorption rate (SAR) value has been calculated to be 885 and 539 W/gm for samples with the iron concentration of 1 and 0.5 mg/ml, respectively. The high SAR value upon exposure to 20 MHz radiofrequency signifies the applicability of as-prepared magnetite nanoparticles for a feasible magnetic hyperthermia treatment.

  14. Pyrolysis of aseptic packages (tetrapak) in a laboratory screw type reactor and secondary thermal/catalytic tar decomposition.

    PubMed

    Haydary, J; Susa, D; Dudáš, J

    2013-05-01

    Pyrolysis of aseptic packages (tetrapak cartons) in a laboratory apparatus using a flow screw type reactor and a secondary catalytic reactor for tar cracking was studied. The pyrolysis experiments were realized at temperatures ranging from 650 °C to 850 °C aimed at maximizing of the amount of the gas product and reducing its tar content. Distribution of tetrapak into the product yields at different conditions was obtained. The presence of H2, CO, CH4, CO2 and light hydrocarbons, HCx, in the gas product was observed. The Aluminum foil was easily separated from the solid product. The rest part of char was characterized by proximate and elemental analysis and calorimetric measurements. The total organic carbon in the tar product was estimated by elemental analysis of tars. Two types of catalysts (dolomite and red clay marked AFRC) were used for catalytic thermal tar decomposition. Three series of experiments (without catalyst in a secondary cracking reactor, with dolomite and with AFRC) at temperatures of 650, 700, 750, 800 and 850 °C were carried out. Both types of catalysts have significantly affected the content of tars and other components in pyrolytic gases. The effect of catalyst on the tetrapack distribution into the product yield on the composition of gas and on the total organic carbon in the tar product is presented in this work. PMID:23428565

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

    NASA Astrophysics Data System (ADS)

    Gómez-Núñez, Alberto; Roura, Pere; López, Concepción; Vilà, Anna

    2016-09-01

    Four inks for the production of ZnO semiconducting films have been prepared with zinc acetate dihydrate as precursor salt and one among the following aminoalcohols: aminopropanol (APr), aminomethyl butanol (AMB), aminophenol (APh) and aminobenzyl alcohol (AB) as stabilizing agent. Their thermal decomposition process has been analyzed in situ by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and evolved gas analysis (EGA), whereas the solid product has been analysed ex-situ by X-ray diffraction (XRD) and infrared spectroscopy (IR). Although, except for the APh ink, crystalline ZnO is already obtained at 300 °C, the films contain an organic residue that evolves at higher temperature in the form of a large variety of nitrogen-containing cyclic compounds. The results indicate that APr can be a better stabilizing agent than ethanolamine (EA). It gives larger ZnO crystal sizes with similar carbon content. However, a common drawback of all the amino stabilizers (EA included) is that nitrogen atoms have not been completely removed from the ZnO film at the highest temperature of our experiments (600 °C).

  16. Synthesis and characterization of CuO-montmorillonite nanocomposite by thermal decomposition method and antibacterial activity of nanocomposite.

    PubMed

    Sohrabnezhad, Sh; Mehdipour Moghaddam, M J; Salavatiyan, T

    2014-05-01

    CuO-montmorillonite (CuO-MMT) nanocomposite was synthesized by thermal decomposition methods and characterized by diffuse reflectance spectroscopy (DRS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). The resultant particles are nearly spherical and particle size is in the range of ~3-5 nm. X-ray diffraction patterns indicate that MMT (1.22 nm) has a d-spacing higher than CuO-MMT nanocomposite (0.97 nm). This result implied that CuO nanoparticles can exist in micropore of MMT. The disappeared of band at 918 cm(-1) and decreasing of intensity of 3630 cm(-1) band in FT-IR spectra confirm substitution of aluminum in octahedral layer by Cu(2+) cations. The diffuse reflectance spectra show that the value of band gap energy for CuO-MMT nanocomposite (2.7 eV) is more than CuO nanoparticles (1.2 eV). It was found that decrease in the particle size of CuO nanoparticles due to quantum size effect. The antibacterial activity of CuO-MMT nanocomposite was tested against Escherichia coli. Nanocomposite showed efficient bactericidal effect. PMID:24531107

  17. Synthesis and characterization of CuO-montmorillonite nanocomposite by thermal decomposition method and antibacterial activity of nanocomposite

    NASA Astrophysics Data System (ADS)

    Sohrabnezhad, Sh.; Mehdipour Moghaddam, M. J.; Salavatiyan, T.

    CuO-montmorillonite (CuO-MMT) nanocomposite was synthesized by thermal decomposition methods and characterized by diffuse reflectance spectroscopy (DRS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). The resultant particles are nearly spherical and particle size is in the range of ˜3-5 nm. X-ray diffraction patterns indicate that MMT (1.22 nm) has a d-spacing higher than CuO-MMT nanocomposite (0.97 nm). This result implied that CuO nanoparticles can exist in micropore of MMT. The disappeared of band at 918 cm-1 and decreasing of intensity of 3630 cm-1 band in FT-IR spectra confirm substitution of aluminum in octahedral layer by Cu2+ cations. The diffuse reflectance spectra show that the value of band gap energy for CuO-MMT nanocomposite (2.7 eV) is more than CuO nanoparticles (1.2 eV). It was found that decrease in the particle size of CuO nanoparticles due to quantum size effect. The antibacterial activity of CuO-MMT nanocomposite was tested against Escherichia coli. Nanocomposite showed efficient bactericidal effect.

  18. Thermal decomposition of tetramethyl orthosilicate in the gas phase: An experimental and theoretical study of the initiation process

    SciTech Connect

    Chu, J.C.S.; Soller, R.; Lin, M.C. ); Melius, C.F. )

    1995-01-12

    The thermal decomposition of Si(OCH[sub 3])[sub 4] (TMOS) has been studied by FTIR at temperatures between 858 and 968 K. The experiment was carried out in a static cell at a constant pressure of 700 Torr under highly diluted conditions. Additional experiments were performed by using toluene as a radical scavenger. The species monitored included TMOS, CH[sub 2]O, CH[sub 4], and CO. According to these measurements, the first-order global rate constants for the disappearance of TMOS without and with toluene can be given by k[sub g] = 1.4 x 10[sup 16] exp(-81 200/RT) s[sup [minus]1] and k[sub g] = 2.0 x 10[sup 14] exp(-74 500/RT) s[sup [minus]1], respectively. The noticeable difference between the two sets of Arrhenius parameters suggests that, in the absence of the inhibitor, the reactant was consumed to a significant extent by radical attacks at higher temperatures. The experimental data were kinetically modeled with the aid of a quantum-chemical calculation using the BAC-MP4 method. The results of the kinetic modeling, using the mechanism constructed on the basis of the quantum-chemical data and the known C/H/O chemistry, identified two rate-controlling reactions whose first-order rate constants are given here. 22 refs., 15 figs., 3 tabs.

  19. Far-reaching geometrical artefacts due to thermal decomposition of polymeric coatings around focused ion beam milled pigment particles.

    PubMed

    Rykaczewski, K; Mieritz, D G; Liu, M; Ma, Y; Iezzi, E B; Sun, X; Wang, L P; Solanki, K N; Seo, D-K; Wang, R Y

    2016-06-01

    Focused ion beam and scanning electron microscope (FIB-SEM) instruments are extensively used to characterize nanoscale composition of composite materials, however, their application to analysis of organic corrosion barrier coatings has been limited. The primary concern that arises with use of FIB to mill organic materials is the possibility of severe thermal damage that occurs in close proximity to the ion beam impact. Recent research has shown that such localized artefacts can be mitigated for a number of polymers through cryogenic cooling of the sample as well as low current milling and intelligent ion beam control. Here we report unexpected nonlocalized artefacts that occur during FIB milling of composite organic coatings with pigment particles. Specifically, we show that FIB milling of pigmented polysiloxane coating can lead to formation of multiple microscopic voids within the substrate as far as 5 μm away from the ion beam impact. We use further experimentation and modelling to show that void formation occurs via ion beam heating of the pigment particles that leads to decomposition and vaporization of the surrounding polysiloxane. We also identify FIB milling conditions that mitigate this issue. PMID:26695001

  20. Thermal decomposition of 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), a novel brominated flame retardant.

    PubMed

    Altarawneh, Mohammednoor; Dlugogorski, Bogdan Z

    2014-12-16

    1,2-Bis(2,4,6-tribromophenoxy)ethane (BTBPE) is currently one of the most commonly applied novel brominated flame retardants. In this contribution, we analyze in detail the mechanisms pertinent to its thermal decomposition in view of analogous experimental findings. We demonstrate that a 1,3-hydrogen shift, leading to 2,4,6-tribromophenol (M9) and 1,3,5-tribromo-2-(vinyloxy)benzene (M10) molecules, dominates direct scission of O-CH2 bonds up to a temperature of ∼ 680 K. H atom abstraction from CH2 sites, followed by a fission of a C-C bond, produce a 2,4,6-tribromophenoxy radical (M2) and a M10 molecule. Bimolecular condensation reactions involving M2, M9, and M10 generate several congeners of brominated diphenyl ethers and their OH/OCHCH2 substituents, which serve as direct precursors for the formation of polybrominated dibenzo-p-dioxins. Reaction of M9 with a model compound of a hydrocarbon chain preferentially yields M2. Strong adsorption energy of the latter on a radical site of a hydrocarbon chain suggests that mechanisms such as Langmuir-Hinshelwood, Eley-Rideal, and Diels-Alder might be operating during the formation of PBDD/Fs from brominated flame retardants (BFRs). Reactions of alkyl primary/secondary radicals and diradical with the BTBPE molecule proceed via H abstraction from a -CH2- moiety. PMID:25340709

  1. Semicarbazide is a minor thermal decomposition product of azodicarbonamide used in the gaskets of certain food jars.

    PubMed

    Stadler, Richard H; Mottier, Pascal; Guy, Philippe; Gremaud, Eric; Varga, Natalia; Lalljie, Sam; Whitaker, Richard; Kintscher, Jurgen; Dudler, Vincent; Read, Wendy A; Castle, Laurence

    2004-03-01

    Evidence is presented for the first time showing that semicarbazide (SEM) is a minor thermal decomposition product of the blowing agent azodicarbonamide (ADC). A novel direct analytical method based on liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESIMS/MS) has been developed to determine SEM in foamed polyvinyl chloride (PVC) seals of metal lids, as well as in commercially available ADC. The direct LC-MS/MS method for gaskets entails extraction of the gaskets in hot water, addition of ((15)N(2)(13)C)-SEM as internal standard, and injection of an aliquot directly into the LC-MS system, achieving good sensitivity (S/N = 348 for 2 ng injected on-column) and monitoring three characteristic mass transitions (m/z 76-->31; 76 -->44; 76-->59). Semicarbazide can be detected in thermally treated ADC, reaching up to 0.93 mmol mol(-1) at 220 degrees C, as determined by the direct LC-MS/MS method. This new method is also compared to the classical derivatization method using 2-nitrobenzaldehyde (2-NBA) that is routinely employed to determine SEM as an indicator of the usage of the antimicrobial drug nitrofurazone, the use of which is not authorized in the European Union (EU). Both methods revealed proportional results, with approx. 3-fold higher levels recorded by the direct SEM approach, probably due to differences in the extraction procedures used. A limited survey of plastic seals from used press twist and twist-off metal lids on food jars (non-foamed and foamed) revealed levels of SEM ranging from 2 to 8689 microg kg(-1)(average = 1593 microg kg(-1), n= 57 determinations). PMID:14978533

  2. The thermal decomposition of the benzyl radical in a heated micro-reactor. II. Pyrolysis of the tropyl radical.

    PubMed

    Buckingham, Grant T; Porterfield, Jessica P; Kostko, Oleg; Troy, Tyler P; Ahmed, Musahid; Robichaud, David J; Nimlos, Mark R; Daily, John W; Ellison, G Barney

    2016-07-01

    Cycloheptatrienyl (tropyl) radical, C7H7, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. The pyrolysis products resulting from C7H7 were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 μs. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C7H7 are only acetylene and cyclopentadienyl radicals. Tropyl radicals do not isomerize to benzyl radicals at reactor temperatures up to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C7H7) radicals but rather only benzyl (C6H5CH2). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C6H5CH2, C6H5CD2, C6D5CH2, and C6H5 (13)CH2. Analysis of the temperature dependence for the pyrolysis of the isotopic species (C6H5CD2, C6D5CH2, and C6H5 (13)CH2) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K). PMID:27394106

  3. The thermal decomposition of the benzyl radical in a heated micro-reactor. II. Pyrolysis of the tropyl radical

    NASA Astrophysics Data System (ADS)

    Buckingham, Grant T.; Porterfield, Jessica P.; Kostko, Oleg; Troy, Tyler P.; Ahmed, Musahid; Robichaud, David J.; Nimlos, Mark R.; Daily, John W.; Ellison, G. Barney

    2016-07-01

    Cycloheptatrienyl (tropyl) radical, C7H7, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. The pyrolysis products resulting from C7H7 were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 μs. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C7H7 are only acetylene and cyclopentadienyl radicals. Tropyl radicals do not isomerize to benzyl radicals at reactor temperatures up to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C7H7) radicals but rather only benzyl (C6H5CH2). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C6H5CH2, C6H5CD2, C6D5CH2, and C6H513CH2. Analysis of the temperature dependence for the pyrolysis of the isotopic species (C6H5CD2, C6D5CH2, and C6H513CH2) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).

  4. Yttrium-succinates coordination polymers: Hydrothermal synthesis, crystal structure and thermal decomposition

    SciTech Connect

    Amghouz, Zakariae; Roces, Laura; Garcia-Granda, Santiago; Garcia, Jose R.; Souhail, Badredine; Mafra, Luis; Shi, Fa-nian; Rocha, Joao

    2009-12-15

    New polymeric yttrium-succinates, Y{sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}(H{sub 2}O){sub 4}.6H{sub 2}O and Y{sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}(H{sub 2}O){sub 2}, have been synthesized, and their structures (solved by single crystal XRD) are compared with that of Y{sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}(H{sub 2}O){sub 2}.H{sub 2}O. Three compounds were obtained as single phases, and their thermal behaviour is described. - Graphical abstract: In the field of coordination polymers or MOF's, few studies report on the polymorphs of Ln(III)-succinic acid. Here, we describe the hydrothermal synthesis and structural characterization of two novel yttrium-succinates coordination polymers, respectively 2D and 3D, Y{sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}(H{sub 2}O){sub 4}.6H{sub 2}O and Y{sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}(H{sub 2}O){sub 2}.

  5. Thermal decomposition of a honeycomb-network sheet: A molecular dynamics simulation study

    NASA Astrophysics Data System (ADS)

    Paturej, J.; Popova, H.; Milchev, A.; Vilgis, T. A.

    2012-08-01

    The thermal degradation of a graphene-like two-dimensional honeycomb membrane with bonds undergoing temperature-induced scission is studied by means of Molecular Dynamics simulation using Langevin thermostat. We demonstrate that at lower temperature the probability distribution of breaking bonds is highly peaked at the rim of the membrane sheet whereas at higher temperature bonds break at random everywhere in the hexagonal flake. The mean breakage time τ is found to decrease with the total number of network nodes N by a power law τ ∝ N-0.5 and reveals an Arrhenian dependence on temperature T. Scission times are themselves exponentially distributed. The fragmentation kinetics of the average number of clusters can be described by first-order chemical reactions between network nodes ni of different coordination. The distribution of fragments sizes evolves with time elapsed from initially a δ-function through a bimodal one into a single-peaked again at late times. Our simulation results are complemented by a set of 1st-order kinetic differential equations for ni which can be solved exactly and compared to data derived from the computer experiment, providing deeper insight into the thermolysis mechanism.

  6. Rapid hydrogen gas generation using reactive thermal decomposition of uranium hydride.

    SciTech Connect

    Kanouff, Michael P.; Van Blarigan, Peter; Robinson, David B.; Shugard, Andrew D.; Gharagozloo, Patricia E.; Buffleben, George M.; James, Scott Carlton; Mills, Bernice E.

    2011-09-01

    Oxygen gas injection has been studied as one method for rapidly generating hydrogen gas from a uranium hydride storage system. Small scale reactors, 2.9 g UH{sub 3}, were used to study the process experimentally. Complimentary numerical simulations were used to better characterize and understand the strongly coupled chemical and thermal transport processes controlling hydrogen gas liberation. The results indicate that UH{sub 3} and O{sub 2} are sufficiently reactive to enable a well designed system to release gram quantities of hydrogen in {approx} 2 seconds over a broad temperature range. The major system-design challenge appears to be heat management. In addition to the oxidation tests, H/D isotope exchange experiments were performed. The rate limiting step in the overall gas-to-particle exchange process was found to be hydrogen diffusion in the {approx}0.5 {mu}m hydride particles. The experiments generated a set of high quality experimental data; from which effective intra-particle diffusion coefficients can be inferred.

  7. Thermal Decomposition of Calcium Perchlorate/Iron-Mineral Mixtures: Implications of the Evolved Oxygen from the Rocknest Eolian Deposit in Gale Crater, Mars

    NASA Technical Reports Server (NTRS)

    Bruck, A. M.; Sutter, B.; Ming, D. W.; Mahaffy, P.

    2014-01-01

    A major oxygen release between 300 and 500 C was detected by the Mars Curiosity Rover Sample Analysis at Mars (SAM) instrument at the Rocknest eolian deposit. Thermal decomposition of perchlorate (ClO4-) salts in the Rocknest samples are a possible explanation for this evolved oxygen release. Releative to Na-, K-, Mg-, and Fe-perchlorate, the thermal decomposition of Ca-perchlorate in laboratory experiments released O2 in the temperature range (400-500degC) closest to the O2 release temperatures observed for the Rocknest material. Furthermore, calcium perchlorate could have been the source of Cl in the chlorinated-hydrocarbons species that were detected by SAM. Different components in the Martian soil could affect the decomposition temperature of calcium per-chlorate or another oxychlorine species. This interaction of the two components in the soil could result in O2 release temperatures consistent with those detected by SAM in the Rocknest materials. The decomposition temperatures of various alkali metal perchlorates are known to decrease in the presence of a catalyst. The objective of this work is to investigate catalytic interactions on calcium perchlorate from various iron-bearing minerals known to be present in the Rocknest material

  8. Correlation between ionic radii of metals and thermal decomposition of supramolecular structure of azodye complexes

    NASA Astrophysics Data System (ADS)

    El-Sonbati, A. Z.; Diab, M. A.; El-Bindary, A. A.; Eldesoky, A. M.; Morgan, Sh. M.

    2015-01-01

    An interesting azodye heterocyclic ligand of copper(II), cobalt(II), nickel(II) and uranyl(II) complexes have been synthesized by the reaction of metal salts with 5-(2,3-dimethyl-1-phenylpyrazol-5-one azo)-2-thioxo-4-thiazolidinone (HL) yields 1:1 and 1:2 (M:L) complexes depending on the reaction conditions. The elemental analysis, magnetic moments, spectral (UV-Vis, IR, 1H and 13C NMR and ESR) and thermal studies were used to characterize the isolated complexes. The molecular structures of the ligand tautomers are optimized theoretically and the quantum chemical parameters are calculated. The IR spectra showed that the ligand (HL) act as monobasic tridentate/neutral bidentate through the (sbnd Ndbnd N), enolic (Csbnd O)- and/or oxygen keto moiety groups forming a five/six-membered structures. According to intramolecular hydrogen bond leads to increasing of the complexes stability. The molar conductivities show that all the complexes are non-electrolytes. The ESR spectra indicate that the free electron is in dxy orbital. The calculated bonding parameter indicates that in-plane σ-bonding is more covalent than in-plane π-bonding. The coordination geometry is five/six-coordinated trigonal bipyramidal for complex (1) and octahedral for complexes (2-6). The value of covalency factor β12 and orbital reduction factor K accounts for the covalent nature of the complexes. The activation thermodynamic parameters are calculated using Coats-Redfern and Horowitz-Metzger methods. The synthesized ligand (HL) and its Cu(II) complexes (1, 2 and 4) are screened for their biological activity against bacterial and fungal species. The ligand (HL) showed antimicrobial activities against Escherichia coli. The ligand (HL) and its Cu(II) complexes (2 and 4) have very high antifungal activity against Penicillium italicum. The inhibitive action of ligand (HL), against the corrosion of C-steel in 2 M HCl solution has been investigated using potentiodynamic polarization and electrochemical

  9. Correlation between ionic radii of metals and thermal decomposition of supramolecular structure of azodye complexes.

    PubMed

    El-Sonbati, A Z; Diab, M A; El-Bindary, A A; Eldesoky, A M; Morgan, Sh M

    2015-01-25

    An interesting azodye heterocyclic ligand of copper(II), cobalt(II), nickel(II) and uranyl(II) complexes have been synthesized by the reaction of metal salts with 5-(2,3-dimethyl-1-phenylpyrazol-5-one azo)-2-thioxo-4-thiazolidinone (HL) yields 1:1 and 1:2 (M:L) complexes depending on the reaction conditions. The elemental analysis, magnetic moments, spectral (UV-Vis, IR, (1)H and (13)C NMR and ESR) and thermal studies were used to characterize the isolated complexes. The molecular structures of the ligand tautomers are optimized theoretically and the quantum chemical parameters are calculated. The IR spectra showed that the ligand (HL) act as monobasic tridentate/neutral bidentate through the (-N=N), enolic (C-O)(-) and/or oxygen keto moiety groups forming a five/six-membered structures. According to intramolecular hydrogen bond leads to increasing of the complexes stability. The molar conductivities show that all the complexes are non-electrolytes. The ESR spectra indicate that the free electron is in dxy orbital. The calculated bonding parameter indicates that in-plane σ-bonding is more covalent than in-plane π-bonding. The coordination geometry is five/six-coordinated trigonal bipyramidal for complex (1) and octahedral for complexes (2-6). The value of covalency factor β1(2) and orbital reduction factor K accounts for the covalent nature of the complexes. The activation thermodynamic parameters are calculated using Coats-Redfern and Horowitz-Metzger methods. The synthesized ligand (HL) and its Cu(II) complexes (1, 2 and 4) are screened for their biological activity against bacterial and fungal species. The ligand (HL) showed antimicrobial activities against Escherichia coli. The ligand (HL) and its Cu(II) complexes (2 and 4) have very high antifungal activity against Penicillium italicum. The inhibitive action of ligand (HL), against the corrosion of C-steel in 2M HCl solution has been investigated using potentiodynamic polarization and electrochemical

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

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

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

  11. Facile synthesis of a mesoporous Co3O4 network for Li-storage via thermal decomposition of an amorphous metal complex.

    PubMed

    Wen, Wei; Wu, Jin-Ming; Cao, Min-Hua

    2014-11-01

    A facile strategy is developed for mass fabrication of porous Co3O4 networks via the thermal decomposition of an amorphous cobalt-based complex. At a low mass loading, the achieved porous Co3O4 network exhibits excellent performance for lithium storage, which has a high capacity of 587 mA h g(-1) after 500 cycles at a current density of 1000 mA g(-1). PMID:25252110

  12. In-situ and self-distributed: A new understanding on catalyzed thermal decomposition process of ammonium perchlorate over Nd{sub 2}O{sub 3}

    SciTech Connect

    Zou, Min Wang, Xin Jiang, Xiaohong Lu, Lude

    2014-05-01

    Catalyzed thermal decomposition process of ammonium perchlorate (AP) over neodymium oxide (Nd{sub 2}O{sub 3}) was investigated. Catalytic performances of nanometer-sized Nd{sub 2}O{sub 3} and micrometer-sized Nd{sub 2}O{sub 3} were evaluated by differential scanning calorimetry (DSC). In contrast to universal concepts, catalysts in different sizes have nearly similar catalytic activities. Based on structural and morphological variation of the catalysts during the reaction, combined with mass spectrum analyses and studies of unmixed style, a new understanding of this catalytic process was proposed. We believed that the newly formed chloride neodymium oxide (NdOCl) was the real catalytic species in the overall thermal decomposition of AP over Nd{sub 2}O{sub 3}. Meanwhile, it was the “self-distributed” procedure which occurred within the reaction that also worked for the improvement of overall catalytic activities. This work is of great value in understanding the roles of micrometer-sized catalysts used in heterogeneous reactions, especially the solid–solid reactions which could generate a large quantity of gaseous species. - Graphical abstract: In-situ and self-distributed reaction process in thermal decomposition of AP catalyzed by Nd{sub 2}O{sub 3}. - Highlights: • Micro- and nano-Nd{sub 2}O{sub 3} for catalytic thermal decomposition of AP. • No essential differences on their catalytic performances. • Structural and morphological variation of catalysts digs out catalytic mechanism. • This catalytic process is “in-situ and self-distributed” one.

  13. Thermal Decomposition of an Impure (Roxbury) Siderite: Relevance to the Presence of Chemically Pure Magnetite Crystals in ALH84001 Carbonate Disks

    NASA Technical Reports Server (NTRS)

    McKay, D.S.; Gibson, E.K.; Thomas-Keprta, K.L.; Clemett, S.J.; Wentworth, S.J.

    2009-01-01

    The question of the origin of nanophase magnetite in Martian meteorite ALH84001 has been widely debated for nearly a decade. Golden et al. have reported producing nearly chemically pure magnetite from thermal decomposition of chemically impure siderite [(Fe, Mg, Mn)CO3]. This claim is significant for three reasons: first, it has been argued that chemically pure magnetite present in the carbonate disks in Martian meteorite ALH84001 could have formed by the thermal decomposition of the impure carbonate matrix in which they are embedded; second, the chemical purity of magnetite has been previously used to identify biogenic magnetite; and, third, previous studies of thermal decomposition of impure (Mg,Ca,Mn)-siderites, which have been investigated under a wide variety of conditions by numerous researchers, invariably yields a mixed metal oxide phase as the product and not chemically pure magnetite. The explanation for this observation is that these siderites all possess the same crystallographic structure (Calcite; R3c) so solid solutions between these carbonates are readily formed and can be viewed on an atomic scale as two chemically different but structurally similar lattices.

  14. TG-MS analysis and kinetic study for thermal decomposition of six representative components of municipal solid waste under steam atmosphere.

    PubMed

    Zhang, Jinzhi; Chen, Tianju; Wu, Jingli; Wu, Jinhu

    2015-09-01

    Thermal decomposition of six representative components of municipal solid waste (MSW, including lignin, printing paper, cotton, rubber, polyvinyl chloride (PVC) and cabbage) was investigated by thermogravimetric-mass spectroscopy (TG-MS) under steam atmosphere. Compared with TG and derivative thermogravimetric (DTG) curves under N2 atmosphere, thermal decomposition of MSW components under steam atmosphere was divided into pyrolysis and gasification stages. In the pyrolysis stage, the shapes of TG and DTG curves under steam atmosphere were almost the same with those under N2 atmosphere. In the gasification stage, the presence of steam led to a greater mass loss because of the steam partial oxidation of char residue. The evolution profiles of H2, CH4, CO and CO2 were well consistent with DTG curves in terms of appearance of peaks and relevant stages in the whole temperature range, and the steam partial oxidation of char residue promoted the generation of more gas products in high temperature range. The multi-Gaussian distributed activation energy model (DAEM) was proved plausible to describe thermal decomposition behaviours of MSW components under steam atmosphere. PMID:26066574

  15. Determination of formal kinetic constants of thermal decomposition of aqueous hydrogen peroxide solution in a mixture of magnetic powder, based on experimental thermogram, obtained in adiabatic conditions

    NASA Astrophysics Data System (ADS)

    Zaripov, Jamshed; Borisov, Boris; Bondarchuk, Sergey

    2014-08-01

    Process of thermal decomposition of hydrogen peroxide aqueous solution with the addition of magnetic powder in the form of toner for printers and lanthanum manganite were considered. Obtained resulting from an experiment in the Dewar container conducted thermogram analyzed using mass balance equations and heat. Formal kinetic parameters determined, and conclude that the magnetic powder in the mixture does not have catalytic properties. The described technique is recommended as a rapid analysis of the kinetics of the various reactions to substances having predefined thermal and thermodynamic properties.

  16. Study of thermal decomposition mechanisms and absorption cross section of nitro-rich phenyl- and bis-series 1,2,3-triazoles.

    PubMed

    Chaudhary, A K; Rao, K S; Sudheer Kumar, A

    2016-02-01

    This paper reports the investigation of thermal decomposition mechanisms and evaluation of thermally released NO2 from two newly synthesized high-energy materials named 1-(4-nitrophenyl)-1H-1,2,3-triazole (S8) and 2,6-bis ((4-(nitromethyl)-1H-1,2,3-triazol-1-yl)methyl) pyridine (S9) using time-resolved pulsed photoacoustic (PA) pyrolysis technique. The PA spectra were recorded between the 30°C and 350°C range and by varying the pressure of compounds vapor using 532 nm wavelength of pulse duration 7 ns at 10 Hz repetition rate obtained from Q-switched Nd:YAG laser pulses. The PA results were cross verified with thermogravimetric-differential thermal analysis data. The quality factor "&=&Q"&=& of the PA cavity was measured to test the thermal stability of the compound. In addition, we have ascertained the molecular density, absorption cross sections of high-energy materials vapor in terms of NO2. The corresponding values are of the order of 0.1-1.2×10(20)  cm-3 and 0.5-6 kilobarn, respectively. These results once again confirm the close agreement between the radiative and nonradiative transitions data and established the role of NO2 during the thermal decomposition process. PMID:26836085

  17. Validation of heat transfer, thermal decomposition, and container pressurization of polyurethane foam using mean value and Latin hypercube sampling approaches

    SciTech Connect

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

    2014-12-09

    In this study, polymer foam encapsulants provide mechanical, electrical, and thermal isolation in engineered systems. It can be advantageous to surround objects of interest, such as electronics, with foams in a hermetically sealed container in order to protect them from hostile environments or from accidents such as fire. In fire environments, gas pressure from thermal decomposition of foams can cause mechanical failure of sealed systems. In this work, a detailed uncertainty quantification study of polymeric methylene diisocyanate (PMDI)-polyether-polyol based polyurethane foam is presented and compared to experimental results to assess the validity of a 3-D finite element model of the heat transfer and degradation processes. In this series of experiments, 320 kg/m3 PMDI foam in a 0.2 L sealed steel container is heated to 1,073 K at a rate of 150 K/min. The experiment ends when the can breaches due to the buildup of pressure. The temperature at key location is monitored as well as the internal pressure of the can. Both experimental uncertainty and computational uncertainty are examined and compared. The mean value method (MV) and Latin hypercube sampling (LHS) approach are used to propagate the uncertainty through the model. The results of the both the MV method and the LHS approach show that while the model generally can predict the temperature at given locations in the system, it is less successful at predicting the pressure response. Also, these two approaches for propagating uncertainty agree with each other, the importance of each input parameter on the simulation results is also investigated, showing that for the temperature response the conductivity of the steel container and the effective conductivity of the foam, are the most important parameters. For the pressure response, the activation energy, effective conductivity, and specific heat are most important. The comparison to experiments and the identification of the drivers of uncertainty allow

  18. Validation of heat transfer, thermal decomposition, and container pressurization of polyurethane foam using mean value and Latin hypercube sampling approaches

    DOE PAGESBeta

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

    2014-12-09

    In this study, polymer foam encapsulants provide mechanical, electrical, and thermal isolation in engineered systems. It can be advantageous to surround objects of interest, such as electronics, with foams in a hermetically sealed container in order to protect them from hostile environments or from accidents such as fire. In fire environments, gas pressure from thermal decomposition of foams can cause mechanical failure of sealed systems. In this work, a detailed uncertainty quantification study of polymeric methylene diisocyanate (PMDI)-polyether-polyol based polyurethane foam is presented and compared to experimental results to assess the validity of a 3-D finite element model of themore » heat transfer and degradation processes. In this series of experiments, 320 kg/m3 PMDI foam in a 0.2 L sealed steel container is heated to 1,073 K at a rate of 150 K/min. The experiment ends when the can breaches due to the buildup of pressure. The temperature at key location is monitored as well as the internal pressure of the can. Both experimental uncertainty and computational uncertainty are examined and compared. The mean value method (MV) and Latin hypercube sampling (LHS) approach are used to propagate the uncertainty through the model. The results of the both the MV method and the LHS approach show that while the model generally can predict the temperature at given locations in the system, it is less successful at predicting the pressure response. Also, these two approaches for propagating uncertainty agree with each other, the importance of each input parameter on the simulation results is also investigated, showing that for the temperature response the conductivity of the steel container and the effective conductivity of the foam, are the most important parameters. For the pressure response, the activation energy, effective conductivity, and specific heat are most important. The comparison to experiments and the identification of the drivers of uncertainty allow for

  19. Synthesis of two nickel (II) complexes bearing pyrrolide-imine ligand and their catalytic effects on thermal decomposition of ammonium perchlorate

    NASA Astrophysics Data System (ADS)

    Zhuo, Ji-Bin; Ma, Zai-He; Lin, Cai-Xia; Xie, Li-Li; Bai, Sha; Yuan, Yao-Feng

    2015-04-01

    Two pyrrolide-imine chelating Ni(II) complexes {[2-(2-CH3O-C6H4-NCH)C4H3N]2Ni (2a) and [(Fc-NCH)]C4H3N]2Ni (2b, Fc = ferrocenyl)} were prepared via treating corresponding Schiff base with 0.5 equiv. NiCl2·6H2O in moderate yields. The crystal structures of 2a and 2b were determined by single-crystal X-ray diffraction. Atom Ni(II) of 2a was coordinated by two pyrrolide-imine ligands in trans position to display a twisted octahedral coordination geometry. Ni(II) of 2b had a distorted square-planar geometry, bonded with two ferrocenyl pyrrole-imine ligands, each ferrocene and pyrrole of ligands adopting a trans conformation. The UV-vis spectroscopy and electrochemical measurements were investigated. The catalytic efficiency of the complexes on the thermal decomposition of ammonium perchlorate (AP) was studied by differential scanning calorimetry (DSC) and thermogravimetry (TG). Compared with the thermal decomposition of pure AP, the decomposition temperatures were decreased by 27 °C, 77 °C, 88 °C and 172 °C, respectively when 1a, 1b, 2a and 2b were added in AP. The results indicated that the Ni(II) complex 2b bearing ferrocene-based pyrrolide-imine N,N-chelate ligand displayed an excellent catalytic efficiency on the thermal decomposition of AP.

  20. An Efficient Approach for Pixel Decomposition to Increase the Spatial Resolution of Land Surface Temperature Images from MODIS Thermal Infrared Band Data

    PubMed Central

    Wang, Fei; Qin, Zhihao; Li, Wenjuan; Song, Caiying; Karnieli, Arnon; Zhao, Shuhe

    2015-01-01

    Land surface temperature (LST) images retrieved from the thermal infrared (TIR) band data of Moderate Resolution Imaging Spectroradiometer (MODIS) have much lower spatial resolution than the MODIS visible and near-infrared (VNIR) band data. The coarse pixel scale of MODIS LST images (1000 m under nadir) have limited their capability in applying to many studies required high spatial resolution in comparison of the MODIS VNIR band data with pixel scale of 250–500 m. In this paper we intend to develop an efficient approach for pixel decomposition to increase the spatial resolution of MODIS LST image using the VNIR band data as assistance. The unique feature of this approach is to maintain the thermal radiance of parent pixels in the MODIS LST image unchanged after they are decomposed into the sub-pixels in the resulted image. There are two important steps in the decomposition: initial temperature estimation and final temperature determination. Therefore the approach can be termed double-step pixel decomposition (DSPD). Both steps involve a series of procedures to achieve the final result of decomposed LST image, including classification of the surface patterns, establishment of LST change with normalized difference of vegetation index (NDVI) and building index (NDBI), reversion of LST into thermal radiance through Planck equation, and computation of weights for the sub-pixels of the resulted image. Since the Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) with much higher spatial resolution than MODIS data was on-board the same platform (Terra) as MODIS for Earth observation, an experiment had been done in the study to validate the accuracy and efficiency of our approach for pixel decomposition. The ASTER LST image was used as the reference to compare with the decomposed LST image. The result showed that the spatial distribution of the decomposed LST image was very similar to that of the ASTER LST image with a root mean square error (RMSE) of

  1. An efficient approach for pixel decomposition to increase the spatial resolution of land surface temperature images from MODIS thermal infrared band data.

    PubMed

    Wang, Fei; Qin, Zhihao; Li, Wenjuan; Song, Caiying; Karnieli, Arnon; Zhao, Shuhe

    2015-01-01

    Land surface temperature (LST) images retrieved from the thermal infrared (TIR) band data of Moderate Resolution Imaging Spectroradiometer (MODIS) have much lower spatial resolution than the MODIS visible and near-infrared (VNIR) band data. The coarse pixel scale of MODIS LST images (1000 m under nadir) have limited their capability in applying to many studies required high spatial resolution in comparison of the MODIS VNIR band data with pixel scale of 250-500 m. In this paper we intend to develop an efficient approach for pixel decomposition to increase the spatial resolution of MODIS LST image using the VNIR band data as assistance. The unique feature of this approach is to maintain the thermal radiance of parent pixels in the MODIS LST image unchanged after they are decomposed into the sub-pixels in the resulted image. There are two important steps in the decomposition: initial temperature estimation and final temperature determination. Therefore the approach can be termed double-step pixel decomposition (DSPD). Both steps involve a series of procedures to achieve the final result of decomposed LST image, including classification of the surface patterns, establishment of LST change with normalized difference of vegetation index (NDVI) and building index (NDBI), reversion of LST into thermal radiance through Planck equation, and computation of weights for the sub-pixels of the resulted image. Since the Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) with much higher spatial resolution than MODIS data was on-board the same platform (Terra) as MODIS for Earth observation, an experiment had been done in the study to validate the accuracy and efficiency of our approach for pixel decomposition. The ASTER LST image was used as the reference to compare with the decomposed LST image. The result showed that the spatial distribution of the decomposed LST image was very similar to that of the ASTER LST image with a root mean square error (RMSE) of 2

  2. Thermal decomposition of [Co(en)3][Fe(CN)6]∙ 2H2O: Topotactic dehydration process, valence and spin exchange mechanism elucidation

    PubMed Central

    2013-01-01

    Background The Prussian blue analogues represent well-known and extensively studied group of coordination species which has many remarkable applications due to their ion-exchange, electron transfer or magnetic properties. Among them, Co-Fe Prussian blue analogues have been extensively studied due to the photoinduced magnetization. Surprisingly, their suitability as precursors for solid-state synthesis of magnetic nanoparticles is almost unexplored. In this paper, the mechanism of thermal decomposition of [Co(en)3][Fe(CN)6] ∙∙ 2H2O (1a) is elucidated, including the topotactic dehydration, valence and spins exchange mechanisms suggestion and the formation of a mixture of CoFe2O4-Co3O4 (3:1) as final products of thermal degradation. Results The course of thermal decomposition of 1a in air atmosphere up to 600°C was monitored by TG/DSC techniques, 57Fe Mössbauer and IR spectroscopy. As first, the topotactic dehydration of 1a to the hemihydrate [Co(en)3][Fe(CN)6] ∙∙ 1/2H2O (1b) occurred with preserving the single-crystal character as was confirmed by the X-ray diffraction analysis. The consequent thermal decomposition proceeded in further four stages including intermediates varying in valence and spin states of both transition metal ions in their structures, i.e. [FeII(en)2(μ-NC)CoIII(CN)4], FeIII(NH2CH2CH3)2(μ-NC)2CoII(CN)3] and FeIII[CoII(CN)5], which were suggested mainly from 57Fe Mössbauer, IR spectral and elemental analyses data. Thermal decomposition was completed at 400°C when superparamagnetic phases of CoFe2O4 and Co3O4 in the molar ratio of 3:1 were formed. During further temperature increase (450 and 600°C), the ongoing crystallization process gave a new ferromagnetic phase attributed to the CoFe2O4-Co3O4 nanocomposite particles. Their formation was confirmed by XRD and TEM analyses. In-field (5 K / 5 T) Mössbauer spectrum revealed canting of Fe(III) spin in almost fully inverse spinel structure of CoFe2O4. Conclusions It has been found

  3. Online evolved gas analysis by Thermogravimetric-Mass Spectroscopy for thermal decomposition of biomass and its components under different atmospheres: part I. Lignin.

    PubMed

    Shen, Dekui; Hu, Jun; Xiao, Rui; Zhang, Huiyan; Li, Shefeng; Gu, Sai

    2013-02-01

    Thermogravimetric-Mass Spectroscopy (TG-MS) study on lignin decomposition under different (oxygen-containing) atmospheres was carried out to investigate thermal performance of lignin during pyrolysis, oxidative gasification, oxy/fuel combustion and CO(2) gasification. Only one significant mass loss stage was observed for lignin decomposition under helium (He), while another stage, representing char oxidation, appeared under oxygen and CO(2) conditions. No significant variation of the activation energy was presented for the first pyrolysis stage under different atmospheres (from 40.4 to 53.2kJ/mol). A much higher temperature was required for char oxidation under CO(2) than those under O(2) atmospheres, giving the activation energy of 541.9kJ/mol as compared to around 160kJ/mol for O(2)-containing atmospheres. The evolution profiles of CO and CO(2) under different atmospheres were in good accordance with the DTG curves regardless of atmospheres. PMID:23313692

  4. On photochemistry of water in solid Xe: Thermal and light-induced decomposition of HXeOH and HXeH and formation of H2O2

    NASA Astrophysics Data System (ADS)

    Khriachtchev, Leonid; Tanskanen, Hanna; Pettersson, Mika; Räsänen, Markku; Ahokas, Jussi; Kunttu, Henrik; Feldman, Vladimir

    2002-04-01

    A photochemical study of water (H2 16O, H2 18O, D2 16O, and D2 18O) in solid Xe is described. The water-Xe samples were irradiated at 193 nm and then annealed at 40-50 K, which led to formation of various isotopomers of Xe-containing molecules, HXeOH and HXeH. This diffusion-controlled formation of HXeH and HXeOH consumes the main part of hydrogen atoms generated in the matrix during photolysis. Both photodecomposition profiles and ultraviolet (UV) absorption spectra of HXeOH and HXeH feature a broad absorption band of these species around 240 nm corresponding to the transition to the repulsive excited states. It is also found that HXeOH and HXeH molecules can be thermally destroyed in similar time scales of ˜10 min at about 54 and 66 K, respectively. This clear difference between the decomposition temperatures for HXeOH and HXeH suggests the intrinsic basis of the decomposition process, which possibly occurs over the barriers of the bending coordinates. The absence of strong H-D isotope effect in this thermal decomposition indicates that tunneling of hydrogen is not essentially involved in the process at these temperatures. However, the local disorder of a Xe matrix seems to produce inhomogeneous broadening of the activation energies of the decomposition as indicated by the observed nonexponential decay kinetics. Upon photolysis and annealing of the H2O-Xe samples, monomeric and complexed hydrogen peroxide is formed originating, at least partially, from water clusters stabilized in solid Xe. In addition, we report the vibrational data on various isotopomers of HXeH, HXeOH, H2O, OH, and OH⋯H2O isolated in solid Xe.

  5. Thermal decomposition of specifically phosphorylated D-glucoses and their role in the control of the Maillard reaction.

    PubMed

    Yaylayan, Varoujan A; Machiels, David; Istasse, Louis

    2003-05-21

    One of the main shortcomings of the information available on the Maillard reaction is the lack of knowledge to control the different pathways, especially when it is desired to direct the reaction away from the formation of carcinogenic and other toxic substances to more aroma and color generation. The use of specifically phosphorylated sugars may impart some elements of control over the aroma profile generated by the Maillard reaction. Thermal decomposition of 1- and 6-phosphorylated glucoses was studied in the presence and absence of ammonia and selected amino acids through pyrolysis/gas chromatography/mass spectrometry using nonpolar PLOT and medium polar DB-1 columns. The analysis of the data has indicated that glucose-1-phosphate relative to glucose undergoes more extensive phosphate-catalyzed ring opening followed by formation of sugar-derived reactive intermediates as was indicated by a 9-fold increase in the amount of trimethylpyrazine and a 5-fold increase in the amount of 2,3-dimethylpyrazine, when pyrolyzed in the presence of glycine. In addition, glucose-1-phosphate alone generated a 6-fold excess of acetol as compared to glucose. On the other hand, glucose-6-phosphate enhanced retro-aldol reactions initiated from a C-6 hydroxyl group and increased the subsequent formation of furfural and 4-cyclopentene-1,3-dione. Furthermore, it also stabilized 1- and 3-deoxyglucosone intermediates and enhanced the formation of six carbon atom-containing Maillard products derived directly from them through elimination reactions such as 1,6-dimethyl-2,4-dihydroxy-3-(2H)-furanone (acetylformoin), 2-acetylpyrrole, 5-methylfurfural, 5-hydroxymethylfurfural, and 4-hydroxy-2,5-dimethyl-3-(2H)-furanone (Furaneol), due to the enhanced leaving group ability of the phosphate moiety at the C-6 carbon. However, Maillard products generated through the nucleophilic action of the C-6 hydroxyl group such as 2-acetylfuran and 2,3-dihydro-3,5-dihydroxy-4H-pyran-4-one were retarded, due

  6. Novel Composite Hydrogen-Permeable Membranes for Non-Thermal Plasma Reactors for the Decomposition of Hydrogen Sulfide

    SciTech Connect

    Morris D. Argyle; John F. Ackerman; Suresh Muknahallipatna; Jerry C. Hamann; Stanislaw Legowski; Guibing Zhao; Sanil John

    2006-09-30

    The goal of this experimental project is to design and fabricate a reactor and membrane test cell to dissociate hydrogen sulfide (H{sub 2}S) in a non-thermal plasma and recover hydrogen (H{sub 2}) through a superpermeable multi-layer membrane. Superpermeability of hydrogen atoms (H) has been reported by some researchers using membranes made of Group V transition metals (niobium, tantalum, vanadium, and their alloys), although it has yet to be confirmed in this study. Several pulsed corona discharge (PCD) reactors have been fabricated and used to dissociate H{sub 2}S into hydrogen and sulfur. Visual observation shows that the corona is not uniform throughout the reactor. The corona is stronger near the top of the reactor in argon, while nitrogen and mixtures of argon or nitrogen with H{sub 2}S produce stronger coronas near the bottom of the reactor. Both of these effects appear to be explainable base on the different electron collision interactions with monatomic versus polyatomic gases. A series of experiments varying reactor operating parameters, including discharge capacitance, pulse frequency, and discharge voltage were performed while maintaining constant power input to the reactor. At constant reactor power input, low capacitance, high pulse frequency, and high voltage operation appear to provide the highest conversion and the highest energy efficiency for H{sub 2}S decomposition. Reaction rates and energy efficiency per H{sub 2}S molecule increase with increasing flow rate, although overall H{sub 2}S conversion decreases at constant power input. Voltage and current waveform analysis is ongoing to determine the fundamental operating characteristics of the reactors. A metal infiltrated porous ceramic membrane was prepared using vanadium as the metal and an alumina tube. Experiments with this type of membrane are continuing, but the results thus far have been consistent with those obtained in previous project years: plasma driven permeation or superpermeability

  7. Kinetics of the Thermal Decomposition of Tetramethylsilane behind the Reflected Shock Waves in a Single Pulse Shock Tube (SPST) and Modeling Study

    NASA Astrophysics Data System (ADS)

    Parandaman, A.; Sudhakar, G.; Rajakumar, B.

    Thermal reactions of Tetramethylsilane (TMS) diluted in argon were studied behind the reflected shock waves in a single-pulse shock tube (SPST) over the temperature range of 1085-1221 K and pressures varied between 10.6 and 22.8 atm. The stable products resulting from the decomposition of TMS were identified and quantified using gas chromatography and also verified with Fourier Transform Infrared (FTIR) spectrometer. The major reaction products are methane (CH4) and ethylene (C2H4). The minor reaction products are ethane (C2H6) and propylene (C3H6). The initiation of mechanism in the decomposition of TMS takes plays via the Si-C bond scission by ejecting the methyl radicals (CH3) and trimethylsilyl radicals ((CH3)3Si). The measured temperature dependent rate coefficient for the total decomposition of TMS was to be ktotal = 1.66 ×1015 exp (-64.46/RT) s-1 and for the formation of CH4 reaction channel was to be k = 2.20 × 1014 exp (-60.15/RT) s-1, where the activation energies are given in kcal mol-1. A kinetic scheme containing 17 species and 28 elementary reactions was used for the simulation using chemical kinetic simulator over the temperature range of 1085-1221 K. The agreement between the experimental and simulated results was satisfactory.

  8. 48 CFR 14.503-2 - Step two.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 48 Federal Acquisition Regulations System 1 2010-10-01 2010-10-01 false Step two. 14.503-2 Section 14.503-2 Federal Acquisition Regulations System FEDERAL ACQUISITION REGULATION CONTRACTING METHODS AND CONTRACT TYPES SEALED BIDDING Two-Step Sealed Bidding 14.503-2 Step two. (a) Sealed...

  9. Thermal decomposition and reconstruction of CaFe-layered double hydroxide studied by X-ray diffractometry and 57Fe Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Bugris, Valéria; Ádok-Sipiczki, Mónika; Anitics, Tamás; Kuzmann, Ernő; Homonnay, Zoltán; Kukovecz, Ákos; Kónya, Zoltán; Sipos, Pál; Pálinkó, István

    2015-06-01

    In spite of numerous investigations on the various processes of the thermal decomposition and rehydration of layered double hydroxides (LDHs) by a variety sophisticated experimental means, many details are still unexplored and some contradictions are still unresolved. In this work, our efforts were focussed on clarifying the composition, structure and properties of thermally decomposed metaphases originating from CaFe-LDH, heat treated in the 373-973 K temperature range. The structure reconstruction ability of mixed metal oxide phases obtained after heat treatments was also investigated, mainly concentrating on the changes in the microenvironment of Fe(III), in the presence of controlled amount of water vapour (i.e., at different relative humidities). All samples were characterised by X-ray diffractometry, and the iron-containing phases were studied by 57Fe Mössbauer spectroscopy.

  10. Understanding the thermal decomposition mechanism of a halogen-free chelated orthoborate-based ionic liquid: a combined computational and experimental study.

    PubMed

    Golets, M; Shimpi, M R; Wang, Y-L; Antzutkin, O N; Glavatskih, S; Laaksonen, A

    2016-08-10

    In the last few decades, ionic liquids (ILs) have gained significant attention as lubricants and lubricant additives due to their polar nature, low vapour pressure and tunable physicochemical properties. In this work, quantum chemistry calculations and atomistic Molecular Dynamics (MD) simulations were employed to predict thermal degradation mechanisms of a potential lubricating agent - the tributyloctylphosphonium bis(oxalato)borate ([P4,4,4,8][BOB]) IL. It was found that the onset of decomposition of the studied IL coincides with a cleavage of the B-O bonds in the [BOB](-) anion. Consequently, a series of chemical reactions of the [P4,4,4,8](+) cation with the [BOB](-) anion was triggered yielding alkylboranes, alkenes, trialkylphosphines, CO and CO2. Another ionic system, consisting of [P4,4,4,8][Cl], was also tested for a comparison. Thermogravimetric measurements have shown a higher thermal stability of [P4,4,4,8][BOB] compared to that of [P4,4,4,8][Cl] at least at the initial stage of decomposition, in accord with the presented calculations. Quantum chemical frequency calculations also agreed with the experimental Fourier Transform Infrared (FTIR) spectroscopy results. PMID:27465515

  11. Preparation of Coaxial-Line and Hollow Mn2O3 Nanofibers by Single-Nozzle Electrospinning and Their Catalytic Performances for Thermal Decomposition of Ammonium Perchlorate.

    PubMed

    Liang, Jiyuan; Yang, Jie; Cao, Weiguo; Guo, Xiangke; Guo, Xuefeng; Ding, Weiping

    2015-09-01

    Coaxial-line and hollow Mn2O3 nanofibers have been synthesized by a simple single-nozzle electrospinning method without using a complicated coaxial jet head, combined with final calcination. The crystal structure and morphology of the Mn2O3 nanofibers were investigated by using the X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The results indicate that the electrospinning distance has important influence on the morphology and structure of the obtained Mn2O3 nanofibers, which changes from hollow fibers for short electrospinning distance to coaxial-line structure for long electrospinning distance after calcination in the air. The formation mechanisms of different structured Mn2O3 fibers are discussed in detail. This facile and effective method is easy to scale up and may be versatile for constructing coaxial-line and hollow fibers of other metal oxides. The catalytic activity of the obtained Mn2O3 nanofibers on thermal decomposition of ammonium perchlorate (AP) was studied by differential scanning calorimetry (DSC). The results show that the hollow Mn2O3 nanofibers have good catalytic activity to promote the thermal decomposition of AP. PMID:26716314

  12. Synthesis and characterization of Fe0.6Zn0.4Fe2O4 ferrite magnetic nanoclusters using simple thermal decomposition method

    NASA Astrophysics Data System (ADS)

    Sharifi, Ibrahim; Zamanian, Ali; Behnamghader, Aliasghar

    2016-08-01

    This paper presents experimental results regarding the effect of the quantity of solvent on formation of the Fe-Zn ferrite nanoparticles during thermal decomposition. A ternary system of Fe0.6Zn0.4Fe2O4 has been synthesized by a thermal decomposition method using metal acetylacetonate in high temperature boiling point solvent and oleic acid. The X-ray diffraction study was used to determine phase purity, crystal structure, and average crystallite size of iron-zinc ferrite nanoparticles. The average crystallite size of nanoparticles was increased from 13 nm to 37 nm as a result of reducing the solvent from 30 ml to 10 ml in a synthesis batch. The diameter of particles and morphology of the particles were determined by transmission electron microscopy (TEM) and field emission scanning electron microscope (FESEM). Mid and far Fourier transform infrared (FT-IR) measurement confirmed monophasic spinel structure of ferrite. Furthermore, the DC magnetic properties of the samples were studied using the vibrating sample magnetometer (VSM). The largest Fe-Zn ferrite nanoparticles exhibited a relatively high saturation magnetization of 96 emu/g. Moreover, Low-field AC susceptibility measurement indicated blocking temperature of nanoparticles around 170-200 K.

  13. A new precursor strategy to prepare ZnCo2O4 nanorods and their excellent catalytic activity for thermal decomposition of ammonium perchlorate

    NASA Astrophysics Data System (ADS)

    Jia, Zhigang; Ren, Daping; Wang, Qiuze; Zhu, Rongsun

    2013-04-01

    We present a new preparation of zinc cobaltite (ZnCo2O4) nanorods via a hydrothermal-annealing method. Zinc cobalt oxalate (ZnCo2(C2O4)3·6H2O) nanorods as the precursor have been firstly synthesized by solvothermal method at 120 °C using the mixed solvents as the reaction medium without the assistance of soft/hard template. It is found that the mixed solvent plays an important role for zinc cobalt oxalate precursor nanorods and 1D growth of zinc cobalt oxalate precursor is gradually improved with the increasing ethylene glycol (EG) in the mixed solvent. The as-prepared zinc cobalt oxalate precursor (ZnCo2(C2O4)3·6H2O) nanorods can convert to 1D zinc cobaltite (ZnCo2O4) nanostructures while maintaining original frame structure. The obtained samples are characterized by means of XRD, SEM, TEM and HRTEM. Furthermore, the effect of zinc cobaltite (ZnCo2O4) nanostructures on the thermal decomposition of ammonium perchlorate (AP) is investigated by differential thermal analysis (DTA). The results show that the addition of zinc cobaltite (ZnCo2O4) nanorods to AP remarkably decreases the decomposition temperature. The as-prepared zinc cobaltite (ZnCo2O4) nanorods are promising as a high-performing ballistic modifier in AP-based composite solid rocket propellants.

  14. Optimal Thermolysis Conditions for Soil Carbon Storage on Plant Residue Burning: Modeling the Trade-Off between Thermal Decomposition and Subsequent Biodegradation.

    PubMed

    Kajiura, Masako; Wagai, Rota; Hayashi, Kentaro

    2015-01-01

    Field burning of plant biomass is a widespread practice that provides charred materials to soils. Its impact on soil C sequestration remains unclear due to the heterogeneity of burning products and difficulty in monitoring the material's biodegradation in fields. Basic information is needed on the relationship between burning conditions and the resulting quantity/quality of residue-derived C altered by thermal decomposition and biodegradation. In this study, we thermolyzed residues (rice straw and husk) at different temperatures (200-600°C) under two oxygen availability conditions and measured thermal mass loss, C compositional change by solid-state C NMR spectroscopy, and biodegradability of the thermally altered residues by laboratory aerobic incubation. A trade-off existed between thermal and microbial decomposition: when burned at higher temperatures, residues experience a greater mass loss but become more recalcitrant via carbonization. When an empirical model accounting for the observed trade-off was projected over 10 to 10 yr, we identified the threshold temperature range (330-400°C) above and below which remaining residue C is strongly reduced. This temperature range corresponded to the major loss of O-alkyl C and increase in aromatic C. The O/C molar ratios of the resultant residues decreased to 0.2 to 0.4, comparable to those of chars in fire-prone field soils reported previously. Although the negative impacts of biomass burning need to be accounted for, the observed relationship may help to assess the long-term fate of burning-derived C and to enhance soil C sequestration. PMID:25602338

  15. Thermal decomposition of 1,3,3-trinitroazetidine (TNAZ): A density functional theory and ab initio study

    SciTech Connect

    Veals, Jeffrey D.; Thompson, Donald L.

    2014-04-21

    Density functional theory and ab initio methods are employed to investigate decomposition pathways of 1,3,3-trinitroazetidine initiated by unimolecular loss of NO{sub 2} or HONO. Geometry optimizations are performed using M06/cc-pVTZ and coupled-cluster (CC) theory with single, double, and perturbative triple excitations, CCSD(T), is used to calculate accurate single-point energies for those geometries. The CCSD(T)/cc-pVTZ energies for NO{sub 2} elimination by N–N and C–N bond fission are, including zero-point energy (ZPE) corrections, 43.21 kcal/mol and 50.46 kcal/mol, respectively. The decomposition initiated by trans-HONO elimination can occur by a concerted H-atom and nitramine NO{sub 2} group elimination or by a concerted H-atom and nitroalkyl NO{sub 2} group elimination via barriers (at the CCSD(T)/cc-pVTZ level with ZPE corrections) of 47.00 kcal/mol and 48.27 kcal/mol, respectively. Thus, at the CCSD(T)/cc-pVTZ level, the ordering of these four decomposition steps from energetically most favored to least favored is: NO{sub 2} elimination by N–N bond fission, HONO elimination involving the nitramine NO{sub 2} group, HONO elimination involving a nitroalkyl NO{sub 2} group, and finally NO{sub 2} elimination by C–N bond fission.

  16. Decomposition of atrazine traces in water by combination of non-thermal electrical discharge and adsorption on nanofiber membrane.

    PubMed

    Vanraes, Patrick; Willems, Gert; Daels, Nele; Van Hulle, Stijn W H; De Clerck, Karen; Surmont, Pieter; Lynen, Frederic; Vandamme, Jeroen; Van Durme, Jim; Nikiforov, Anton; Leys, Christophe

    2015-04-01

    In recent decades, several types of persistent substances are detected in the aquatic environment at very low concentrations. Unfortunately, conventional water treatment processes are not able to remove these micropollutants. As such, advanced treatment methods are required to meet both current and anticipated maximally allowed concentrations. Plasma discharge in contact with water is a promising new technology, since it produces a wide spectrum of oxidizing species. In this study, a new type of reactor is tested, in which decomposition by atmospheric pulsed direct barrier discharge (pDBD) plasma is combined with micropollutant adsorption on a nanofiber polyamide membrane. Atrazine is chosen as model micropollutant with an initial concentration of 30 μg/L. While the H2O2 and O3 production in the reactor is not influenced by the presence of the membrane, there is a significant increase in atrazine decomposition when the membrane is added. With membrane, 85% atrazine removal can be obtained in comparison to only 61% removal without membrane, at the same experimental parameters. The by-products of atrazine decomposition identified by HPLC-MS are deethylatrazine and ammelide. Formation of these by-products is more pronounced when the membrane is added. These results indicate the synergetic effect of plasma discharge and pollutant adsorption, which is attractive for future applications of water treatment. PMID:25482844

  17. Combustion of Organic Molecules by the Thermal Decomposition of Perchlorate Salts: Implications for Organics at the Mars Phoenix Scout Landing Site

    NASA Technical Reports Server (NTRS)

    Ming, D.W.; Morris, R.V.; Niles, B.; Lauer, H.V.; Archer, P.D.; Sutter, B.; Boynton, W.V.; Golden, D.C.

    2009-01-01

    The Mars 2007 Phoenix Scout Mission successfully landed on May 25, 2008 and operated on the northern plains of Mars for 150 sols. The primary mission objective was to study the history of water and evaluate the potential for past and present habitability in Martian arctic ice-rich soil [1]. Phoenix landed near 68 N latitude on polygonal terrain created by ice layers that are a few centimeters under loose soil materials. The Phoenix Mission is assessing the potential for habitability by searching for organic molecules in the ice or icy soils at the landing site. Organic molecules are necessary building blocks for life, although their presence in the ice or soil does not indicate life itself. Phoenix searched for organic molecules by heating soil/ice samples in the Thermal and Evolved-Gas Analyzer (TEGA, [2]). TEGA consists of 8 differential scanning calorimeter (DSC) ovens integrated with a magnetic-sector mass spectrometer with a mass range of 2-140 daltons [2]. Endothermic and exothermic reactions are recorded by the TEGA DSC as samples are heated from ambient to 1000 C. Evolved gases, including any organic molecules and their fragments, are simultaneously measured by the mass spectrometer during heating. Phoenix TEGA data are still under analysis; however, no organic fragments have been identified to date in the evolved gas analysis (EGA). The MECA Wet Chemistry Lab (WCL) discovered a perchlorate salt in the Phoenix soils and a mass 32 peak evolved between 325 and 625 C for one surface sample dubbed Baby Bear [3]. The mass 32 peak is attributed to evolved O2 generated during the thermal decomposition of the perchlorate salt. Perchlorates are very strong oxidizers when heated, so it is possible that organic fragments evolved in the temperature range of 300-600 C were combusted by the O2 released during the thermal decomposition of the perchlorate salt. The byproduct of the combustion of organic molecules is CO2. There is a prominent release of CO2 between 200

  18. Thermal image enhancement using bi-dimensional empirical mode decomposition in combination with relevance vector machine for rotating machinery fault diagnosis

    NASA Astrophysics Data System (ADS)

    Tran, Van Tung; Yang, Bo-Suk; Gu, Fengshou; Ball, Andrew

    2013-07-01

    In this study, a novel fault diagnosis system for rotating machinery using thermal imaging is proposed. This system consists of bi-dimensional empirical mode decomposition (BEMD) for image enhancement, a generalized discriminant analysis (GDA) for feature reduction, and a relevance vector machine (RVM) for fault classification. Firstly, the thermal image obtained from machine conditions is decomposed into intrinsic mode functions (IMFs) by using BEMD. At each decomposed level, the IMF is expanded and fused with the residue by gray-scale transformation and principal component analysis fusion technique, respectively. The enhanced image is then formed by the improved IMFs in reconstruction process. Subsequently, feature extraction is applied for the enhanced images to obtain histogram features which characterize the thermal image and contain useful information for diagnosis. The high dimensionality of the achieved feature set can be reduced by GDA implementation. Moreover, GDA also assists in the increase of the feature cluster separation. Finally, the diagnostic results are performed by RVM. The proposed system is applied and validated with the thermal images of a fault simulator. A comparative study of the classification results obtained from RVM, support vector machines, and adaptive neuro-fuzzy inference system is also performed to appraise the accuracy of these models. The results show that the proposed diagnosis system is capable of improving the classification accuracy and efficiently assisting in rotating machinery fault diagnosis.

  19. Perfluoropolyalkylether decomposition on catalytic aluminas

    NASA Technical Reports Server (NTRS)

    Morales, Wilfredo

    1994-01-01

    The decomposition of Fomblin Z25, a commercial perfluoropolyalkylether liquid lubricant, was studied using the Penn State Micro-oxidation Test, and a thermal gravimetric/differential scanning calorimetry unit. The micro-oxidation test was conducted using 440C stainless steel and pure iron metal catalyst specimens, whereas the thermal gravimetric/differential scanning calorimetry tests were conducted using catalytic alumina pellets. Analysis of the thermal data, high pressure liquid chromatography data, and x-ray photoelectron spectroscopy data support evidence that there are two different decomposition mechanisms for Fomblin Z25, and that reductive sites on the catalytic surfaces are responsible for the decomposition of Fomblin Z25.

  20. Semi-empirical method for calculating the activation energies of the unimolecular thermal decomposition of vinyl ethers

    NASA Astrophysics Data System (ADS)

    Sargsyan, G. N.; Shakhrokh, B.; Harutyunyan, A. B.

    2015-02-01

    A semi-empirical method is proposed for calculating the activation energy of the unimolecular decomposition of complex compounds using the example of vinyl (ethyl, propyl, and butyl) ethers. The method is based on the concept of the formation of intramolecular hydrogen bonds and the possibility of calculating the energy of deformation of ether molecules upon activation, resulting in the potential surface of the transition state undergoing distortion and the transfer of a hydrogen atom from an alkyl group to a vinyl group. The energy of deformation is calculated using the Mathcad 2001i and MM2 computer programs.

  1. Mass-dependent and Mass-independent Sulphur Isotope Fractionation Accompanying Thermal- and Photo-chemical Decomposition of Sulphur Bearing Organic Compounds

    NASA Astrophysics Data System (ADS)

    Oduro, Harry; Izon, Gareth; Ono, Shuhei

    2014-05-01

    The bimodal S-isotope record, specifically the transition from mass independent (MIF) to mass dependent fractionation (MDF), is perhaps the most widely cited line of evidence for an irreversible rise in atmospheric oxygen at ca. 2.4Ga. The production and preservation of S-MIF, manifested in both Δ33S and Δ36S, within the geological record are linked to atmospheric O2 via a number of arguments. However, to date, the only mechanism capable of generating S-MIF consistent with the Archaean sedimentary records involves gas-phase ultraviolet irradiation of SO21 photolysis. More recently, Δ33S S-MIF trends have been reported from en vitro thermochemical sulphate reduction (TSR) experiments, prompting authors to question the importance of S-MIF as a proxy for Earth oxidation2. Importantly, whilst emerging TSR experiments3,4 affirm the reported Δ33S trends2, these experiments fail to identify correlated S-MIF between Δ33S and Δ36S values3,4. Realization that S-MIF is confined to Δ33S during TSR, precludes TSR as a mechanism responsible for the origin of the Archaean S-MIF record but strongly suggests the effect originating from a magnetic isotope effect (MIE) associated with 33S nucleus3,4. Clearly, photochemical and thermochemical processes impart different Δ36S/Δ33S trends with significant variation in δ34S; however, a complete experimental elucidation of mechanisms responsible for the S-MIF and S-MIE signatures is lacking. Interestingly, a complete understanding of the S-isotope chemistry during thermal- and photo-chemical decomposition may reveal wavelength and thermal dependence archived in the sedimentary record. Here we extend the experimental database to explore the magnitude and sign of Δ36S/Δ33S and δ34S produced during both photo- and thermochemical processes. Here the organic sulphur compounds (OSC) utilized in these experiments carries diagnostic Δ36S/Δ33S patterns that differ from those reported from photolysis experiment SO2 and from the

  2. High temperature shock tube studies on the thermal decomposition of O3 and the reaction of dimethyl carbonate with O-atoms.

    PubMed

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

    2013-05-01

    The shock tube technique was used to study the thermal decomposition of ozone, O3, with a view to using this as a thermal precursor of O-atoms at high temperatures. The formation of O-atoms was measured behind reflected shock waves by using atomic resonance absorption spectrometry (ARAS). The experiments span a T-range, 819 K ≤ T ≤ 1166 K, at pressures 0.13 bar ≤ P ≤ 0.6 bar. Unimolecular rate theory provides an excellent representation of the falloff characteristics from the present and literature data on ozone decomposition at high temperatures. The present decomposition study on ozone permits its usage as a thermal source for O-atoms allowing measurements for, O + CH3OC(O)OCH3 → OH + CH3OC(O)OCH2 [A]. Reflected shock tube experiments monitoring the formation and decay of O-atoms were performed on reaction A using mixtures of O3 and CH3OC(O)OCH3, (DMC), in Kr bath gas over the T-range, 862 K ≤ T ≤ 1167 K, and pressure range, 0.15 bar ≤ P ≤ 0.33 bar. A detailed model was used to fit the O-atom temporal profile to obtain experimental rate constants for reaction A. Rate constants from the present experiments for O + DMC can be represented by the Arrhenius expression: kA(T) = 2.70 × 10(-11) exp(-2725 K/T) cm(3) molecule(-1) s(-1) (862-1167 K). Transition state theory calculations employing CCSD(T)/cc-pv∞z//M06-2X/cc-pvtz energetics and molecular properties for reaction A are in good agreement with the experimental rate constants. The theoretical rate constants can be well represented (to within ±10%) over the 500-2000 K temperature range by: kA(T) = 1.87 × 10(-20)T(2.924) exp(-2338 K/T) cm(3) molecule(-1) s(-1). The present study represents the first experimental measurement and theoretical study on this bimolecular reaction which is of relevance to the high temperature oxidation of DMC. PMID:23510082

  3. A general method for preparing lanthanide oxide nanoparticles via thermal decomposition of lanthanide(III) complexes with 1-hydroxy-2-naphthoic acid and hydrazine ligands

    NASA Astrophysics Data System (ADS)

    Parimalagandhi, Karuppannan; Premkumar, Thathan; Vairam, Sundararajan

    2016-09-01

    Six new lanthanide(III) complexes (i.e., [Ln(L)2(NA)1.5]·3H2O, where Ln=La(III), Pr(III), Nd(III), Sm(III), Gd(III), and Ce(III) and L and NA indicate N2H4 and C10H6(1-O)(2-COO), respectively) with 1-hydroxy-2-naphthoic acid [C10H6(1-O)(2-COOH)] and hydrazine (N2H4) as co-ligands were characterized by elemental, FTIR, UV-visible, and XRD techniques. In the FT-IR spectra, the N-N stretching frequency in the range of 981-949 cm-1 demonstrates evidence of the presence of coordinated N2H4, indicating the bidentate bridging nature of hydrazine in the complexes. These complexes show symmetric and asymmetric COO- stretching from 1444 to 1441 cm-1 and 1582 to 1557 cm-1, respectively, indicating bidentate coordination. TG-DTA studies revealed that the compounds underwent endothermic dehydration from 98 to 110 °C. This was followed by the exothermic decomposition of oxalate intermediates to yield the respective metal oxides as the end products. From SEM images, the average size of the metal oxide particles prepared by thermal decomposition of the complexes was determined to be 39-42 nm. The powder X-ray and SEM coupled with energy dispersive X-ray (EDX) studies revealed the presence of the respective nano-sized metal oxides. The kinetic parameters of the decomposition of the complexes were calculated using the Coats-Redfern equation.

  4. Synthesis and characterization of ZnO and Ni doped ZnO nanorods by thermal decomposition method for spintronics application

    SciTech Connect

    Saravanan, R.; Santhi, Kalavathy; Sivakumar, N.; Narayanan, V.; Stephen, A.

    2012-05-15

    Zinc oxide nanorods and diluted magnetic semiconducting Ni doped ZnO nanorods were prepared by thermal decomposition method. This method is simple and cost effective. The decomposition temperature of acetate and formation of oxide were determined by TGA before the actual synthesis process. The X-ray diffraction result indicates the single phase hexagonal structure of zinc oxide. The transmission electron microscopy and scanning electron microscopy images show rod like structure of ZnO and Ni doped ZnO samples with the diameter {approx} 35 nm and the length in few micrometers. The surface analysis was performed using X-ray photoelectron spectroscopic studies. The Ni doped ZnO exhibits room temperature ferromagnetism. This diluted magnetic semiconducting Ni doped ZnO nanorods finds its application in spintronics. - Highlights: Black-Right-Pointing-Pointer The method used is very simple and cost effective compared to all other methods for the preparation DMS materials. Black-Right-Pointing-Pointer ZnO and Ni doped ZnO nanorods Black-Right-Pointing-Pointer Ferromagnetism at room temperature.

  5. Complex transition metal hydrides incorporating ionic hydrogen: thermal decomposition pathway of Na2Mg2FeH8 and Na2Mg2RuH8.

    PubMed

    Humphries, Terry D; Matsuo, Motoaki; Li, Guanqiao; Orimo, Shin-Ichi

    2015-03-28

    Complex transition metal hydrides have potential technological application as hydrogen storage materials, smart windows and sensors. Recent exploration of these materials has revealed that the incorporation of anionic hydrogen into these systems expands the potential number of viable complexes, while varying the countercation allows for optimisation of their thermodynamic stability. In this study, the optimised synthesis of Na2Mg2TH8 (T = Fe, Ru) has been achieved and their thermal decomposition properties studied by ex situ Powder X-ray Diffraction, Gas Chromatography and Pressure-Composition Isotherm measurements. The temperature and pathway of decomposition of these isostructural compounds differs considerably, with Na2Mg2FeH8 proceeding via NaMgH3 in a three-step process, while Na2Mg2RuH8 decomposes via Mg2RuH4 in a two-step process. The first desorption maxima of Na2Mg2FeH8 occurs at ca. 400 °C, while Na2Mg2RuH8 has its first maxima at 420 °C. The enthalpy and entropy of desorption for Na2Mg2TH8 (T = Fe, Ru) has been established by PCI measurements, with the ΔHdes for Na2Mg2FeH8 being 94.5 kJ mol(-1) H2 and 125 kJ mol(-1) H2 for Na2Mg2RuH8. PMID:25732233

  6. Ion chromatography electrospray ionization mass spectrometry method development and investigation of lithium hexafluorophosphate-based organic electrolytes and their thermal decomposition products.

    PubMed

    Kraft, Vadim; Grützke, Martin; Weber, Waldemar; Winter, Martin; Nowak, Sascha

    2014-08-01

    A method based on the coupling of ion chromatography (IC) and electrospray ionization mass spectrometry (ESI-MS) for the separation and determination of thermal decomposition products of LiPF6-based organic electrolytes is presented. The utilized electrolytes, LP30 and LP50, are commercially available and consist of 1mol/l LiPF6 dissolved in ethylene carbonate/dimethyl carbonate and ethylene carbonate/ethyl methyl carbonate, respectively. For the separation method development three ion chromatographic columns with different capacity and stationary phase were used and compared. Besides the known hydrolysis products of lithium hexafluorophosphate, several new organophosphates were separated and identified with the developed IC-ESI-MS method during aging investigations of the electrolytes. The chemical structures were elucidated with IC-ESI-MS/MS. PMID:24939088

  7. Cu2Te Synthesis and In-Vacuum Thermal Decomposition: Chemical-Kinetics Analysis and Comparison to Equilibrium Vapor-Pressure Measurements

    SciTech Connect

    Teeter, G.

    2007-01-01

    In this study, polycrystalline Cu-foil substrates are exposed to elemental Te vapor at substrate temperatures below 373 K. Auger electron spectroscopy measurements indicate that copper-telluride films are formed at the substrate surface that have a 2:1 Cu-to-Te ratio, as predicted by the Cu--Te phase diagram. When these films are annealed above about 700 K in vacuum, Te desorbs from the substrate with zero-order kinetics. An analysis of Te-desorption traces that assumes the reaction Cu{sub 2}Te(s) {yields} 2Cu(s) + {alpha}Te(?) + 1/2(1 - {alpha})Te2({nu}) finds a thermal-decomposition activation energy of 217 {+-} 3 kJ mol{sup -1}. These Te-desorption data are compared to the Te impingement rate calculated from Cu{sub 2}Te equilibrium vapor-pressure data from the literature and found to be in excellent agreement.

  8. Thermal decomposition assisted synthesis and upconversion property of Fe3O4@YPO4:Tm/Yb hybrid nano-composite phosphor

    NASA Astrophysics Data System (ADS)

    Tiwari, S. P.; Kumar, K.; Rai, V. K.

    2015-06-01

    Hybrid nano-composite phosphor has been successfully synthesized through thermal decomposition method. The dual phase of samples assigned by XRD analysis shows the formation of nano-composite with crystallite size 20 nm and 12 nm for YPO4: Tm/Yb and Fe3O4@YPO4:Tm/Yb respectively. The FESEM images show the spherical shape and non agglomerated formation of nanoparticles. Three bands in upconversion emission mode were found in intense blue at 472 nm, red at 662 nm and NIR at 798 nm regions corresponding to1G4 → 3H6, 1G4 → 3F4 and 3H4 → 3H6 transition states respectively. The lifetime for1G4 → 3H6 level is found 1150 microsecond and 1400 microsecond for YPO4: Tm/Yb and Fe3O4@YPO4:Tm/Yb samples respectively.

  9. Improved microstructure and performance of PbS thin films via in-situ thermal decomposition of lead xanthate precursors using self-assembling monolayer

    NASA Astrophysics Data System (ADS)

    Wang, Jingni; Yao, Kai; Jia, Zhenrong; Wang, Xiaofeng; Li, Fan

    2016-09-01

    Microstructure control is critical to achieve thin film-based devices with high performance. The surface properties of the substrates on which thin films grow are expected to greatly influence the morphology and the resulting performance. Generally, homogeneous, dense and highly crystalline films are required. However, "island" like structures are usually obtained mainly due to the non-uniform nucleation. In this article, the self-assembling monolayer (SAM) strategy was applied to efficiently realize the uniform nucleation and modulate the microstructure of lead sulfide (PbS) thin films, which were fabricated on the modified ZnO-coated substrates with 3-mercaptopropionic acid (MPA) SAM via in-situ thermal decomposition of lead xanthate precursors. The results showed that PbS thin films with reduced pin-holes and uniform crystalline grains were fabricated with the incorporation of MPA SAM. More importantly, PbS thin films modulated by MPA showed better photoelectric response.

  10. Synthesis of copper micro-rods with layered nano-structure by thermal decomposition of the coordination complex Cu(BTA)2.

    PubMed

    Qu, Botao; Lu, Xinrong; Wu, Yan; You, Xiaozeng; Xu, Xiangxing

    2015-01-01

    Porous metallic copper was successfully prepared by a simple thermal decomposition strategy. A coordination compound of Cu(BTA)2 with the morphology of micro-rod crystal was synthesized as the precursor. The precursor to copper transformation was performed and annealed at 600°C with the shape preserved. The copper micro-rods are assembled from unique thin lamellar layers, each with the thickness of approximately 200 nm and nano-pores of approximately 20 to 100 nm. This morphology is highly related to the crystal structure of the precursor. The mechanism of the morphology formation is proposed, which would be able to offer a guideline toward porous metals with controllable macro/micro/nano-structures by the precursor crystal growth and design. PMID:25852339

  11. Meso/macroporous {gamma}-Al{sub 2}O{sub 3} fabricated by thermal decomposition of nanorods ammonium aluminium carbonate hydroxide

    SciTech Connect

    Li, Guang-Ci; Liu, Yun-Qi; Guan, Li-Li; Hu, Xiao-Fu; Liu, Chen-Guang

    2012-04-15

    Highlights: Black-Right-Pointing-Pointer Rod-like AACH were synthesized by a hydrothermal treatment. Black-Right-Pointing-Pointer AACH was formed via a Al(OH){sub 3} {yields} (NH{sub 4}){sub 2}Al{sub 6}(CO{sub 3}){sub 3}(OH){sub 14}{center_dot}xH{sub 2}O {yields} NH{sub 4}Al(OH){sub 2}CO{sub 3}{center_dot}H{sub 2}O {yields} NH{sub 4}Al(OH){sub 2}CO{sub 3} path. Black-Right-Pointing-Pointer Alumina derived from AACH has a good thermal stability. Black-Right-Pointing-Pointer The obtained alumina possesses large pore volume and bimodal porosity. -- Abstract: Through exploring the reaction parameters during the synthesis of the AACH, rod-like ammonium aluminium carbonate hydroxide (AACH) with high crystallinity has been successfully prepared via a facile hydrothermal method. The synthesis parameters like time, the molar ratio of NH{sub 4}HCO{sub 3}/Al and the properties of starting materials were systematically investigated. The structure was characterized using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), IR and transmission electron microscopy (TEM). The experimental results display that the obtained {gamma}-Al{sub 2}O{sub 3} materials possess meso/macroporosity and large pore volume, which are mainly attributed to the removal of gas molecules during the decomposition of AACH. Moreover, using the rod-like AACH as precursor, {gamma}-Al{sub 2}O{sub 3} nanorods were obtained via a low-temperature thermal decomposition method.

  12. Synthesis, crystal structure and catalytic effect on thermal decomposition of RDX and AP: An energetic coordination polymer [Pb2(C5H3N5O5)2(NMP)·NMP]n

    NASA Astrophysics Data System (ADS)

    Liu, Jin-jian; Liu, Zu-Liang; Cheng, Jian; Fang, Dong

    2013-04-01

    An energetic lead(II) coordination polymer based on the ligand ANPyO has been synthesized and its crystal structure has been got. The polymer was characterized by FT-IR spectroscopy, elemental analysis, DSC and TG-DTG technologies. Thermal analysis shows that there are one endothermic process and two exothermic decomposition stages in the temperature range of 50-600 °C with final residues 57.09%. The non-isothermal kinetic has also been studied on the main exothermic decomposition using the Kissinger's and Ozawa-Doyle's methods, the apparent activation energy is calculated as 195.2 KJ/mol. Furthermore, DSC measurements show that the polymer has significant catalytic effect on the thermal decomposition of ammonium perchlorate.

  13. NTO decomposition studies

    SciTech Connect

    Oxley, J.C.; Smith, J.L.; Yeager, K.E.; Rogers, E.; Dong, X.X.

    1996-07-01

    To examine the thermal decomposition of 5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one (NTO) in detail, isotopic labeling studies were undertaken. NTO samples labeled with {sup 15}N in three different locations [N(1) and N(2), N(4), and N(6)] were prepared. Upon thermolysis, the majority of the NTO condensed-phase product was a brown, insoluble residue, but small quantities of 2,4-dihydro-3H-1,2,4-triazol-3-one (TO) and triazole were detected. Gases comprised the remainder of the NTO decomposition products. The analysis of these gases is reported along with mechanistic implications of these observations.

  14. Decomposition of ammonia and hydrogen sulfide in simulated sludge drying waste gas by a novel non-thermal plasma.

    PubMed

    Lu, Shengyong; Chen, Lu; Huang, Qunxing; Yang, Liqin; Du, Changming; Li, Xiaodong; Yan, Jianhua

    2014-12-01

    To efficiently clean NH3 and H2S contained in municipal sewage sludge drying waste gas, experiments were conducted with a novel gliding arc discharge plasma reactor. Important parameters including applied voltage and gas velocity which can strongly influence the removal efficiency, energy cost and by-products yields were investigated. Maximum removal efficiencies were all obtained at the applied voltage of 11 kV and gas velocity of 4.72 m s−1. When NH3 and H2S were treated together, the total energy cost decreased by 38%. NO and SO2 were observed as main decomposition by-products, and the presence of NH3 may inhibit the production of SO2 whose yield decreased from 223.8 to 27.8 mg m−3. Tests performed on lab scale reactor showed that gliding arc discharge is efficient in decreasing the NH3 and H2S concentrations, and experiments will also be conducted on a larger scale reactor in the future. PMID:25461948

  15. The evolution of solid density within a thermal explosion. I. Proton radiography of pre-ignition expansion, material motion, and chemical decomposition

    NASA Astrophysics Data System (ADS)

    Smilowitz, L.; Henson, B. F.; Romero, J. J.; Asay, B. W.; Saunders, A.; Merrill, F. E.; Morris, C. L.; Kwiatkowski, K.; Grim, G.; Mariam, F.; Schwartz, C. L.; Hogan, G.; Nedrow, P.; Murray, M. M.; Thompson, T. N.; Espinoza, C.; Lewis, D.; Bainbridge, J.; McNeil, W.; Rightley, P.; Marr-Lyon, M.

    2012-05-01

    We report proton transmission images obtained during direct heating of a sample of PBX 9501 (a plastic bonded formulation of the explosive nitramine octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX)) prior to the ignition of a thermal explosion. We describe the application of proton radiography using the 800 MeV proton accelerator at Los Alamos National Laboratory to obtain transmission images in these thermal explosion experiments. We have obtained images at two spatial magnifications and viewing both the radial and the transverse axes of a solid cylindrical sample encased in aluminum. During heating we observe the slow evolution of proton transmission through the samples, with particular detail during material flow associated with the HMX β-δ phase transition. We also directly observe the loss of solid density to decomposition associated with elevated temperatures in the volume defining the ignition location in these experiments. We measure a diameter associated with this volume of 1-2 mm, in agreement with previous estimations of the diameter using spatially resolved fast thermocouples.

  16. Structural determination; vibration study and thermal decomposition of [C5H6N5]2SeO4ṡ2H2O

    NASA Astrophysics Data System (ADS)

    Ben Hassen, C.; Boujelbene, M.; Mhiri, T.

    2015-01-01

    The present paper reports the chemical synthesis, structure study, thermal analysis, and vibrational properties of new hybrid compound called: bis (adeninium) selenate bihydrates. It is crystallized in the triclinic system with P-1 space group and the following parameters a = 7.804(5) Å; b = 9.686 (5) Å; c = 11.771 (5) Å; α = 84.421(5)°; ß = 77.556(5)°; γ = 81.186 (5)°; Z = 2 and V = 856.7(8) Å3. The structure is built up from tunnels containing all the components of the structure and following to the c axis, linked via three types of hydrogen bonds (Nsbnd H…O, Nsbnd H…N and Osbnd H…O). The thermal decomposition of precursors studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), indicate the existence of two mass loss region correspond to dehydration and degradation of the title compound, respectively. The existence of vibrational modes correspond to the organic and inorganic groups and water molecular are identified by the IR and Raman spectroscopy in the frequency ranges 400-4000 and 300-1600 cm-1, respectively.

  17. Structural and optical properties of thermal decomposition assisted Gd2O3:Ho(3+)/Yb(3+) upconversion phosphor annealed at different temperatures.

    PubMed

    Kumar, A; Tiwari, S P; Kumar, K; Rai, V K

    2016-10-01

    The infrared to visible upconversion fluorescent nanoparticles of Ho(3+)/Yb(3+) codoped Gd2O3 phosphor is synthesized via thermal decomposition route. The as-synthesized sample was annealed at 800, 1000 and 1200°C for 3h and then structural and optical properties were studied. The Rietveld refinement of X-ray diffraction (XRD) data was analyzed to probe the effect of Ho(3+)/Yb(3+) dopant on the structural parameters of Gd2O3 host. The upconversion emission spectra of as-synthesized and annealed samples are compared using 980nm diode laser excitation and five emission bands noticed at 490, 539, 550, 667 and 757nm corresponding to the (5)F3→(5)I8, (5)F4→(5)I8, (5)S2→(5)I8,(5)F5→(5)I8 and (5)I4→(5)I8 manifolds, respectively. The local temperature induced by laser light is also calculated. The fluorescence intensity ratio (FIR) of two thermally coupled transitions (5)F4→(5)I8 and (5)S2→(5)I8 is plotted against the sample temperature and sensor sensitivity of sample is calculated. PMID:27284763

  18. An ordered bcc CuPd nanoalloy synthesised via the thermal decomposition of Pd nanoparticles covered with a metal-organic framework under hydrogen gas.

    PubMed

    Li, Guangqin; Kobayashi, Hirokazu; Kusada, Kohei; Taylor, Jared M; Kubota, Yoshiki; Kato, Kenichi; Takata, Masaki; Yamamoto, Tomokazu; Matsumura, Syo; Kitagawa, Hiroshi

    2014-11-18

    Presented here is the synthesis of an ordered bcc copper-palladium nanoalloy, via the decomposition of a Pd nanoparticle@metal-organic framework composite material. In situ XRD measurements were performed in order to understand the mechanism of the decomposition process. This result gives a further perspective into the synthesis of new nanomaterials via metal-organic framework decomposition. PMID:25251225

  19. Rate constants for the thermal decomposition of ethanol and its bimolecular reactions with OH and D: reflected shock tube and theoretical studies.

    PubMed

    Sivaramakrishnan, R; Su, M-C; Michael, J V; Klippenstein, S J; Harding, L B; Ruscic, B

    2010-09-01

    The thermal decomposition of ethanol and its reactions with OH and D have been studied with both shock tube experiments and ab initio transition state theory-based master equation calculations. Dissociation rate constants for ethanol have been measured at high T in reflected shock waves using OH optical absorption and high-sensitivity H-atom ARAS detection. The three dissociation processes that are dominant at high T are C2H5OH--> C2H4+H2O (A) -->CH3+CH2OH (B) -->C2H5+OH (C).The rate coefficient for reaction C was measured directly with high sensitivity at 308 nm using a multipass optical White cell. Meanwhile, H-atom ARAS measurements yield the overall rate coefficient and that for the sum of reactions B and C , since H-atoms are instantaneously formed from the decompositions of CH(2)OH and C(2)H(5) into CH(2)O + H and C(2)H(4) + H, respectively. By difference, rate constants for reaction 1 could be obtained. One potential complication is the scavenging of OH by unreacted ethanol in the OH experiments, and therefore, rate constants for OH+C2H5OH-->products (D)were measured using tert-butyl hydroperoxide (tBH) as the thermal source for OH. The present experiments can be represented by the Arrhenius expression k=(2.5+/-0.43) x 10(-11) exp(-911+/-191 K/T) cm3 molecule(-1) s(-1) over the T range 857-1297 K. For completeness, we have also measured the rate coefficient for the reaction of D atoms with ethanol D+C2H5OH-->products (E) whose H analogue is another key reaction in the combustion of ethanol. Over the T range 1054-1359 K, the rate constants from the present experiments can be represented by the Arrhenius expression, k=(3.98+/-0.76) x10(-10) exp(-4494+/-235 K/T) cm3 molecule(-1) s(-1). The high-pressure rate coefficients for reactions B and C were studied with variable reaction coordinate transition state theory employing directly determined CASPT2/cc-pvdz interaction energies. Reactions A , D , and E were studied with conventional transition state theory

  20. Rate constants for the thermal decomposition of ethanol and its bimolecular reactions with OH and D : reflected shock tube and theoretical studies.

    SciTech Connect

    Sivaramakrishnan, R.; Su, M.-C.; Michael, J. V.; Klippenstein, S. J.; Harding, L. B.; Ruscic, B.

    2010-09-09

    The thermal decomposition of ethanol and its reactions with OH and D have been studied with both shock tube experiments and ab initio transition state theory-based master equation calculations. Dissociation rate constants for ethanol have been measured at high T in reflected shock waves using OH optical absorption and high-sensitivity H-atom ARAS detection. The three dissociation processes that are dominant at high T are: C{sub 2}H{sub 5}OH {yields} C{sub 2}H{sub 4} + H{sub 2}O; C{sub 2}H{sub 5}OH {yields} CH{sub 3} + CH{sub 2}OH; C{sub 2}H{sub 5}OH {yields} C{sub 2}H{sub 5} + OH. The rate coefficient for reaction C was measured directly with high sensitivity at 308 nm using a multipass optical White cell. Meanwhile, H-atom ARAS measurements yield the overall rate coefficient and that for the sum of reactions B and C, since H-atoms are instantaneously formed from the decompositions of CH{sub 2}OH and C{sub 2}H{sub 5} into CH{sub 2}O + H and C{sub 2}H{sub 4} + H, respectively. By difference, rate constants for reaction 1 could be obtained. One potential complication is the scavenging of OH by unreacted ethanol in the OH experiments, and therefore, rate constants for OH + C{sub 2}H{sub 5}OH {yields} products were measured using tert-butyl hydroperoxide (tBH) as the thermal source for OH. The present experiments can be represented by the Arrhenius expression k = (2.5 {+-} 0.43) x 10{sup -11} exp(- 911 {+-} 191 K/T) cm{sup 3} molecule{sup -1} s{sup -1} over the T range 857-1297 K. For completeness, we have also measured the rate coefficient for the reaction of D atoms with ethanol D + C{sub 2}H{sub 5}OH {yields} products whose H analogue is another key reaction in the combustion of ethanol. Over the T range 1054-1359 K, the rate constants from the present experiments can be represented by the Arrhenius expression, k = (3.98 {+-} 0.76) x 10{sup -10} exp(- 4494 {+-} 235 K/T) cm{sup 3} molecule{sup -1} s{sup -1}. The high-pressure rate coefficients for reactions B and C

  1. Ozone decomposition

    PubMed Central

    Batakliev, Todor; Georgiev, Vladimir; Anachkov, Metody; Rakovsky, Slavcho

    2014-01-01

    Catalytic ozone decomposition is of great significance because ozone is a toxic substance commonly found or generated in human environments (aircraft cabins, offices with photocopiers, laser printers, sterilizers). Considerable work has been done on ozone decomposition reported in the literature. This review provides a comprehensive summary of the literature, concentrating on analysis of the physico-chemical properties, synthesis and catalytic decomposition of ozone. This is supplemented by a review on kinetics and catalyst characterization which ties together the previously reported results. Noble metals and oxides of transition metals have been found to be the most active substances for ozone decomposition. The high price of precious metals stimulated the use of metal oxide catalysts and particularly the catalysts based on manganese oxide. It has been determined that the kinetics of ozone decomposition is of first order importance. A mechanism of the reaction of catalytic ozone decomposition is discussed, based on detailed spectroscopic investigations of the catalytic surface, showing the existence of peroxide and superoxide surface intermediates. PMID:26109880

  2. Ozone decomposition.

    PubMed

    Batakliev, Todor; Georgiev, Vladimir; Anachkov, Metody; Rakovsky, Slavcho; Zaikov, Gennadi E

    2014-06-01

    Catalytic ozone decomposition is of great significance because ozone is a toxic substance commonly found or generated in human environments (aircraft cabins, offices with photocopiers, laser printers, sterilizers). Considerable work has been done on ozone decomposition reported in the literature. This review provides a comprehensive summary of the literature, concentrating on analysis of the physico-chemical properties, synthesis and catalytic decomposition of ozone. This is supplemented by a review on kinetics and catalyst characterization which ties together the previously reported results. Noble metals and oxides of transition metals have been found to be the most active substances for ozone decomposition. The high price of precious metals stimulated the use of metal oxide catalysts and particularly the catalysts based on manganese oxide. It has been determined that the kinetics of ozone decomposition is of first order importance. A mechanism of the reaction of catalytic ozone decomposition is discussed, based on detailed spectroscopic investigations of the catalytic surface, showing the existence of peroxide and superoxide surface intermediates. PMID:26109880

  3. Thermal decomposition of CH{sub 3}CHO studied by matrix infrared spectroscopy and photoionization mass spectroscopy

    SciTech Connect

    Vasiliou, AnGayle K.; Piech, Krzysztof M.; Reed, Beth; Ellison, G. Barney; Zhang Xu; Nimlos, Mark R.; Ahmed, Musahid; Golan, Amir; Kostko, Oleg; Osborn, David L.; David, Donald E.; Urness, Kimberly N.; Daily, John W.; Stanton, John F.

    2012-10-28

    A heated SiC microtubular reactor has been used to decompose acetaldehyde and its isotopomers (CH{sub 3}CDO, CD{sub 3}CHO, and CD{sub 3}CDO). The pyrolysis experiments are carried out by passing a dilute mixture of acetaldehyde (roughly 0.1%-1%) entrained in a stream of a buffer gas (either He or Ar) through a heated SiC reactor that is 2-3 cm long and 1 mm in diameter. Typical pressures in the reactor are 50-200 Torr with the SiC tube wall temperature in the range 1200-1900 K. Characteristic residence times in the reactor are 50-200 {mu}s after which the gas mixture emerges as a skimmed molecular beam at a pressure of approximately 10 {mu}Torr. The reactor has been modified so that both pulsed and continuous modes can be studied, and results from both flow regimes are presented. Using various detection methods (Fourier transform infrared spectroscopy and both fixed wavelength and tunable synchrotron radiation photoionization mass spectrometry), a number of products formed at early pyrolysis times (roughly 100-200 {mu}s) are identified: H, H{sub 2}, CH{sub 3}, CO, CH{sub 2}=CHOH, HC{identical_to}CH, H{sub 2}O, and CH{sub 2}=C=O; trace quantities of other species are also observed in some of the experiments. Pyrolysis of rare isotopomers of acetaldehyde produces characteristic isotopic signatures in the reaction products, which offers insight into reaction mechanisms that occur in the reactor. In particular, while the principal unimolecular processes appear to be radical decomposition CH{sub 3}CHO (+M) {yields} CH{sub 3}+ H + CO and isomerization of acetaldehyde to vinyl alcohol, it appears that the CH{sub 2}CO and HCCH are formed (perhaps exclusively) by bimolecular reactions, especially those involving hydrogen atom attacks.

  4. High temperature shock tube and theoretical studies on the thermal decomposition of dimethyl carbonate and its bimolecular reactions with H and D-atoms.

    PubMed

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

    2013-05-01

    The shock tube technique was used to study the high temperature thermal decomposition of dimethyl carbonate, CH3OC(O)OCH3 (DMC). The formation of H-atoms was measured behind reflected shock waves by using atomic resonance absorption spectrometry (ARAS). The experiments span a T-range of 1053-1157 K at pressures ∼0.5 atm. The H-atom profiles were simulated using a detailed chemical kinetic mechanism for DMC thermal decomposition. Simulations indicate that the formation of H-atoms is sensitive to the rate constants for the energetically lowest-lying bond fission channel, CH3OC(O)OCH3 → CH3 + CH3OC(O)O [A], where H-atoms form instantaneously at high temperatures from the sequence of radical β-scissions, CH3OC(O)O → CH3O + CO2 → H + CH2O + CO2. A master equation analysis was performed using CCSD(T)/cc-pv∞z//M06-2X/cc-pvtz energetics and molecular properties for all thermal decomposition processes in DMC. The theoretical predictions were found to be in good agreement with the present experimentally derived rate constants for the bond fission channel (A). The theoretically derived rate constants for this important bond-fission process in DMC can be represented by a modified Arrhenius expression at 0.5 atm over the T-range 1000-2000 K as, kA(T) = 6.85 × 10(98)T (-24.239) exp(-65250 K/T) s(-1). The H-atom temporal profiles at long times show only minor sensitivity to the abstraction reaction, H + CH3OC(O)OCH3 → H2 + CH3OC(O)OCH2 [B]. However, H + DMC is an important fuel destruction reaction at high temperatures. Consequently, measurements of D-atom profiles using D-ARAS allowed unambiguous rate constant measurements for the deuterated analog of reaction B, D + CH3OC(O)OCH3 → HD + CH3OC(O)OCH2 [C]. Reaction C is a surrogate for H + DMC since the theoretically predicted kinetic isotope effect at high temperatures (1000 - 2000K) is close to unity, kC ≈ 1.2 kB. TST calculations employing CCSD(T)/cc-pv∞z//M06-2X/cc-pvtz energetics and molecular properties

  5. Decomposition techniques

    USGS Publications Warehouse

    Chao, T.T.; Sanzolone, R.F.

    1992-01-01

    Sample decomposition is a fundamental and integral step in the procedure of geochemical analysis. It is often the limiting factor to sample throughput, especially with the recent application of the fast and modern multi-element measurement instrumentation. The complexity of geological materials makes it necessary to choose the sample decomposition technique that is compatible with the specific objective of the analysis. When selecting a decomposition technique, consideration should be given to the chemical and mineralogical characteristics of the sample, elements to be determined, precision and accuracy requirements, sample throughput, technical capability of personnel, and time constraints. This paper addresses these concerns and discusses the attributes and limitations of many techniques of sample decomposition along with examples of their application to geochemical analysis. The chemical properties of reagents as to their function as decomposition agents are also reviewed. The section on acid dissolution techniques addresses the various inorganic acids that are used individually or in combination in both open and closed systems. Fluxes used in sample fusion are discussed. The promising microwave-oven technology and the emerging field of automation are also examined. A section on applications highlights the use of decomposition techniques for the determination of Au, platinum group elements (PGEs), Hg, U, hydride-forming elements, rare earth elements (REEs), and multi-elements in geological materials. Partial dissolution techniques used for geochemical exploration which have been treated in detail elsewhere are not discussed here; nor are fire-assaying for noble metals and decomposition techniques for X-ray fluorescence or nuclear methods be discussed. ?? 1992.

  6. Microwave-assisted synthesis of layered basic zinc acetate nanosheets and their thermal decomposition into nanocrystalline ZnO

    PubMed Central

    2014-01-01

    We have developed a low-cost technique using a conventional microwave oven to grow layered basic zinc acetate (LBZA) nanosheets (NSs) from a zinc acetate, zinc nitrate and HMTA solution in only 2 min. The as-grown crystals and their pyrolytic decomposition into ZnO nanocrystalline NSs are characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), atomic force microscopy (AFM), X-ray diffraction (XRD) and photoluminescence (PL). SEM and AFM measurements show that the LBZA NSs have typical lateral dimensions of 1 to 5 μm and thickness of 20 to 100 nm. Annealing in air from 200°C to 1,000°C results in the formation of ZnO nanocrystalline NSs, with a nanocrystallite size ranging from 16 nm at 200°C to 104 nm at 1,000°C, as determined by SEM. SEM shows evidence of sintering at 600°C. PL shows that the shape of the visible band is greatly affected by the annealing temperature and that the exciton band to defect band intensity ratio is maximum at 400°C and decreases by a factor of 15 after annealing at 600°C. The shape and thickness of the ZnO nanocrystalline NSs are the same as LBZA NSs. This structure provides a high surface-to-volume ratio of interconnected nanoparticles that is favorable for applications requiring high specific area and low resistivity such as gas sensing and dye-sensitized solar cells (DSCs). We show that resistive gas sensors fabricated with the ZnO NSs showed a response of 1.12 and 1.65 to 12.5 ppm and 200 ppm of CO at 350°C in dry air, respectively, and that DSCs also fabricated from the material had an overall efficiency of 1.3%. PACS 81.07.-b; 62.23.Kn; 61.82.Fk PMID:24397935

  7. Microwave-assisted synthesis of layered basic zinc acetate nanosheets and their thermal decomposition into nanocrystalline ZnO.

    PubMed

    Tarat, Afshin; Nettle, Chris J; Bryant, Daniel T J; Jones, Daniel R; Penny, Mark W; Brown, Richard A; Majitha, Ravish; Meissner, Kenith E; Maffeis, Thierry G G

    2014-01-01

    We have developed a low-cost technique using a conventional microwave oven to grow layered basic zinc acetate (LBZA) nanosheets (NSs) from a zinc acetate, zinc nitrate and HMTA solution in only 2 min. The as-grown crystals and their pyrolytic decomposition into ZnO nanocrystalline NSs are characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), atomic force microscopy (AFM), X-ray diffraction (XRD) and photoluminescence (PL). SEM and AFM measurements show that the LBZA NSs have typical lateral dimensions of 1 to 5 μm and thickness of 20 to 100 nm. Annealing in air from 200°C to 1,000°C results in the formation of ZnO nanocrystalline NSs, with a nanocrystallite size ranging from 16 nm at 200°C to 104 nm at 1,000°C, as determined by SEM. SEM shows evidence of sintering at 600°C. PL shows that the shape of the visible band is greatly affected by the annealing temperature and that the exciton band to defect band intensity ratio is maximum at 400°C and decreases by a factor of 15 after annealing at 600°C. The shape and thickness of the ZnO nanocrystalline NSs are the same as LBZA NSs. This structure provides a high surface-to-volume ratio of interconnected nanoparticles that is favorable for applications requiring high specific area and low resistivity such as gas sensing and dye-sensitized solar cells (DSCs). We show that resistive gas sensors fabricated with the ZnO NSs showed a response of 1.12 and 1.65 to 12.5 ppm and 200 ppm of CO at 350°C in dry air, respectively, and that DSCs also fabricated from the material had an overall efficiency of 1.3%. PACS: 81.07.-b; 62.23.Kn; 61.82.Fk. PMID:24397935

  8. Characterization and photo-chemical applications of nano-ZnO prepared by wet chemical and thermal decomposition methods

    SciTech Connect

    Mousa, M.A.; Bayoumy, W.A.A.; Khairy, M.

    2013-11-15

    Graphical abstract: - Highlights: • Nano-ZnO particles were synthesized by soft-wet precipitation and dry methods. • ZnO nanoparticle with different morphologies was obtained. • Nano ZnO samples showed a high photocatalytic activity. • ZnO nanoparticle showed strong ultraviolet emission at room temperature. • The samples showed high biological activity depending on their synthetic method. - Abstract: Nano-crystalline ZnO particles were synthesized using two different routes: soft-wet and dry methods. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to identify the particles structures and morphologies, while X-ray diffraction (XRD) was used for verifying the particles crystal structure. The thermal stabilities of the particles were examined through thermal gravimetric analysis technique and their surface areas were calculated using BET method. Moreover, the photocatalytic activities were evaluated using UV–vis spectroscopy and photoluminescence (PL) characterization. The results showed that all the prepared ZnO samples possess a hexagonal wurtzite structure with high purity. Different particle sizes and morphologies of spheres, rods and wires were obtained depending on the preparation method used. Particle sizes obtained by the dry method are smaller than that found by the wet chemical method. The effects of both particle size and morphology on each of surface as well as optical properties, photocatalytic activity, dye/ZnO solar cell efficiency and biological activity have been studied and discussed.

  9. A 2-Step Laemmli and Antigen Retrieval Method Improves Immunodetection.

    PubMed

    Scalia, Carla R; Gendusa, Rossella; Cattoretti, Giorgio

    2016-07-01

    Detection by immunohistochemistry of antigens relies on reproducibly optimal preanalytical and analytical variables such as fixation conditions, antigen retrieval (AR), and the resolutive power of the detection system. There is a need to improve immunodetection on routinely fixed and embedded material, particularly for scarcely represented but relevant antigens. We devised a 2-step method and applied it to a panel of antigens of common use for diagnosis, prognosis, individualized therapy use, or research. The first step consists of a 10 minutes. Incubation at 95°C with a modified Laemmli extraction buffer. This was followed by a traditional AR method. Detection of the vast majority of antigens was improved over a simple AR with preservation of tissue integrity, as shown by quantitative image analysis. The mechanism underlying the improved detection may be controlled denaturation followed by heat-mediated retrieval, a method we dubbed "antigen relaxing" and which will improve routine detection of scarce antigens in formalin-fixed, paraffin-embedded material. PMID:26067142

  10. A novel surface-sensitive X-ray absorption spectroscopic detector to study the thermal decomposition of cathode materials for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Nonaka, Takamasa; Okuda, Chikaaki; Oka, Hideaki; Nishimura, Yusaku F.; Makimura, Yoshinari; Kondo, Yasuhito; Dohmae, Kazuhiko; Takeuchi, Yoji

    2016-09-01

    A surface-sensitive conversion-electron-yield X-ray absorption fine structure (CEY-XAFS) detector that operates at elevated temperatures is developed to investigate the thermal decomposition of cathode materials for Li-ion batteries. The detector enables measurements with the sample temperature controlled from room temperature up to 450 °C. The detector is applied to the LiNi0.75Co0.15Al0.05Mg0.05O2 cathode material at 0% state of charge (SOC) and 50% SOC to examine the chemical changes that occur during heating in the absence of an electrolyte. The combination of surface-sensitive CEY-XAFS and bulk-sensitive transmission-mode XAFS shows that the reduction of Ni and Co ions begins at the surface of the cathode particles at around 150 °C, and propagates inside the particle upon further heating. These changes with heating are irreversible and are more obvious at 50% SOC than at 0% SOC. The fraction of reduced Ni ions is larger than that of reduced Co ions. These results demonstrate the capability of the developed detector to obtain important information for the safe employment of this cathode material in Li-ion batteries.

  11. Simple cerium-triethanolamine complex: Synthesis, characterization, thermal decomposition and its application to prepare ceria support for platinum catalysts used in methane steam reforming

    NASA Astrophysics Data System (ADS)

    Wattanathana, Worawat; Nootsuwan, Nollapan; Veranitisagul, Chatchai; Koonsaeng, Nattamon; Laosiripojana, Navadol; Laobuthee, Apirat

    2015-06-01

    Cerium-triethanolamine complex was synthesized by simple complexation method in 1-propanol solvent using cerium(III) chloride as a metal source and triethanolamine as a ligand. The structures of the prepared complex were proposed based on FT-IR, FT-Raman and ESI-MS results as equimolar of triethanolamine and cerium chelated complex having monomeric tricyclic structure with and without chloride anion as another coordinating group known as ceratrane. The complex was used as a precursor for ceria material done by thermal decomposition. XRD result revealed that when calcined at 600 °C for 2 h, the cerium complex was totally turned into pure ceria with cubic fluorite structure. The obtained ceria was then employed to synthesize platinum doped ceria catalysts for methane steam reforming. Various amounts of platinum i.e. 1, 3, 5 and 10 mol percents were introduced on the ceria support by microwave-assisted wetness impregnation using ammonium tetrachloroplatinate(II). The platinum-impregnated ceria powders were subjected to calcination in 10% hydrogen/helium atmosphere at 500 °C for 3 h to reduce platinum(II) to platinum(0). XRD patterns of the catalysts confirmed that the platinum particles doped on the ceria support were in the form of platinum(0). Catalytic activity test showed that the catalytic activities got higher as the amounts of platinum doped increased. Besides, the portions of coke formation on the surface of catalysts were reduced as the amounts of platinum doped increased.

  12. A one-step thermal decomposition method to prepare anatase TiO2 nanosheets with improved adsorption capacities and enhanced photocatalytic activities

    NASA Astrophysics Data System (ADS)

    Li, Wenting; Shang, Chunli; Li, Xue

    2015-12-01

    Anatase TiO2 nanosheets (NSs) with high surface area have been prepared via a one-step thermal decomposition of titanium tetraisopropoxide (TTIP) in oleylamine (OM), and their adsorption capacities and photocatalytic activities are investigated by using methylene blue (MB) and methyl orange (MO) as model pollutants. During the synthesis procedure, only one type of surfactant, oleylamine (OM), is used as capping agents and no other solvents are added. Structure and properties of the TiO2 NSs were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N2 adsorption analysis, UV-vis spectrum, X-ray photoelectron spectroscopy (XPS) and Photoluminescence (PL) methods. The results indicate that the TiO2 NSs possess high surface area up to 378 m2 g-1. The concentration of capping agents is found to be a key factor controlling the morphology and crystalline structure of the product. Adsorption and photodegradation experiments reveal that the prepared TiO2 NSs possess high adsorption capacities of model pollutants MB and high photocatalytic activity, showing that TiO2 NSs can be used as efficient pollutant adsorbents and photocatalytic degradation catalysts of MB in wastewater treatment.

  13. Thermochemical cycles for energy storage: Thermal decomposition of ZnCO{sub 4} systems. Final topical report, January 1, 1982--December 31, 1984

    SciTech Connect

    Wentworth, W.E.

    1992-04-01

    The overall objective of our research has been to develop thermochemical cycles that can be used for energy storage. A specific cycle involving ammonium hydrogen sulfate (NH{sub 4}HSO{sub 4}) has been proposed. Each reaction in the proposed cycle has been examined experimentally. Emphasis has been placed on the basic chemistry of these reactions. In the concluding phase of this research, reported herein, we have shown that when NH{sub 4}HSO{sub 4} is mixed with ZnO and decomposed, the resulting products can be released stepwise (H{sub 2}A{sub (g)} at {approximately}163{degrees}C, NH{sub 3(g)} at 365--418{degrees}C, and a mixture of SO{sub 2(g)} and SO{sub 3(g)} at {approximately}900{degrees}C) and separated by controlling the reaction temperature. Side reactions do not appear to be significant and the respective yields are high as would be required for the successful use of this energy storage reaction in the proposed cycle. Thermodynamic, kinetic, and other reaction parameters have been measured for the various steps of the reaction. Finally we have completed a detailed investigation of one particular reaction: the thermal decomposition of zinc sulfate (ZnSO{sub 4}). We have demonstrated that this reaction can be accelerated and the temperature required reduced by the addition of excess ZnO, V{sub 2}A{sub 5} and possibly other metal oxides.

  14. Highly crystalline LiCuXFe1‑XPO4 nanoparticles synthesized by high temperature thermal decomposition: a morphological and electrical transport study

    NASA Astrophysics Data System (ADS)

    Martinez, P.; Ruiz, F.; Curiale, J.; Vasquez Mansilla, M.; Zysler, R. D.; Dada, L.; Moreno, M. S.; Rodríguez, L.; Fregenal, D.; Bernardi, G.; Lima, E., Jr.

    2016-08-01

    In this work, we report the morphological and electrical characterization of highly crystalline \\text{LiC}{{\\text{u}}\\text{X}}\\text{F}{{\\text{e}}1-\\text{X}}\\text{P}{{\\text{O}}4} nanoparticles synthesized via the high-temperature (380 °C) thermal decomposition of organometallic precursors. The mean diameter of the studied nanoparticles was 30–40 nm. The Cu/Fe relations of 0, 0.001 and 0.042 for the three studied samples were obtained via particle-induced x-ray emission spectroscopy. Crystallographic and morphological studies were performed using x-ray diffraction, transmission electron microscopy and high-resolution transmission electron microscopy techniques. We investigated the effects of incorporating copper on the electric transport properties of this highly crystalline nanometric system using impedance spectroscopy and DC transport techniques. The experimental evidence allowed us to conclude that in the frequency range f  <  1 kHz the transport is dominated by the diffusion of Li and the presence of Cu atoms in the systems hinders this transport mechanism, despite the high crystallinity of the system.

  15. Preparation, crystal structure, thermal decomposition, quantum chemical calculations on [K(ZTO)ṡH2O]∞ and its ligand ZTO

    NASA Astrophysics Data System (ADS)

    Ma, Cong; Huang, Jie; Ma, Hai-Xia; Xu, Kang-Zhen; Lv, Xing-Qiang; Song, Ji-Rong; Zhao, Ning-Ning; He, Jian-Yun; Zhao, Yi-Sha

    2013-03-01

    A novel potassium complex has been synthesized and characterized under the non-isothermal conditions by DSC and TG-DTG method. The 4,4-azo-1,2,4-triazol-5-one (ZTO) has the molecular formula C4H4N8O2. The thermodynamic parameters, HOMO-LUMO energy gap, total energy and electrostatic potential (MEP) of ZTO are conducted by density functional theory DFT/B3LYP calculation method with 6-311G basis set. In the coordination polymer, with the ligand anion (ZTO-) as space linkers, two types of potassium atoms centers are joined together to form three-dimensional frameworks. The enthalpy, apparent activation energy and pre-exponential factor of the second exothermic decomposition reaction are 85.43 kJ mol-1, 414.4 kJ mol-1and 1037.92 s-1, respectively. The critical temperature of thermal explosion (Tb) for [K(ZTO)ṡH2O]∞ is 275.08 °C. [K(ZTO)ṡH2O]∞ CCDC: 902339.

  16. Thermal decomposition of alkane hydrocarbons inside a porous Ni anode for fuel supply of direct carbon fuel cell: Effects of morphology and crystallinity of carbon

    NASA Astrophysics Data System (ADS)

    Li, Chengguo; Yi, Hakgyu; Jalalabadi, Tahereh; Lee, Donggeun

    2015-10-01

    This study improved the physical contact between anode and fuel in a direct carbon fuel cell (DCFC) by directly generating carbon in a porous Ni anode through thermal decomposition of three kinds of hydrocarbons (CH4, C2H6, C3H8). From electron microscope observations of the carbon particles generated from each hydrocarbon, carbon spheres (CS), carbon nanotubes (CNT) and carbon nanofibers (CNF) were identified with increasing carbon number. Raman scattering analysis was performed to determine the crystallinity of the carbon samples. As a result, the carbon samples (CS, CNT, and CNF) produced from CH4, C2H6 and C3H8 were found to be less crystalline and more flexible with increasing the carbon number. DCFC performance was measured at 700 °C for the anode fueled with the same mass of the carbon sample. It was found that the 1-dimensional CNT and CNF were more active to produce 148% and 210% times higher power density than the CS. The difference was partly attributed to the finding that the less-crystalline CNT and CNF had much lower charge transfer resistances than the CS. A lifetime test found that the CNT and CNF, which are capable of transporting electrons for much longer periods, maintained the power density much longer, as compared to the CS which can lose their point contacts between the particles shortly at high current density.

  17. Structural and Thermal Characterization of Zolpidem Hemitartrate Hemihydrate (Form E) and Its Decomposition Products by Laboratory X-Ray Powder Diffraction

    SciTech Connect

    Halasz, I.; Dinnebier, R

    2010-01-01

    The crystal structure of zolpidem hemitartrate hemihydrate (I, Form E) has been solved from high-resolution laboratory powder diffraction data. It crystallizes in the orthorhombic P2{sub 1}2{sub 1}2{sub 1} space group with a = 22.4664(6) {angstrom}, b = 26.0420(7) {angstrom}, and c = 7.4391(1) {angstrom}. Protonation of zolpidem molecules could not be unambiguously determined. Thermal stability of Form E has been investigated by TG-DTA and in situ by temperature resolved X-ray powder diffraction. Water loss occurs between 50 C {le} t {le} 100 C while structure decomposition commences at approximately 120 C yielding zolpidem tartrate (II) and pure zolpidem base (III) in approximately equimolar amounts. Crystal structures of II and III have been solved simultaneously from a single powder pattern of thermally decomposed I. Zolpidem tartrate crystallizes in the orthorhombic P2{sub 1}2{sub 1}2{sub 1} space group with a = 19.9278(8) {angstrom}, b = 15.1345(8) {angstrom}, and c = 7.6246(2) {angstrom} (at 140 C). Zolpidem base crystallizes in the orthorhombic Pcab space group with a = 9.9296(4) {angstrom}, b = 18.4412(9) {angstrom}, and c = 18.6807(9) {angstrom} (at 140 C). In the reported crystal structures zolpidem molecules form stacks through {pi}-{pi} interaction or dipole-dipole interactions while tartrate moieties, if present, form hydrogen bonded chains. Water molecule in I forms a hydrogen bond to the imidazole nitrogen atom of the zolpidem molecule. Free space in the crystal structure of I could allow for the additional water molecules and thus a variable water content.

  18. Description of Chemically and Thermally Treated Multi-Walled Carbon Nanotubes Using Sequential Decomposition of Adsorption Isotherms

    NASA Astrophysics Data System (ADS)

    Albesa, Alberto G.; Rafti, Matías; Vicente, José Luis

    2016-03-01

    The effect of wet acid oxidation by means of sulfuric/nitric acid mixtures, and high-temperature treatment of commercial arc-discharge synthesized multi-walled carbon nanotubes (MWCNTs) was studied. In order to analyze the adsorption capacities of differently treated MWCNTs, we employed a multistep method that considers separately different pressure ranges (zones) on the experimentally obtained isotherms. The method is based on simple gas isotherm measurements (N2, CO2, CH4, etc.). Low pressure ranges can be described using Dubinin’s model, while high pressure regimes can be fitted using different models such as BET multilayer and Freundlich equations. This analysis allows to elucidate how different substrate treatments (chemical and thermal) can affect the adsorbate-adsorbent interactions; moreover, theoretical description of adsorbate-adsorbate interactions can be improved if a combination of adsorption mechanisms are used instead of a unique model. The results hereby presented also show that, while MWCNTs are a promising material for storage applications, gas separation applications should carefully consider the effect of wide nanotube size distribution present on samples after activation procedures.

  19. Synthesis, spectroscopic characterization, electrochemical behaviour and thermal decomposition studies of some transition metal complexes with an azo derivative

    NASA Astrophysics Data System (ADS)

    Sujamol, M. S.; Athira, C. J.; Sindhu, Y.; Mohanan, K.

    2010-01-01

    Complexes of manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) with a novel heterocyclic azo derivative, formed by coupling diazotized 2-amino-3-carbethoxy-4,5-dimethylthiophene with acetylacetone were synthesized and characterized on the basis of elemental analyses, molar conductance, magnetic susceptibility measurements, UV-vis, IR, 1H NMR and EPR spectral data. Spectral studies revealed that the ligand existed in an internally hydrogen bonded azo-enol form rather than the keto-hydrazone form and coordinated to the metal ion in a tridentate fashion. Analytical data revealed that all the complexes exhibited 1:1 metal-ligand ratio. On the basis of electronic spectral data and magnetic susceptibility measurements, suitable geometry was proposed for each complex. The nickel(II) complex has undergone facile transesterification reaction when refluxed in methanol for a long period. The ligand and the copper(II) complex were subjected to X-ray diffraction study. The electrochemical behaviour of copper(II) complex was investigated by cyclic voltammetry. The thermal behaviour of the same complex was also examined by thermogravimetry.

  20. Synthesis, spectroscopic characterization, electrochemical behaviour and thermal decomposition studies of some transition metal complexes with an azo derivative.

    PubMed

    Sujamol, M S; Athira, C J; Sindhu, Y; Mohanan, K

    2010-01-01

    Complexes of manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) with a novel heterocyclic azo derivative, formed by coupling diazotized 2-amino-3-carbethoxy-4,5-dimethylthiophene with acetylacetone were synthesized and characterized on the basis of elemental analyses, molar conductance, magnetic susceptibility measurements, UV-vis, IR, (1)H NMR and EPR spectral data. Spectral studies revealed that the ligand existed in an internally hydrogen bonded azo-enol form rather than the keto-hydrazone form and coordinated to the metal ion in a tridentate fashion. Analytical data revealed that all the complexes exhibited 1:1 metal-ligand ratio. On the basis of electronic spectral data and magnetic susceptibility measurements, suitable geometry was proposed for each complex. The nickel(II) complex has undergone facile transesterification reaction when refluxed in methanol for a long period. The ligand and the copper(II) complex were subjected to X-ray diffraction study. The electrochemical behaviour of copper(II) complex was investigated by cyclic voltammetry. The thermal behaviour of the same complex was also examined by thermogravimetry. PMID:19910244

  1. Shock wave study and theoretical modeling of the thermal decomposition of c-C4F8.

    PubMed

    Cobos, C J; Hintzer, K; Sölter, L; Tellbach, E; Thaler, A; Troe, J

    2015-12-28

    The thermal dissociation of octafluorocyclobutane, c-C4F8, was studied in shock waves over the range 1150-2300 K by recording UV absorption signals of CF2. It was found that the primary reaction nearly exclusively produces 2 C2F4 which afterwards decomposes to 4 CF2. A primary reaction leading to CF2 + C3F6 is not detected (an upper limit to the yield of the latter channel was found to be about 10 percent). The temperature range of earlier single pulse shock wave experiments was extended. The reaction was shown to be close to its high pressure limit. Combining high and low temperature results leads to a rate constant for the primary dissociation of k1 = 10(15.97) exp(-310.5 kJ mol(-1)/RT) s(-1) in the range 630-1330 K, over which k1 varies over nearly 14 orders of magnitude. Calculations of the energetics of the reaction pathway and the rate constants support the conclusions from the experiments. Also they shed light on the role of the 1,4-biradical CF2CF2CF2CF2 as an intermediate of the reaction. PMID:26577435

  2. Woodland Decomposition.

    ERIC Educational Resources Information Center

    Napier, J.

    1988-01-01

    Outlines the role of the main organisms involved in woodland decomposition and discusses some of the variables affecting the rate of nutrient cycling. Suggests practical work that may be of value to high school students either as standard practice or long-term projects. (CW)

  3. Direct studies of the thermal decomposition of N{sub 2}O and CO{sub 2} and of the reaction of CO with O{sub 2}

    SciTech Connect

    Sutherland, J.W.; Patterson, P.M.; Klemm, R.B.

    1992-02-01

    The thermal decompositions of N{sub 2}O and CO{sub 2} was investigated by monitoring the kinetics of formation of O({sup 3}P) atoms in the reflected shock regime using atomic resonance absorption spectrophotometry (A.R.A.S.). The temperature range was 1805K to 2379K for N{sub 2}O and 2332K to 2869K for CO{sub 2}. Total densities were 3--4 {times} 10{sup 18} molecules cm{sup {minus}3} and hence the reported rate constants are at or near the low pressure limit for unimolecular decomposition. The results were expressed by the following Arrhenius equations: CO{sub 2} k(T) = (1.63 {plus_minus} 1.96) {times} 10{sup {minus}8} exp({minus}122565 {plus_minus} 5183/RT) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1} N{sub 2}O k(T) = (6.02 {plus_minus} 2.81) {times} 10{sup 10} exp({minus}53397 {plus_minus} 1865/RT) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. Uncertainties in the Arrhenius expressions are given at the one standard deviation level and the mean deviations of the experimental data from the respective expression are {plus_minus} 18.6% and {plus_minus} 30.7%. Corresponding values for the reverse reaction, k{sub rev}(CO{sub 2}) were computed from the expression k{sub for}/k{sub rev} = K{sub c}. The value obtained for k{sub rev}(CO{sub 2}) was (2.18 {plus_minus} 0.83) {times} 10{sup {minus}34} cm{sup 6} molecule{sup {minus}2} s{sup {minus}1}, independent of temperature from 2332K to 2869K. Preliminary results are also reported for the direct determination of the rate constant for the reaction, CO + O{sub 2} {yields} CO{sub 2} + O, from measurements of the initial rate of formation of O({sup 3}P) atoms. 35 refs., 9 figs., 4 tabs.

  4. Direct studies of the thermal decomposition of N sub 2 O and CO sub 2 and of the reaction of CO with O sub 2

    SciTech Connect

    Sutherland, J.W.; Patterson, P.M.; Klemm, R.B.

    1992-01-01

    The thermal decompositions of N{sub 2}O and CO{sub 2} was investigated by monitoring the kinetics of formation of O({sup 3}P) atoms in the reflected shock regime using atomic resonance absorption spectrophotometry (A.R.A.S.). The temperature range was 1805K to 2379K for N{sub 2}O and 2332K to 2869K for CO{sub 2}. Total densities were 3--4 {times} 10{sup 18} molecules cm{sup {minus}3} and hence the reported rate constants are at or near the low pressure limit for unimolecular decomposition. The results were expressed by the following Arrhenius equations: CO{sub 2} k(T) = (1.63 {plus minus} 1.96) {times} 10{sup {minus}8} exp({minus}122565 {plus minus} 5183/RT) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1} N{sub 2}O k(T) = (6.02 {plus minus} 2.81) {times} 10{sup 10} exp({minus}53397 {plus minus} 1865/RT) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. Uncertainties in the Arrhenius expressions are given at the one standard deviation level and the mean deviations of the experimental data from the respective expression are {plus minus} 18.6% and {plus minus} 30.7%. Corresponding values for the reverse reaction, k{sub rev}(CO{sub 2}) were computed from the expression k{sub for}/k{sub rev} = K{sub c}. The value obtained for k{sub rev}(CO{sub 2}) was (2.18 {plus minus} 0.83) {times} 10{sup {minus}34} cm{sup 6} molecule{sup {minus}2} s{sup {minus}1}, independent of temperature from 2332K to 2869K. Preliminary results are also reported for the direct determination of the rate constant for the reaction, CO + O{sub 2} {yields} CO{sub 2} + O, from measurements of the initial rate of formation of O({sup 3}P) atoms. 35 refs., 9 figs., 4 tabs.

  5. Novel Composite Hydrogen-Permeable Membranes for Non-Thermal Plasma Reactors for the Decomposition of Hydrogen Sulfide

    SciTech Connect

    Morris D. Argyle; John F. Ackerman; Suresh Muknahallipatna; Jerry C. Hamann; Stanislaw Legowski; Guibling Zhao; Ji-Jun Zhang; Sanil John

    2005-10-01

    The goal of this experimental project is to design and fabricate a reactor and membrane test cell to dissociate hydrogen sulfide (H{sub 2}S) in a non-thermal plasma and recover hydrogen (H{sub 2}) through a superpermeable multi-layer membrane. Superpermeability of hydrogen atoms (H) has been reported by some researchers using membranes made of Group V transition metals (niobium, tantalum, vanadium, and their alloys), although it has yet to be confirmed in this study. A pulsed corona discharge (PCD) reactor has been fabricated and used to dissociate H{sub 2}S into hydrogen and sulfur. A nonthermal plasma cannot be produced in pure H{sub 2}S with our reactor geometry, even at discharge voltages of up to 30 kV, because of the high dielectric strength of pure H{sub 2}S ({approx}2.9 times higher than air). Therefore, H{sub 2}S was diluted in another gas with lower breakdown voltage (or dielectric strength). Breakdown voltages of H{sub 2}S in four balance gases (Ar, He, N{sub 2} and H{sub 2}) have been measured at different H{sub 2}S concentrations and pressures. Breakdown voltages are proportional to the partial pressure of H{sub 2}S and the balance gas. H{sub 2}S conversion and the reaction energy efficiency depend on the balance gas and H{sub 2}S inlet concentrations. With increasing H{sub 2}S concentrations, H{sub 2}S conversion initially increases, reaches a maximum, and then decreases. H{sub 2}S conversion in atomic balance gases, such as Ar and He, is more efficient than that in diatomic balance gases, such as N{sub 2} and H{sub 2}. These observations can be explained by the proposed reaction mechanism of H{sub 2}S dissociation in different balance gases. The results show that nonthermal plasmas are effective for dissociating H{sub 2}S into hydrogen and sulfur.

  6. NOVEL COMPOSITE HYDROGEN-PERMEABLE MEMBRANES FOR NON-THERMAL PLASMA REACTORS FOR THE DECOMPOSITION OF HYDROGEN SULFIDE

    SciTech Connect

    Morris D. Argyle; John F. Ackerman; Suresh Muknahallipatna; Jerry C. Hamann; Stanislaw Legowski; Ji-Jun Zhang; Guibing Zhao; Robyn J. Alcanzare; Linna Wang; Ovid A. Plumb

    2004-07-01

    The goal of this experimental project is to design and fabricate a reactor and membrane test cell to dissociate hydrogen sulfide (H{sub 2}S) in a non-thermal plasma and recover hydrogen (H{sub 2}) through a superpermeable multi-layer membrane. Superpermeability of hydrogen atoms (H) has been reported by some researchers using membranes made of Group V transition metals (niobium, tantalum, vanadium, and their alloys), although it has yet to be confirmed in this study. Experiments involving methane conversion reactions were conducted with a preliminary pulsed corona discharge reactor design in order to test and improve the reactor and membrane designs using a non-toxic reactant. This report details the direct methane conversion experiments to produce hydrogen, acetylene, and higher hydrocarbons utilizing a co-axial cylinder (CAC) corona discharge reactor, pulsed with a thyratron switch. The reactor was designed to accommodate relatively high flow rates (655 x 10{sup -6} m{sup 3}/s) representing a pilot scale easily converted to commercial scale. Parameters expected to influence methane conversion including pulse frequency, charge voltage, capacitance, residence time, and electrode material were investigated. Conversion, selectivity and energy consumption were measured or estimated. C{sub 2} and C{sub 3} hydrocarbon products were analyzed with a residual gas analyzer (RGA). In order to obtain quantitative results, the complex sample spectra were de-convoluted via a linear least squares method. Methane conversion as high as 51% was achieved. The products are typically 50%-60% acetylene, 20% propane, 10% ethane and ethylene, and 5% propylene. First Law thermodynamic energy efficiencies for the system (electrical and reactor) were estimated to range from 38% to 6%, with the highest efficiencies occurring at short residence time and low power input (low specific energy) where conversion is the lowest (less than 5%). The highest methane conversion of 51% occurred at a

  7. Laser lift-off technique for freestanding GaN substrate using an In droplet formed by thermal decomposition of GaInN and its application to light-emitting diodes

    SciTech Connect

    Iida, Daisuke Kawai, Syunsuke; Ema, Nobuaki; Tsuchiya, Takayoshi; Iwaya, Motoaki; Takeuchi, Tetsuya; Kamiyama, Satoshi; Akasaki, Isamu

    2014-08-18

    We developed a laser lift-off technique for a freestanding GaN substrate using an In droplet formed by thermal decomposition of GaInN. A combination of an In droplet formed by thermal decomposition of GaInN during growth and a pulsed second-harmonic neodymium-doped yttrium aluminum garnet laser (λ = 532 nm) realized the lift-off GaN substrate. After laser lift-off of the GaN substrate, it was used to achieve 380 nm ultraviolet light-emitting diodes with light output enhanced 1.7-fold. In this way, the light extraction can be improved by removing the GaN substrate.

  8. The thermal stability of sideronatrite and its decomposition products in the system Na2O-Fe2O3-SO2-H2O

    NASA Astrophysics Data System (ADS)

    Ventruti, Gennaro; Scordari, Fernando; Della Ventura, Giancarlo; Bellatreccia, Fabio; Gualtieri, Alessandro F.; Lausi, Andrea

    2013-09-01

    The thermal stability of sideronatrite, ideally Na2Fe3+(SO4)2(OH)·3(H2O), and its decomposition products were investigated by combining thermogravimetric and differential thermal analysis, in situ high-temperature X-ray powder diffraction (HT-XRPD) and Fourier transform infrared spectroscopy (HT-FTIR). The data show that for increasing temperature there are four main dehydration/transformation steps in sideronatrite: (a) between 30 and 40 °C sideronatrite transforms into metasideronatrite after the loss of two water molecules; both XRD and FTIR suggest that this transformation occurs via minor adjustments in the building block. (b) between 120 and 300 °C metasideronatrite transforms into metasideronatrite II, a still poorly characterized phase with possible orthorhombic symmetry, consequently to the loss of an additional water molecule; X-ray diffraction data suggest that metasideronatrite disappears from the assemblage above 175 °C. (c) between 315 and 415 °C metasideronatrite II transforms into the anhydrous Na3Fe(SO4)3 compound. This step occurs via the loss of hydroxyl groups that involves the breakdown of the [Fe3+(SO4)2(OH)]{∞/2-} chains and the formation of an intermediate transient amorphous phase precursor of Na3Fe(SO4)3. (d) for T > 500 °C, the Na3Fe(SO4)3 compound is replaced by the Na-sulfate thenardite, Na2SO4, plus Fe-oxides, according to the Na3Fe3+(SO4)3 → 3/2 Na2(SO4) + 1/2 Fe2O3 + SOx reaction products. The Na-Fe sulfate disappears around 540 °C. For higher temperatures, the Na-sulfates decomposes and only hematite survives in the final product. The understanding of the thermal behavior of minerals such as sideronatrite and related sulfates is important both from an environmental point of view, due to the presence of these phases in evaporitic deposits, soils and sediments including extraterrestrial occurrences, and from the technological point of view, due to the use of these materials in many industrial applications.

  9. Magnetic and Cytotoxicity Properties of La1−xSrxMnO3(0 ≤ x ≤ 0.5) Nanoparticles Prepared by a Simple Thermal Hydro-Decomposition

    PubMed Central

    2009-01-01

    This study reports the magnetic and cytotoxicity properties of magnetic nanoparticles of La1−xSrxMnO3(LSMO) withx = 0, 0.1, 0.2, 0.3, 0.4, and 0.5 by a simple thermal decomposition method by using acetate salts of La, Sr, and Mn as starting materials in aqueous solution. To obtain the LSMO nanoparticles, thermal decomposition of the precursor was carried out at the temperatures of 600, 700, 800, and 900 °C for 6 h. The synthesized LSMO nanoparticles were characterized by XRD, FT-IR, TEM, and SEM. Structural characterization shows that the prepared particles consist of two phases of LaMnO3(LMO) and LSMO with crystallite sizes ranging from 20 nm to 87 nm. All the prepared samples have a perovskite structure with transformation from cubic to rhombohedral at thermal decomposition temperature higher than 900 °C in LSMO samples ofx ≤ 0.3. Basic magnetic characteristics such as saturated magnetization (MS) and coercive field (HC) were evaluated by vibrating sample magnetometry at room temperature (20 °C). The samples show paramagnetic behavior for all the samples withx = 0 or LMO, and a superparamagnetic behavior for the other samples havingMSvalues of ~20–47 emu/g and theHCvalues of ~10–40 Oe, depending on the crystallite size and thermal decomposition temperature. Cytotoxicity of the synthesized LSMO nanoparticles was also evaluated with NIH 3T3 cells and the result shows that the synthesized nanoparticles were not toxic to the cells as determined from cell viability in response to the liquid extract of LSMO nanoparticles. PMID:20596291

  10. Synthesis of porous sheet-like Co{sub 3}O{sub 4} microstructure by precipitation method and its potential applications in the thermal decomposition of ammonium perchlorate

    SciTech Connect

    Lu Shanshan; Jing Xiaoyan; Liu Jingyuan; Wang Jun; Liu Qi; Zhao Yanhua; Jamil, Saba; Zhang Milin; Liu Lianhe

    2013-01-15

    Porous sheet-like cobalt oxide (Co{sub 3}O{sub 4}) were successfully synthesized by precipitation method combined with calcination of cobalt hydroxide precursors. The structure, morphology and porosity properties of the products were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and nitrogen adsorption-desorption measurement. The as-prepared sheet-like microstructures were approximately 2-3 {mu}m in average diameter, and the morphology of the cobalt hydroxide precursors was retained after the calcination process. However, it appeared a large number of uniform pores in the sheets after calcination. In order to calculate the potential catalytic activity, the thermal decomposition of ammonium perchlorate (AP) has been analyzed, in which cobalt oxide played a role of an additive and the porous sheet-like Co{sub 3}O{sub 4} microstructures exhibited high catalytic performance and considerable decrease in the thermal decomposition temperature of AP. Moreover, a formation mechanism for the sheet-like microstructures has been discussed. - Graphical abstract: Porous sheet-like Co{sub 3}O{sub 4} were synthesized by facile precipitation method combined with calcination of {beta}-Co(OH){sub 2} precursors. Thermogravimetric-differential scanning calorimetric analysis indicates potential catalytic activity in the thermal decomposition of ammonium perchlorate. Highlights: Black-Right-Pointing-Pointer Synthesis of sheet-like {beta}-Co(OH){sub 2} precursors by precipitation method. Black-Right-Pointing-Pointer Porous sheet-like Co{sub 3}O{sub 4} were obtained by calcining {beta}-Co(OH){sub 2} precursors. Black-Right-Pointing-Pointer The possible formation mechanism of porous sheet-like Co{sub 3}O{sub 4} has been discussed. Black-Right-Pointing-Pointer Porous sheet-like Co{sub 3}O{sub 4} decrease the thermal decomposition temperature of ammonium perchlorate.

  11. Deep ultra violet and visible Raman spectroscopy studies of ion implanted 6H-SiC: Recrytallisation behaviour and thermal decomposition/thermal etching of the near surface region

    NASA Astrophysics Data System (ADS)

    Kuhudzai, R. J.; Malherbe, J. B.; van der Berg, N. G.; Hlatshwayo, T. T.; Odutemowo, O.; Prinsloo, L. C.; Buys, A. V.; Erasmus, R.; Wendler, E.

    2015-12-01

    The recystallisation behaviour and thermal decomposition of the near surface amorphised region of 6H-SiC have been investigated by Raman spectroscopy. 360 keV ions of iodine and silver were implanted at room temperature into wafers of 6H-SiC resulting in the amorphisation of the near surface region. Vacuum annealing of the samples was performed at 1200 °C for 5 h and then sequentially from 1200 to 1600 °C in steps of 100 °C for 30 h at each annealing temperature. Raman spectroscopy was performed using two laser wavelength excitation regimes, the 514 nm laser (visible region) and the 244 nm laser (deep ultraviolet region, DUV). Measurements in the visible region for samples annealed at 1200 °C for 5 h showed that the characteristic 6H-SiC peaks, namely, the Transverse Optical (TO) and Longitudinal Optical (LO) are similar to the virgin samples, albeit with lower intensity due to some retained defects upon recystallisation of the SiC surface region. The similarities between the virgin spectra and the annealed sample were due to the deep penetration of the 514 nm laser into 6H-SiC resulting in the signal from the bulk undamaged 6H-SiC contributing to the overall spectra. However, DUV laser excitation, which only probes the near surface region, shows that after annealing the peaks are broader and asymmetrical compared to the virgin samples. DUV Raman spectra of samples annealed at 1600 °C indicate that SiC has completely decomposed and the top surface layer is now covered by a carbon layer. However the deeper penetrating laser in the visible region showed that the extent of decomposition at 1600 °C was greater for the silver implanted samples than for the iodine implanted samples.

  12. Structural, magnetic, and electronic properties of iron selenide Fe6-7Se8 nanoparticles obtained by thermal decomposition in high-temperature organic solvents.

    PubMed

    Lyubutin, I S; Lin, Chun-Rong; Funtov, K O; Dmitrieva, T V; Starchikov, S S; Siao, Yu-Jhan; Chen, Mei-Li

    2014-07-28

    Iron selenide nanoparticles with the NiAs-like crystal structure were synthesized by thermal decomposition of iron chloride and selenium powder in a high-temperature organic solvent. Depending on the time of the compound processing at 340 °C, the nanocrystals with monoclinic (M)-Fe3Se4 or hexagonal (H)-Fe7Se8 structures as well as a mixture of these two phases can be obtained. The magnetic behavior of the monoclinic and hexagonal phases is very different. The applied-field and temperature dependences of magnetization reveal a complicated transformation between ferrimagnetic (FRM) and antiferromagnetic (AFM) structures, which can be related to the spin rotation process connected with the redistribution of cation vacancies. From XRD and Mössbauer data, the 3c type superstructure of vacancy ordering was found in the hexagonal Fe7Se8. Redistribution of vacancies in Fe7Se8 from random to ordered leads to the transformation of the magnetic structure from FRM to AFM. The Mössbauer data indicate that vacancies in the monoclinic Fe3Se4 prefer to appear near the Fe(3+) ions and stimulate the magnetic transition with the rotation of the Fe(3+) magnetic moments. Unusually high coercive force Hc was found in both (H) and (M) nanocrystals with the highest ("giant") value of about 25 kOe in monoclinic Fe3Se4. This is explained by the strong surface magnetic anisotropy which is essentially larger than the core anisotropy. Such a large coercivity is rare for materials without rare earth or noble metal elements, and the Fe3Se4-based compounds can be the low-cost, nontoxic alternative materials for advanced magnets. In addition, an unusual effect of "switching" of magnetization in a field of 10 kOe was found in the Fe3Se4 nanoparticles below 280 K, which can be important for applications. PMID:25084934

  13. Superparamagnetic Fe3O4 Nanoparticles: Synthesis by Thermal Decomposition of Iron(III) Glucuronate and Application in Magnetic Resonance Imaging.

    PubMed

    Patsula, Vitalii; Kosinová, Lucie; Lovrić, Marija; Ferhatovic Hamzić, Lejla; Rabyk, Mariia; Konefal, Rafal; Paruzel, Aleksandra; Šlouf, Miroslav; Herynek, Vít; Gajović, Srećko; Horák, Daniel

    2016-03-23

    Monodisperse superparamagnetic Fe3O4 nanoparticles coated with oleic acid were prepared by thermal decomposition of Fe(III) glucuronate. The shape, size, and particle size distribution were controlled by varying the reaction parameters, such as the reaction temperature, concentration of the stabilizer, and type of high-boiling-point solvents. Magnetite particles were characterized by transmission electron microscopy (TEM), as well as electron diffraction (SAED), X-ray diffraction (XRD), dynamic light scattering (DLS), and magnetometer measurements. The particle coating was analyzed by atomic absorption spectroscopy (AAS) and attenuated total reflection (ATR) Fourier transform infrared spectroscopy (FTIR) spectroscopy. To make the Fe3O4 nanoparticles dispersible in water, the particle surface was modified with α-carboxyl-ω-bis(ethane-2,1-diyl)phosphonic acid-terminated poly(3-O-methacryloyl-α-D-glucopyranose) (PMG-P). For future practical biomedical applications, nontoxicity plays a key role, and the PMG-P&Fe3O4 nanoparticles were tested on rat mesenchymal stem cells to determine the particle toxicity and their ability to label the cells. MR relaxometry confirmed that the PMG-P&Fe3O4 nanoparticles had high relaxivity but rather low cellular uptake. Nevertheless, the labeled cells still provided visible contrast enhancement in the magnetic resonance image. In addition, the cell viability was not compromised by the nanoparticles. Therefore, the PMG-P&Fe3O4 nanoparticles have the potential to be used in biomedical applications, especially as contrast agents for magnetic resonance imaging. PMID:26928653

  14. Method validation for control determination of mercury in fresh fish and shrimp samples by solid sampling thermal decomposition/amalgamation atomic absorption spectrometry.

    PubMed

    Torres, Daiane Placido; Martins-Teixeira, Maristela Braga; Cadore, Solange; Queiroz, Helena Müller

    2015-01-01

    A method for the determination of total mercury in fresh fish and shrimp samples by solid sampling thermal decomposition/amalgamation atomic absorption spectrometry (TDA AAS) has been validated following international foodstuff protocols in order to fulfill the Brazilian National Residue Control Plan. The experimental parameters have been previously studied and optimized according to specific legislation on validation and inorganic contaminants in foodstuff. Linearity, sensitivity, specificity, detection and quantification limits, precision (repeatability and within-laboratory reproducibility), robustness as well as accuracy of the method have been evaluated. Linearity of response was satisfactory for the two range concentrations available on the TDA AAS equipment, between approximately 25.0 and 200.0 μg kg(-1) (square regression) and 250.0 and 2000.0 μg kg(-1) (linear regression) of mercury. The residues for both ranges were homoscedastic and independent, with normal distribution. Correlation coefficients obtained for these ranges were higher than 0.995. Limits of quantification (LOQ) and of detection of the method (LDM), based on signal standard deviation (SD) for a low-in-mercury sample, were 3.0 and 1.0 μg kg(-1), respectively. Repeatability of the method was better than 4%. Within-laboratory reproducibility achieved a relative SD better than 6%. Robustness of the current method was evaluated and pointed sample mass as a significant factor. Accuracy (assessed as the analyte recovery) was calculated on basis of the repeatability, and ranged from 89% to 99%. The obtained results showed the suitability of the present method for direct mercury measurement in fresh fish and shrimp samples and the importance of monitoring the analysis conditions for food control purposes. Additionally, the competence of this method was recognized by accreditation under the standard ISO/IEC 17025. PMID:25996815

  15. Erbium hydride decomposition kinetics.

    SciTech Connect

    Ferrizz, Robert Matthew

    2006-11-01

    Thermal desorption spectroscopy (TDS) is used to study the decomposition kinetics of erbium hydride thin films. The TDS results presented in this report are analyzed quantitatively using Redhead's method to yield kinetic parameters (E{sub A} {approx} 54.2 kcal/mol), which are then utilized to predict hydrogen outgassing in vacuum for a variety of thermal treatments. Interestingly, it was found that the activation energy for desorption can vary by more than 7 kcal/mol (0.30 eV) for seemingly similar samples. In addition, small amounts of less-stable hydrogen were observed for all erbium dihydride films. A detailed explanation of several approaches for analyzing thermal desorption spectra to obtain kinetic information is included as an appendix.

  16. The thermal decomposition of 1,3,5-trinitrohexahydro-1,3,5-triazine (RDX) and RDXd6 at high temperatures. [burning rate

    NASA Technical Reports Server (NTRS)

    Miller, P. J.; Nauflett, G. W.; Carlson, D. W.; Brasch, J. W., Sr.

    1980-01-01

    The ballistics behavior of nitramine propellants containing RDX in an inert binder was examined. It is shown that at 2000 to 5000 psi, depending on the particle size, a slope break or discontinuity in the log burning rate versus log pressure curve occurs. It is shown that at higher pressures the nitramine decomposition proceeds predominately by C-N bond rupture and gives CH2 and N20. At still higher pressures (after the slope break) the decomposition proceeds by N-N rupture. The decomposition of RDX was investigated from 170 to 800 C at atmospheric pressure. The major decomposition products were CH2, CO, CO2, N20, N2, and H20. The ratio of the products varied with the pyrolysis rate and temperature.

  17. Thermal decomposition behavior of the rare-earth ammonium sulfate R{sub 2}(SO{sub 4}){sub 3}.(NH{sub 4}){sub 2}SO{sub 4}

    SciTech Connect

    Nagai, Tsukasa; Tamura, Shinji; Imanaka, Nobuhito

    2010-07-15

    Rare-earth ammonium sulfate octahydrates of R{sub 2}(SO{sub 4}){sub 3}.(NH{sub 4}){sub 2}SO{sub 4}.8H{sub 2}O (R=Pr, Nd, Sm, and Eu) were synthesized by a wet process, and the stable temperature region for the anhydrous R{sub 2}(SO{sub 4}){sub 3}.(NH{sub 4}){sub 2}SO{sub 4} form was clarified by thermogravimetry/differential thermal analysis, infrared, Raman, and electrical conductivity measurements. Detailed characterization of these double salts demonstrated that the thermal stability of anhydrous R{sub 2}(SO{sub 4}){sub 3}.(NH{sub 4}){sub 2}SO{sub 4} is different between the Pr, Nd salts and the Sm, Eu salts, and the thermal decomposition behavior of these salts was quite different from the previous reports. - Graphical abstract: Stable temperature range of anhydrous rare-earth ammonium sulfate R{sub 2}(SO{sub 4}){sub 3}.(NH{sub 4}){sub 2}SO{sub 4} was clarified by thermogravimetry/differential thermal analysis, infrared, Raman, and electrical conductivity measurements. Since the previous reports were based only on thermal analysis, the present work has more accurately determined the exact thermal stability of rare-earth ammonium sulfate solids.

  18. Non-isothermal decomposition kinetics, heat capacity and thermal safety of 37.2/44/16/2.2/0.2/0.4-GAP/CL-20/Al/N-100/PCA/auxiliaries mixture.

    PubMed

    Zhang, Jiao-Qiang; Gao, Hong-Xu; Ji, Tie-Zheng; Xu, Kang-Zhen; Hu, Rong-Zu

    2011-10-15

    The specific heat capacity (C(p)) of 37.2/44/16/2.2/0.2/0.4-GAP/CL-20/Al/N-100/PCA/auxiliaries mixture was determined with the continuous C(p) mode of microcalorimeter. The equation of C(p) with temperature was obtained. The standard molar heat capacity of GAP/CL-20/Al/N-100/PCA/auxiliaries mixture was 1.225 J mol(-1)K(-1) at 298.15K. With the help of the peak temperature (T(p)) from the non-isothermal DTG curves of the mixture at different heating rates (β), the apparent activation energy (E(k) and E(o)) and pre-exponential constant (A(K)) of thermal decomposition reaction obtained by Kissinger's method and Ozawa's method. Using density (ρ) and thermal conductivity (λ), the decomposition heat (Q(d), taking half-explosion heat), Zhang-Hu-Xie-Li's formula, the values (T(e0) and T(p0)) of T(e) and T(p) corresponding to β → 0, thermal explosion temperature (T(be) and T(bp)), adiabatic time-to-explosion (t(TIad)), 50% drop height (H(50)) of impact sensitivity, and critical temperature of hot-spot initiation (T(cr,hot spot)) of thermal explosion of the mixture were calculated. The following results of evaluating the thermal safety of the mixture were obtained: T(be) = 441.64K, T(bp) = 461.66 K, t(Tlad) = 78.0 s (n = 2), t(Tlad) = 74.87 s (n = 1), t(Tlad) = 71.85 s (n = 0), H(50) = 21.33 cm. PMID:21820242

  19. Effect of content of Mg(NO3)2 x 6H2O on fabrication of alpha-alumina nanopowders by thermal decomposition of ammonium aluminum carbonate (AACH).

    PubMed

    Oh, Yong-Taeg; Shin, Dong-Chan

    2011-02-01

    An alpha-Al2O3 and MgAl2O3 spinel phase doped alpha-Al2O3 nanopowders were fabricated by the thermal decomposition and synthetic of ammonium aluminum carbonate hydroxide (AACH). Crystallite size of 5 to 8 nm were fabricated when reaction temperature of AACH was low, 8 degrees C, and the highest [NH4+][AlO(OH)2-][HCO3] ionic concentration of pH 10 from the ammonium hydrogen carbonate (AHC) aqueous solution. The phase transformation of amorphous-s, theta-, alpha-Al2O3, MgAl2O3 spinel phases was examined at each temperature according to the amount of Mg(NO3)2 x 6H2O and AACH. A time-temperature-transformation (TTT) diagram for thermal decomposition in air was determined. Homogeneous, spherical alpha-Al2O3 nanopowders with a particle size of 60 nm were obtained by firing the crystallites, which had been synthesized from AACH at pH 10 and 8 degrees C, at 1050 degrees C for 6 h in air. PMID:21456289

  20. Ab initio studies on the reactivity of the CF3OCH 2O radical: thermal decomposition vs. reaction with O2.

    PubMed

    Singh, Hari Ji; Mishra, Bhupesh Kumar

    2010-09-01

    Hydrofluoroethers are being considered as potential candidates for third generation refrigerants. The present investigation involves the ab initio quantum mechanical study of the decomposition mechanism of CF(3)OCH(2)O radical formed from a hydrofluoroether, CF(3)OCH(3) (HFE-143a) in the atmosphere. The geometries of the reactant, products and transition states involved in the decomposition pathways are optimized and characterized at the DFT (B3LYP) level of theory using 6-311G(d,p) basis set. Energy calculations have been performed at the G2(MP2) and G2M(CC,MP2) level of theory. Two prominent decomposition channels, C-O bond scission and reaction with atmospheric O(2) have been considered for detailed investigation. Studies performed at the G2(MP2) level reveals that the decomposition channel involving C-O bond scission occurs with a barrier height of 23.8 kcal mol(-1) whereas the oxidative pathway occurring with O(2) proceeds with an energy barrier of 7.2 kcal mol(-1). On the other hand the corresponding values at G2M(CC,MP2) are 24.5 and 5.9 kcal mol(-1) respectively. Using canonical transition state theory (CTST) rate constants for the two pathways considered are calculated at 298 K and 1 atm pressure and found to be 5.9 x 10(-6) s(-1) and 2.3 x 10(-5) s(-1) respectively. The present study concludes that reaction with O(2) is the dominant path for the consumption of CF(3)OCH(2)O in the atmosphere. Transition states are searched and characterized on the potential energy surfaces involved in both of the reaction channels. The existence of transition state on the corresponding potential energy surface is ascertained by performing intrinsic reaction coordinate (IRC) calculation. PMID:20169381

  1. Development of CdS Nanostructures by Thermal Decomposition of Aminocaproic Acid-Mixed Cd-Thiourea Complex Precursor: Structural, Optical and Photocatalytic Characterization.

    PubMed

    Patel, Jayesh D; Mighri, Frej; Ajji, Abdellah; Chaudhuri, Tapas K

    2015-04-01

    The present work deals with two different CdS nanostructures produced via hydrothermal and solvothermal decompositions of aminocaproic acid (ACA)-mixed Cd-thiourea complex precursor at 175 °C. Both nanostructures were extensively characterized for their structural, morphological and optical properties. The powder X-ray diffraction characterization showed that the two CdS nanostructures present a wurtzite morphology. Scanning electron microscopy and energy-dispersive X-ray characterizations revealed that the hydrothermal decomposition produced well-shaped CdS flowers composed of six dendritic petals, and the solvothermal decomposition produced CdS microspheres with close stoichiometric chemical composition. The UV-vis absorption and photoluminescence spectra of CdS dendritic flowers and microsphere nanostructures showed that both nanostructures present a broad absorption between 200 and 700 nm and exhibit strong green emissions at 576 and 520 nm upon excitations at 290 nm and 260 nm, respectively. The transmission electron microscopy (TEM) and Brunauer-Emmett-Teller (BET) characterizations confirmed that CdS microspheres were mesoporous and were composed of small nanocrystals. A possible growth mechanism in the formation of the CdS nanostructures was proposed based on morphology evolution as a function of the reaction time. Furthermore, the as-synthesized CdS nanostructures were found to exhibit highly efficient photocatalytic activities for the degradation of methyl orange (MeO) and rhodamine B (RhB) dyes. PMID:26353487

  2. Critical analysis of nitramine decomposition data: Activation energies and frequency factors for HMX and RDX decomposition

    NASA Technical Reports Server (NTRS)

    Schroeder, M. A.

    1980-01-01

    A summary of a literature review on thermal decomposition of HMX and RDX is presented. The decomposition apparently fits first order kinetics. Recommended values for Arrhenius parameters for HMX and RDX decomposition in the gaseous and liquid phases and for decomposition of RDX in solution in TNT are given. The apparent importance of autocatalysis is pointed out, as are some possible complications that may be encountered in interpreting extending or extrapolating kinetic data for these compounds from measurements carried out below their melting points to the higher temperatures and pressure characteristic of combustion.

  3. Synthesis, crystal structure and catalytic effect on thermal decomposition of RDX and AP: An energetic coordination polymer [Pb{sub 2}(C{sub 5}H{sub 3}N{sub 5}O{sub 5}){sub 2}(NMP)·NMP]{sub n}

    SciTech Connect

    Liu, Jin-jian; Liu, Zu-Liang; Cheng, Jian; Fang, Dong

    2013-04-15

    An energetic lead(II) coordination polymer based on the ligand ANPyO has been synthesized and its crystal structure has been got. The polymer was characterized by FT-IR spectroscopy, elemental analysis, DSC and TG-DTG technologies. Thermal analysis shows that there are one endothermic process and two exothermic decomposition stages in the temperature range of 50–600 °C with final residues 57.09%. The non-isothermal kinetic has also been studied on the main exothermic decomposition using the Kissinger's and Ozawa–Doyle's methods, the apparent activation energy is calculated as 195.2 KJ/mol. Furthermore, DSC measurements show that the polymer has significant catalytic effect on the thermal decomposition of ammonium perchlorate. - Graphical abstract: An energetic lead(II) coordination polymer of ANPyO has been synthesized, structurally characterized and properties tested. Highlights: ► We have synthesized and characterized an energetic lead(II) coordination polymer. ► We have measured its molecular structure and thermal decomposition. ► It has significant catalytic effect on thermal decomposition of AP.

  4. Ferrocene-based sulfonyl dihydropyrazole derivatives: Synthesis, structure, electrochemistry and effect on thermal decomposition of NH4ClO4

    NASA Astrophysics Data System (ADS)

    Zhuo, Ji-Bin; Li, Heng-Dong; Lin, Cai-Xia; Xie, Li-Li; Bai, Sha; Yuan, Yao-Feng

    2014-06-01

    Three ferrocene-based sulfonyl-substituted dihydropyrazoles 3a-c have been synthesized, from the corresponding α,β-unsaturated diketones, and fully characterized. The crystal structures of 3a-c have been confirmed by X-ray crystallography, and electrochemistry behaviors of 3a-c have been examined by cyclic voltammetry (CV). Representatively, the mechanism of the electron transfer in redox process of 3a has been verified by density functional theory (DFT) calculation. It has been found that the activity of catalytic decomposition of ammonium perchlorate (AP) is significantly lowered (by 62.9-104.7 °C) with an addition of 3a-c. We expect that the ferrocene-based sulfonyl dihydropyrazole derivatives would have a great value in burning rate catalyst as composite solid propellants.

  5. Magnéli phases Ti{sub 4}O{sub 7} and Ti{sub 8}O{sub 15} and their carbon nanocomposites via the thermal decomposition-precursor route

    SciTech Connect

    Conze, S.; Veremchuk, I.; Reibold, M.; Matthey, B.; Michaelis, A.; Grin, Yu.; Kinski, I.

    2015-09-15

    A new synthetic approach for producing nano-powders of the Magnéli phases Ti{sub 4}O{sub 7}, Ti{sub 8}O{sub 15} and their carbon nanocomposites by thermal decomposition-precursor route is proposed. The formation mechanism of the single-phase carbon nanocomposites (Ti{sub 4}O{sub 7}/C and Ti{sub 8}O{sub 15}/C) from metal–organic precursors is studied using FT-IR, elemental analysis, TG, STA-MS and others. The synthesis parameters and conditions were optimized to prepare the target oxides with the desired microstructure and physical properties. The electrical and transport properties of Ti{sub 4}O{sub 7}/C and Ti{sub 8}O{sub 15}/C are investigated. These nano-materials are n-type semiconductors with relatively low thermal conductivity in contrast to the bulk species. The nanostructured carbon nanocomposites of Magnéli phases achieve a low thermal conductivity close to 1 W/m K at RT. The maximum ZT{sub 570} {sub °C} values are 0.04 for Ti{sub 4}O{sub 7}/C powder nanocomposite and 0.01 for Ti{sub 8}O{sub 15}/C bulk nanocomposite. - Graphical abstract: From the precursor to the produced titanium oxide pellet and its microstructure (SEM, TEM micrographs) as well as results of phase and thermoelectric analyses. - Highlights: • Magnéli phases Ti{sub 4}O{sub 7}/Ti{sub 8}O{sub 15} via thermal decomposition-precursor route is proposed. • The formation mechanism of the nanocomposites Ti{sub 4}O{sub 7}/C and Ti{sub 8}O{sub 15}/C are investigated. • Microstructure of Ti{sub 4}O{sub 7}/C and Ti{sub 8}O{sub 15}/C are examined. • The electrical and transport properties of Ti{sub 4}O{sub 7}/C and Ti{sub 8}O{sub 15}/C are investigated. • The maximum figure of mertit ZT{sub 570} {sub °C} of Ti{sub 4}O{sub 7}/C and Ti{sub 8}O{sub 15}/C are 0.01 and 0.04.

  6. Utilizing carbon dioxide as a reaction medium to mitigate production of polycyclic aromatic hydrocarbons from the thermal decomposition of styrene butadiene rubber.

    PubMed

    Kwon, Eilhann E; Yi, Haakrho; Castaldi, Marco J

    2012-10-01

    The CO(2) cofeed impact on the pyrolysis of styrene butadiene rubber (SBR) was investigated using thermogravimetric analysis (TGA) coupled to online gas chromatography/mass spectroscopy (GC/MS). The direct comparison of the chemical species evolved from the thermal degradation of SBR in N(2) and CO(2) led to a preliminary mechanistic understanding of the formation and relationship of light hydrocarbons (C(1-4)), aromatic derivatives, and polycyclic aromatic hydrocarbons (PAHs), clarifying the role of CO(2) in the thermal degradation of SBR. The identification and quantification of over 50 major and minor chemical species from hydrogen and benzo[ghi]perylene were carried out experimentally in the temperature regime between 300 and 500 °C in N(2) and CO(2). The significant amounts of benzene derivatives from the direct bond dissociation of the backbone of SBR, induced by thermal degradation, provided favorable conditions for PAHs by the gas-phase addition reaction at a relatively low temperature compared to that with conventional fuels such as coal and petroleum-derived fuels. However, the formation of PAHs in a CO(2) atmosphere was decreased considerably (i.e., ∼50%) by the enhanced thermal cracking behavior, and the ultimate fates of these species were determined by different pathways in CO(2) and N(2) atmospheres. Consequently, this work has provided a new approach to mitigate PAHs by utilizing CO(2) as a reaction medium in thermochemical processes. PMID:22950720

  7. Nested Taylor decomposition in multivariate function decomposition

    NASA Astrophysics Data System (ADS)

    Baykara, N. A.; Gürvit, Ercan

    2014-12-01

    Fluctuationlessness approximation applied to the remainder term of a Taylor decomposition expressed in integral form is already used in many articles. Some forms of multi-point Taylor expansion also are considered in some articles. This work is somehow a combination these where the Taylor decomposition of a function is taken where the remainder is expressed in integral form. Then the integrand is decomposed to Taylor again, not necessarily around the same point as the first decomposition and a second remainder is obtained. After taking into consideration the necessary change of variables and converting the integration limits to the universal [0;1] interval a multiple integration system formed by a multivariate function is formed. Then it is intended to apply the Fluctuationlessness approximation to each of these integrals one by one and get better results as compared with the single node Taylor decomposition on which the Fluctuationlessness is applied.

  8. One Step Synthesis of NiO Nanoparticles via Solid-State Thermal Decomposition at Low-Temperature of Novel Aqua(2,9-dimethyl-1,10-phenanthroline)NiCl2 Complex

    PubMed Central

    Barakat, Assem; Al-Noaimi, Mousa; Suleiman, Mohammed; Aldwayyan, Abdullah S.; Hammouti, Belkheir; Ben Hadda, Taibi; Haddad, Salim F.; Boshaala, Ahmed; Warad, Ismail

    2013-01-01

    [NiCl2(C14H12N2)(H2O)] complex has been synthesized from nickel chloride hexahydrate (NiCl2·6H2O) and 2,9-dimethyl-1,10-phenanthroline (dmphen) as N,N-bidentate ligand. The synthesized complex was characterized by elemental analysis, infrared (IR) spectroscopy, ultraviolet-visible (UV-vis) spectroscopy and differential thermal/thermogravimetric analysis (TG/DTA). The complex was further confirmed by single crystal X-ray diffraction (XRD) as triclinic with space group P-1. The desired complex, subjected to thermal decomposition at low temperature of 400 ºC in an open atmosphere, revealed a novel and facile synthesis of pure NiO nanoparticles with uniform spherical particle; the structure of the NiO nanoparticles product was elucidated on the basis of Fourier transform infrared (FT-IR), UV-vis spectroscopy, TG/DTA, XRD, scanning electron microscopy (SEM), energy-dispersive X-ray spectrometry (EDXS) and transmission electron microscopy (TEM). PMID:24351867

  9. Characterization of Cobalt Oxide Nanoparticles Prepared by the Thermal Decomposition of [Co(NH3)5(H2O)](NO3)3 Complex and Study of Their Photocatalytic Activity.

    PubMed

    Farhadi, Saeed; Javanmard, Masoumeh; Nadri, Gholamali

    2016-01-01

    In this work, thermal decomposition of the [Co(NH3)5(H2O)](NO3)3 precursor complex was investigated under solid state conditions. Thermal analysis (TG/DTA) showed that the complexwas easily decomposed into the Co3O4 nanoparticles at low temperature (175 °C) without using any expensive and toxic solvent or a complicated equipment. The obtained product was identified by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDX). Optical and magnetic properties of the products were studied by UV-visible spectroscopy and a vibrating sample magnetometer (VSM), respectively. FT-IR, XRD and EDX analyses confirmed the formation of highly pure spinel-type Co3O4 phase with cubic structure. SEM and TEM images showed that the Co3O4 nanoparticles have a sphere-like morphology with an average size of 17.5 nm. The optical absorption spectrum of the Co3O4 nanoparticles showed two band gaps of 2.20 and 3.45 eV, which in turn confirmed the semiconducting properties. The magnetic measurement showed a weak ferromagnetic order at room temperature. Photocatalytic degradation of methylene blue (MB) demonstrated that the as-prepared Co3O4 nanoparticles have good photocatalytic activity under visible-light irradiation. PMID:27333557

  10. 15 CFR 732.2 - Steps regarding scope of the EAR.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ....) Editorial Note: For Federal Register citations affecting § 732.2, see the List of CFR Sections Affected... 15 Commerce and Foreign Trade 2 2013-01-01 2013-01-01 false Steps regarding scope of the EAR. 732... FOR USING THE EAR § 732.2 Steps regarding scope of the EAR. Steps 1 though 6 are designed to aid...

  11. 15 CFR 732.2 - Steps regarding scope of the EAR.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 15 Commerce and Foreign Trade 2 2010-01-01 2010-01-01 false Steps regarding scope of the EAR. 732... FOR USING THE EAR § 732.2 Steps regarding scope of the EAR. Steps 1 though 6 are designed to aid you in determining the scope of the EAR. A flow chart describing these steps is contained in...

  12. 15 CFR 732.2 - Steps regarding scope of the EAR.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ....) Editorial Note: For Federal Register citations affecting § 732.2, see the List of CFR Sections Affected... 15 Commerce and Foreign Trade 2 2012-01-01 2012-01-01 false Steps regarding scope of the EAR. 732... FOR USING THE EAR § 732.2 Steps regarding scope of the EAR. Steps 1 though 6 are designed to aid...

  13. 15 CFR 732.2 - Steps regarding scope of the EAR.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... section. (2) Editorial Note: For Federal Register citations affecting § 732.2, see the List of CFR... 15 Commerce and Foreign Trade 2 2014-01-01 2014-01-01 false Steps regarding scope of the EAR. 732... FOR USING THE EAR § 732.2 Steps regarding scope of the EAR. Steps 1 though 6 are designed to aid...

  14. 15 CFR 732.2 - Steps regarding scope of the EAR.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 15 Commerce and Foreign Trade 2 2011-01-01 2011-01-01 false Steps regarding scope of the EAR. 732... FOR USING THE EAR § 732.2 Steps regarding scope of the EAR. Steps 1 though 6 are designed to aid you in determining the scope of the EAR. A flow chart describing these steps is contained in...

  15. Fast intensity-modulated arc therapy based on 2-step beam segmentation

    SciTech Connect

    Bratengeier, Klaus; Gainey, Mark; Sauer, Otto A.; Richter, Anne; Flentje, Michael

    2011-01-15

    Purpose: Single or few arc intensity-modulated arc therapy (IMAT) is intended to be a time saving irradiation method, potentially replacing classical intensity-modulated radiotherapy (IMRT). The aim of this work was to evaluate the quality of different IMAT methods with the potential of fast delivery, which also has the possibility of adapting to the daily shape of the target volume. Methods: A planning study was performed. Novel double and triple IMAT techniques based on the geometrical analysis of the target organ at risk geometry (2-step IMAT) were evaluated. They were compared to step and shoot IMRT reference plans generated using direct machine parameter optimization (DMPO). Volumetric arc (VMAT) plans from commercial preclinical software (SMARTARC) were used as an additional benchmark to classify the quality of the novel techniques. Four cases with concave planning target volumes (PTV) with one dominating organ at risk (OAR), viz., the PTV/OAR combination of the ESTRO Quasimodo phantom, breast/lung, spine metastasis/spinal cord, and prostate/rectum, were used for the study. The composite objective value (COV) and other parameters representing the plan quality were studied. Results: The novel 2-step IMAT techniques with geometry based segment definition were as good as or better than DMPO and were superior to the SMARTARC VMAT techniques. For the spine metastasis, the quality measured by the COV differed only by 3%, whereas the COV of the 2-step IMAT for the other three cases decreased by a factor of 1.4-2.4 with respect to the reference plans. Conclusions: Rotational techniques based on geometrical analysis of the optimization problem (2-step IMAT) provide similar or better plan quality than DMPO or the research version of SMARTARC VMAT variants. The results justify pursuing the goal of fast IMAT adaptation based on 2-step IMAT techniques.

  16. Development of a hydrophilic interaction liquid chromatography-mass spectrometry method for detection and quantification of urea thermal decomposition by-products in emission from diesel engine employing selective catalytic reduction technology.

    PubMed

    Yassine, Mahmoud M; Dabek-Zlotorzynska, Ewa; Celo, Valbona

    2012-03-16

    The use of urea based selective catalytic reduction (SCR) technology for the reduction of NOx from the exhaust of diesel-powered vehicles has the potential to emit at least six thermal decomposition by-products, ammonia, and unreacted urea from the tailpipe. These compounds may include: biuret, dicyandiamine, cyanuric acid, ammelide, ammeline and melamine. In the present study, a simple, sensitive and reliable hydrophilic interaction liquid chromatography (HILIC)-electrospray ionization (ESI)/mass spectrometry (MS) method without complex sample pre-treatment was developed for identification and determination of urea decomposition by-products in diesel exhaust. Gradient separation was performed on a SeQuant ZIC-HILIC column with a highly polar zwitterionic stationary phase, and using a mobile phase consisting of acetonitrile (eluent A) and 15 mM ammonium formate (pH 6; eluent B). Detection and quantification were performed using a quadrupole ESI/MS operated simultaneously in negative and positive mode. With 10 μL injection volume, LODs for all target analytes were in the range of 0.2-3 μg/L. The method showed a good inter-day precision of retention time (RSD<0.5%) and peak area (RSD<3%). Satisfactory extraction recoveries from spiked blanks ranged between 96 and 98%. Analyses of samples collected during transient chassis dynamometer tests of a bus engine equipped with a diesel particulate filter (DPF) and urea based SCR technology showed the presence of five target analytes with cyanuric acid and ammelide the most abundant compounds in the exhaust. PMID:22318005

  17. Thermal decomposition behavior of Cu–Al layered double hydroxide, and ethylenediaminetetraacetate-intercalated Cu–Al layered double hydroxide reconstructed from Cu–Al oxide for uptake of Y{sup 3+} from aqueous solution

    SciTech Connect

    Kameda, Tomohito; Hoshi, Kazuaki; Yoshioka, Toshiaki

    2012-12-15

    Graphical abstract: Display Omitted Highlights: ► Decomposition of CO{sub 3}·Cu–Al LDH occurred in four stages. ► The edta·Cu–Al LDH was found to take up Y{sup 3+} in aqueous solution. ► The edta·Cu–Al LDH could selectively take up rare earth ions from a mixed solution. -- Abstract: CO{sub 3}{sup 2−}-intercalated Cu–Al layered double hydroxide (CO{sub 3}·Cu–Al LDH) was calcined to yield Cu–Al oxide, and then ethylenediaminetetraacetate-intercalated Cu–Al LDH (edta·Cu–Al LDH) was prepared by reconstructing Cu–Al oxide in edta solution. Decomposition of CO{sub 3}·Cu–Al LDH occurred in four stages. The production of Cu–Al oxide was caused by the thermal decomposition of CO{sub 3}·Cu–Al LDH until the third stage. The first stage was the elimination of adsorbed surface water and interlayer water in CO{sub 3}·Cu–Al LDH. The second and third stages were the dehydroxylation of the brucite-like octahedral layers and the elimination of CO{sub 3}{sup 2−} intercalated in the interlayers. The edta·Cu–Al LDH was found to take up Y{sup 3+} in aqueous solution. The uptake of Y{sup 3+} was caused not only by the chelating function of Hedta{sup 3−} in the interlayer but also by the chemical behavior of Cu–Al LDH itself. The edta·Cu–Al LDH was found to selectively take up rare earth ions from a mixed solution. The degree of uptake was high, in the order Sc{sup 3+} > Y{sup 3+} > La{sup 3+} for all time durations, which was attributable to differences among the stabilities of Sc(edta){sup −}, Y(edta){sup −} and La(edta){sup −}.

  18. MgCoAl and NiCoAl LDHs synthesized by the hydrothermal urea hydrolysis method: Structural characterization and thermal decomposition

    SciTech Connect

    Chagas, L.H.; De Carvalho, G.S.G.; Do Carmo, W.R.; San Gil, R.A.S.; Chiaro, S.S.X.; Leitão, A.A.; Diniz, R.; De Sena, L.A.; Achete, C.A.

    2015-04-15

    Highlights: • We synthesized MgCoAl and NiCoAl LDHs by the urea hydrolysis method. • Aluminum rich and crystalline materials have been formed. • The calcination of the LDHs generated mixed oxides with high surface areas. - Abstract: Layered double hydroxides (LDHs) with Mg/Co/Al and Ni/Co/Al were synthesized for the first time by the urea hydrolysis method. The experimental conditions promoted aluminum rich and crystalline materials. The formation of LDHs was investigated by powder X-ray diffraction (XRD), chemical analysis, solid state nuclear magnetic resonance with magic angle spinning ({sup 27}Al-MAS-NMR), simultaneous thermogravimetric/differential thermal analysis (TGA/DTA), FTIR spectroscopy, scanning electron microscopy (SEM), and N{sub 2} adsorption–desorption experiments. A single phase corresponding to LDH could be obtained in all the investigated compositions. Thermal calcination of these LDHs at 500 °C resulted in the formation of solid solutions in which Al{sup 3+} was dissolved. All the calcined materials have rock-salt like structures and high surface areas.

  19. Non-isothermal decomposition kinetics of diosgenin

    NASA Astrophysics Data System (ADS)

    Chen, Fei-xiong; Fu, Li; Feng, Lu; Liu, Chuo-chuo; Ren, Bao-zeng

    2013-10-01

    The thermal stability and kinetics of isothermal decomposition of diosgenin were studied by thermogravimetry (TG) and Differential Scanning Calorimeter (DSC). The activation energy of the thermal decomposition process was determined from the analysis of TG curves by the methods of Flynn-Wall-Ozawa, Doyle, Šatava-Šesták and Kissinger, respectively. The mechanism of thermal decomposition was determined to be Avrami-Erofeev equation ( n = 1/3, n is the reaction order) with integral form G(α) = [-ln(1 - α)]1/3 (α = 0.10-0.80). E a and log A [s-1] were determined to be 44.10 kJ mol-1 and 3.12, respectively. Moreover, the thermodynamics properties of Δ H ≠, Δ S ≠, and Δ G ≠ of this reaction were 38.18 kJ mol-1, -199.76 J mol-1 K-1, and 164.36 kJ mol-1 in the stage of thermal decomposition.

  20. Controlled synthesis of nanoporous nickel oxide with two-dimensional shapes through thermal decomposition of metal-cyanide hybrid coordination polymers.

    PubMed

    Zakaria, Mohamed B; Hu, Ming; Salunkhe, Rahul R; Pramanik, Malay; Takai, Kimiko; Malgras, Victor; Choi, Seyong; Dou, Shi Xue; Kim, Jung Ho; Imura, Masataka; Ishihara, Shinsuke; Yamauchi, Yusuke

    2015-02-23

    The urgent need for nanoporous metal oxides with highly crystallized frameworks is motivating scientists to try to discover new preparation methods, because of their wide use in practical applications. Recent work has demonstrated that two-dimensional (2D) cyanide-bridged coordination polymers (CPs) are promising materials and appropriate for this purpose (Angew. Chem. Int. Ed.- 2013, 52, 1235). After calcination, 2D CPs can be transformed into nanoporous metal oxides with a highly accessible surface area. Here, this strategy is adopted in order to form 2D nanoporous nickel oxide (NiO) with tunable porosity and crystallinity, using trisodium citrate dihydrate as a controlling agent. The presence of trisodium citrate dihydrate plays a key role in the formation of 2D nanoflakes by controlling the nucleation rate and the crystal growth. The size of the nanoflakes gradually increases by augmenting the amount of trisodium citrate dihydrate in the reaction. After heating the as-prepared CPs in air at different temperatures, nanoporous NiO can be obtained. During this thermal treatment, organic units (carbon and nitrogen) are completely removed and only the metal content remains to take part in the formation of nanoporous NiO. In the case of large-sized 2D CP nanoflakes, the original 2D flake-shapes are almost retained, even after thermal treatment at low temperature, but they are completely destroyed at high temperature because of further crystallization in the framework. Nanoporous NiO with high surface area shows significant efficiency and interesting results for supercapacitor application. PMID:25639533

  1. Research on anisotropic bonded Nd-Fe-B magnets by 2-step compaction process

    NASA Astrophysics Data System (ADS)

    Ma, Bin; Sun, Aizhi; Lu, Zhenwen; Cheng, Chuan; Xu, Chen

    2016-03-01

    In this paper, a novel 2-step compaction process, called a cold preforming step and a warm alignment and densification step, is proposed to prepare anisotropic bonded Nd-Fe-B magnets with high magnetic properties. The morphology of Nd-Fe-B particles is characterized by scanning electron microscopy. Research shows that the lower the density of preforms, the higher the (BH)max and DOA of Nd-Fe-B magnets. The (BH)max of Nd-Fe-B magnets prepared by 2-step compaction process is higher than that of traditional warm compaction process at the apace rate of 20% when the preform density is lower than 4.06 g/cm3. The (BH)max and DOA first increase and then decline with increasing space rate, the maximum is obtained at the space rate of 25% when the preform density is 3.98 g/cm3. By means of 2-step compaction process, not only (BH)max and DOA of Nd-Fe-B magnets are increased by 32.2% and 61.3% at the space rate of 25%, but also problems such as the easy damage of mould and the inhomogeneous of particle packing are solved, which are in favour of the extension of mould life. The changes of coercivity is not obvious during the research. The mechanrsms of space rate on DOA and density are analyzed and discussed.

  2. Room temperature synthesis of rod-like FeC2O4·2H2O and its transition to maghemite, magnetite and hematite nanorods through controlled thermal decomposition

    NASA Astrophysics Data System (ADS)

    Zhou, Weiwei; Tang, Kaibin; Zeng, Suyuan; Qi, Yunxia

    2008-02-01

    FeC2O4·2H2O nanorods with diameter of about 50 nm and length of up to several micrometers were synthesized at room temperature in a surfactant-assisted system, which was obtained by dissolving bis(2-ethylhexyl)sodium sulfosuccinate (AOT) in a mixed solution composed of water and ethylene glycol (EG). The influence of reaction conditions on the morphology of FeC2O4·2H2O is discussed in detail. Through direct thermal decomposition of FeC2O4·2H2O under different calcination conditions, maghemite (γ-Fe2O3), magnetite (Fe3O4) and hematite (α-Fe2O3) can be selectively obtained, preserving the rod-like morphology. Transmission electron microscope (TEM) and high-resolution transmission electron microscope (HRTEM) characterizations showed that the as-obtained iron oxide nanorods were composed of fine particles with different crystal orientations. The magnetic properties of the as-obtained iron oxide nanorods were systematically investigated.

  3. Selective synthesis of the [Ni36Co8C8(CO)48]6- octa-carbide carbonyl cluster by thermal decomposition of the [H2Ni22Co6C6(CO)36]4- hexa-carbide.

    PubMed

    Ciabatti, Iacopo; Fabrizi de Biani, Fabrizia; Femoni, Cristina; Iapalucci, Maria Carmela; Longoni, Giuliano; Zacchini, Stefano

    2013-07-14

    The thermal decomposition in thf solution of [H2Ni22Co6C6(CO)36](4-) results in the new [HNi36Co8C8(CO)48](5-) bimetallic Ni-Co octa-carbide, which can be converted into the closely related [H6-nNi36Co8C8(CO)48](n-) (n = 3-6) polyhydrides by means of acid-base reactions. The structure of the [Ni36Co8C8(CO)48](6-) hexa-anion has been established via X-ray crystallography, showing that the eight interstitial carbide atoms are lodged within different metal cages. Thus, two C-atoms are enclosed within regular square anti-prismatic Ni8C cages, four within irregular Ni8C square anti-prismatic cages, and the last two within mono-capped trigonal prismatic Ni5Co2C cages. The structure of [Ni36Co8C8(CO)48](6-) is non-compact and closely related to [Ni32C6(CO)38](6-) and [HNi38C6(CO)44](5-). [Ni36Co8C8(CO)48](6-) approaches the nanosize regime and the whole molecular ion has a diameter (measured from the outer oxygen atoms) of ca. 1.61 nm. PMID:23676989

  4. Structural refinement of Nd[Fe(CN) 6]·4H 2O and study of NdFeO 3 obtained by its oxidative thermal decomposition at very low temperatures

    NASA Astrophysics Data System (ADS)

    Navarro, M. Carolina; Pannunzio-Miner, Elisa V.; Pagola, Silvina; Gómez, M. Inés; Carbonio, Raúl E.

    2005-03-01

    The crystal structure of Nd[Fe(CN) 6]·4H 2O has been refined by Rietveld analysis using high resolution synchrotron powder X-ray diffraction data. It belonged to the orthorhombic crystal system, Cmcm space group, with cell parameters: a=7.473952(1) Å, b=12.919104(2) Å and c=13.800549(2) Å. The change in space group from P6 3/ m which is observed in the pentahydrates (LnFe(CN) 6·5H 2O) to Cmcm in the tetrahydrates has been analyzed to be a consequence of the change in 9-fold coordination of Nd 3+ in the pentahydrates to 8-fold coordination in the tetrahydrates, which changes the Nd 3+ environment from tricapped trigonal prism to a distorted tricapped trigonal prism or square antiprism. Its decomposition process in air to produce NdFeO 3 has been followed by thermogravimetric and differential thermal analysis, IR spectroscopy and laboratory powder XRD. We found that it is possible to synthesize crystalline NdFeO 3 at temperatures as low as 380 °C and refine the structure of single phase crystalline NdFeO 3 synthesized by this method at 600 °C.

  5. STUDIES OF THERMALLY UNSTABLE ACCRETION DISKS AROUND BLACK HOLES WITH ADAPTIVE PSEUDOSPECTRAL DOMAIN DECOMPOSITION METHOD. II. LIMIT-CYCLE BEHAVIOR IN ACCRETION DISKS AROUND KERR BLACK HOLES

    SciTech Connect

    Xue Li; Lu Jufu; Sadowski, Aleksander; Abramowicz, Marek A. E-mail: lujf@xmu.edu.cn

    2011-07-01

    For the first time ever, we derive equations governing the time evolution of fully relativistic slim accretion disks in the Kerr metric and numerically construct their detailed non-stationary models. We discuss applications of these general results to a possible limit-cycle behavior of thermally unstable disks. Our equations and numerical method are applicable in a wide class of possible viscosity prescriptions, but in this paper we use a diffusive form of the 'standard alpha prescription' that assumes that the viscous torque is proportional to the total pressure. In this particular case, we find that the parameters that dominate the limit-cycle properties are the mass-supply rate and the value of the alpha-viscosity parameter. Although the duration of the cycle (or the outburst) does not exhibit any clear dependence on the black hole spin, the maximal outburst luminosity (in the Eddington units) is positively correlated with the spin value. We suggest a simple method for a rough estimate of the black hole spin based on the maximal luminosity and the ratio of outburst to cycle durations. We also discuss a temperature-luminosity relation for the Kerr black hole accretion disk limit cycle. Based on these results, we discuss the limit-cycle behavior observed in microquasar GRS 1915+105. We also extend this study to several non-standard viscosity prescriptions, including a 'delayed heating' prescription recently addressed by the MHD simulations of accretion disks.

  6. Photocatalytic decomposition of selected estrogens and their estrogenic activity by UV-LED irradiated TiO2 immobilized on porous titanium sheets via thermal-chemical oxidation.

    PubMed

    Arlos, Maricor J; Liang, Robert; Hatat-Fraile, Melisa M; Bragg, Leslie M; Zhou, Norman Y; Servos, Mark R; Andrews, Susan A

    2016-11-15

    The removal of endocrine disrupting compounds (EDCs) remains a big challenge in water treatment. Risks associated with these compounds are not clearly defined and it is important that the water industry has additional options to increase the resiliency of water treatment systems. Titanium dioxide (TiO2) has potential applications for the removal of EDCs from water. TiO2 has been immobilized on supports using a variety of synthesis methods to increase its feasibility for water treatment. In this study, we immobilized TiO2 through the thermal-chemical oxidation of porous titania sheets. The efficiency of the material to degrade target EDCs under UV-LED irradiation was examined under a wide range of pH conditions. A yeast-estrogen screen assay was used to complement chemical analysis in assessing removal efficiency. All compounds but 17β-estradiol were degraded and followed a pseudo first-order kinetics at all pH conditions tested, with pH 4 and pH 11 showing the most and the least efficient treatments respectively. In addition, the total estrogenic activity was substantially reduced even with the inefficient degradation of 17β-estradiol. Additional studies will be required to optimize different treatment conditions, UV-LED configurations, and membrane fouling mitigation measures to make this technology a more viable option for water treatment. PMID:27469042

  7. Obtaining aluminas from the thermal decomposition of their different precursors: An {sup 27}Al MAS NMR and X-ray powder diffraction studies

    SciTech Connect

    Chagas, L.H.; De Carvalho, G.S.G.; San Gil, R.A.S.; Chiaro, S.S.X.; Leitão, A.A.; Diniz, R.

    2014-01-01

    Graphical abstract: - Highlights: • We synthesized three precursors of alumina from different methods. • The calcination of the precursors generated several alumina polymorphs. • XRD and NMR were used for structural investigation of the polymorphs. • The synthesis route determines the structural and textural properties of the solids. - Abstract: A commercial sample of Boehmite was used as precursor of alumina polymorphs. For comparison, three other precursors were synthesized from different methods. Particularly, the use of excess of urea promoted a very crystalline form of basic aluminum carbonate. The characteristics of the four precursors were investigated by thermal, vibrational and X-ray powder diffraction (XRD) analysis. Additionally, the nuclear magnetic resonance, with magic angle spinning ({sup 27}Al MAS NMR), was used to verify the coordination of aluminum cations. Each precursor was calcined at various temperatures generating alumina polymorphs, which were structurally analyzed by XRD and {sup 27}Al MAS NMR. Due to interest in catalysis supports, special attention was given to the γ-Al{sub 2}O{sub 3} phase, which in addition to structural investigation was subjected to textural analysis. The results showed that, from different synthesis procedures and common route of calcination, one can obtain materials with the same composition but with different structural and textural properties, which in turn can significantly influence the performance of a supported catalyst.

  8. Orthogonal tensor decompositions

    SciTech Connect

    Tamara G. Kolda

    2000-03-01

    The authors explore the orthogonal decomposition of tensors (also known as multi-dimensional arrays or n-way arrays) using two different definitions of orthogonality. They present numerous examples to illustrate the difficulties in understanding such decompositions. They conclude with a counterexample to a tensor extension of the Eckart-Young SVD approximation theorem by Leibovici and Sabatier [Linear Algebra Appl. 269(1998):307--329].

  9. Isothermal Decomposition of Hydrogen Peroxide Dihydrate

    NASA Technical Reports Server (NTRS)

    Loeffler, M. J.; Baragiola, R. A.

    2011-01-01

    We present a new method of growing pure solid hydrogen peroxide in an ultra high vacuum environment and apply it to determine thermal stability of the dihydrate compound that forms when water and hydrogen peroxide are mixed at low temperatures. Using infrared spectroscopy and thermogravimetric analysis, we quantified the isothermal decomposition of the metastable dihydrate at 151.6 K. This decomposition occurs by fractional distillation through the preferential sublimation of water, which leads to the formation of pure hydrogen peroxide. The results imply that in an astronomical environment where condensed mixtures of H2O2 and H2O are shielded from radiolytic decomposition and warmed to temperatures where sublimation is significant, highly concentrated or even pure hydrogen peroxide may form.

  10. Thermal Decomposition of Nitrated Tributyl Phosphate

    SciTech Connect

    Paddleford, D.F.; Hou, Y.; Barefield, E.K.; Tedder, D.W.; Abdel-Khalik, S.I.

    1995-01-01

    Contact between tributyl phosphate and aqueous solutions of nitric acid and/or heavy metal nitrate salts at elevated temperatures can lead to exothermic reactions of explosive violence. Even though such operations have been routinely performed safely for decades as an intrinsic part of the Purex separation processes, several so-called ``red oil`` explosions are known to have occurred in the United States, Canada, and the former Soviet Union. The most recent red oil explosion occurred at the Tomsk-7 separations facility in Siberia, in April 1993. That explosion destroyed part of the unreinforced masonry walls of the canyon-type building in which the process was housed, and allowed the release of a significant quantity of radioactive material.

  11. Decomposing Nekrasov decomposition

    NASA Astrophysics Data System (ADS)

    Morozov, A.; Zenkevich, Y.

    2016-02-01

    AGT relations imply that the four-point conformal block admits a decomposition into a sum over pairs of Young diagrams of essentially rational Nekrasov functions — this is immediately seen when conformal block is represented in the form of a matrix model. However, the q-deformation of the same block has a deeper decomposition — into a sum over a quadruple of Young diagrams of a product of four topological vertices. We analyze the interplay between these two decompositions, their properties and their generalization to multi-point conformal blocks. In the latter case we explain how Dotsenko-Fateev all-with-all (star) pair "interaction" is reduced to the quiver model nearest-neighbor (chain) one. We give new identities for q-Selberg averages of pairs of generalized Macdonald polynomials. We also translate the slicing invariance of refined topological strings into the language of conformal blocks and interpret it as abelianization of generalized Macdonald polynomials.

  12. Decomposition of Copper (II) Sulfate Pentahydrate: A Sequential Gravimetric Analysis.

    ERIC Educational Resources Information Center

    Harris, Arlo D.; Kalbus, Lee H.

    1979-01-01

    Describes an improved experiment of the thermal dehydration of copper (II) sulfate pentahydrate. The improvements described here are control of the temperature environment and a quantitative study of the decomposition reaction to a thermally stable oxide. Data will suffice to show sequential gravimetric analysis. (Author/SA)

  13. Decomposition characteristics of toluene by a corona radical shower system.

    PubMed

    Wu, Zu-liang; Gao, Xiang; Luo, Zhong-yang; Ni, Ming-jiang; Cen, Ke-fa

    2004-01-01

    Non-thermal plasma technologies offer an innovative approach to decomposing various volatile organic compounds(VOCs). The decomposition of toluene from simulated flue gas was investigated using a pipe electrode with nozzles for the generation of free radicals. Corona characteristics and decomposition of toluene were investigated experimentally. In addition, the decomposition mechanism of toluene was explored in view of reaction rate. The experimental results showed that the humidity of additional gas has an important effect on corona characteristics and modes and stable streamer corona can be generated through optimizing flow rate and humidity of additional gas. Applied voltage, concentration of toluene, humidity of toluene and resident time are some important factors affecting decomposition efficiency. Under optimizing conditions, the decomposition efficiency of toluene can reach 80%. These results can give a conclusion that the corona radical shower technology is feasible and effective on the removal of toluene in the flue gas. PMID:15495952

  14. A cyanide-bridged heterometallic coordination polymer constructed from square-planar [Ni(CN)4](2-): synthesis, crystal structure, thermal decomposition, electron paramagnetic resonance (EPR) spectrum and magnetic properties.

    PubMed

    Qin, Ying Lian; Yang, Bin Wu; Wang, Gao Feng; Sun, Hong

    2016-07-01

    Square-planar complexes are commonly formed by transition metal ions having a d(8) electron configuration. Planar cyanometallate anions have been used extensively as design elements in supramolecular coordination systems. In particular, square-planar tetracyanometallate(II) ions, i.e. [M(CN)4](2-) (M(II) = Ni, Pd or Pt), are used as good building blocks for bimetallic Hofmann-type assemblies and their analogues. Square-planar tetracyanonickellate(II) complexes have been extensively developed with N-donor groups as additional co-ligands, but studies of these systems using O-donor ligands are scarce. A new cyanide-bridged Cu(II)-Ni(II) heterometallic compound, poly[[diaquatetra-μ2-cyanido-κ(8)C:N-nickel(II)copper(II)] monohydrate], {[Cu(II)Ni(II)(CN)4(H2O)2]·H2O}n, has been synthesized and characterized by X-ray single-crystal diffraction analyses, vibrational spectroscopy (FT-IR), thermal analysis, electron paramagnetic resonance (EPR) and magnetic moment measurements. The structural analysis revealed that it has a two-dimensional grid-like structure built up of cationic [Cu(H2O)2](2+) and anionic [Ni(CN)4](2-) units connected through bridging cyanide ligands. The overall three-dimensional supramolecular network is expanded by a combination of interlayer O-H...N and intralayer O-H...O hydrogen-bond interactions. The first decomposition reactions take place at 335 K under a static air atmosphere, which illustrates the existence of guest water molecules in the interlayer spaces. The electron paramagnetic resonance (EPR) spectrum confirms that the Cu(II) cation has an axial coordination symmetry and that the unpaired electrons occupy the d(x(2)-y(2)) orbital. In addition, magnetic investigations showed that antiferromagnetic interactions exist in the Cu(II) atoms through the diamagnetic [Ni(CN)4](2-) ion. PMID:27377277

  15. Structural, magnetic, and electronic properties of iron selenide Fe{sub 6-7}Se{sub 8} nanoparticles obtained by thermal decomposition in high-temperature organic solvents

    SciTech Connect

    Lyubutin, I. S. E-mail: crlin@mail.npue.edu.tw; Funtov, K. O.; Dmitrieva, T. V.; Starchikov, S. S.; Lin, Chun-Rong E-mail: crlin@mail.npue.edu.tw; Siao, Yu-Jhan; Chen, Mei-Li

    2014-07-28

    Iron selenide nanoparticles with the NiAs-like crystal structure were synthesized by thermal decomposition of iron chloride and selenium powder in a high-temperature organic solvent. Depending on the time of the compound processing at 340 °C, the nanocrystals with monoclinic (M)-Fe{sub 3}Se{sub 4} or hexagonal (H)-Fe{sub 7}Se{sub 8} structures as well as a mixture of these two phases can be obtained. The magnetic behavior of the monoclinic and hexagonal phases is very different. The applied-field and temperature dependences of magnetization reveal a complicated transformation between ferrimagnetic (FRM) and antiferromagnetic (AFM) structures, which can be related to the spin rotation process connected with the redistribution of cation vacancies. From XRD and Mössbauer data, the 3c type superstructure of vacancy ordering was found in the hexagonal Fe{sub 7}Se{sub 8}. Redistribution of vacancies in Fe{sub 7}Se{sub 8} from random to ordered leads to the transformation of the magnetic structure from FRM to AFM. The Mössbauer data indicate that vacancies in the monoclinic Fe{sub 3}Se{sub 4} prefer to appear near the Fe{sup 3+} ions and stimulate the magnetic transition with the rotation of the Fe{sup 3+} magnetic moments. Unusually high coercive force H{sub c} was found in both (H) and (M) nanocrystals with the highest (“giant”) value of about 25 kOe in monoclinic Fe{sub 3}Se{sub 4}. This is explained by the strong surface magnetic anisotropy which is essentially larger than the core anisotropy. Such a large coercivity is rare for materials without rare earth or noble metal elements, and the Fe{sub 3}Se{sub 4}-based compounds can be the low-cost, nontoxic alternative materials for advanced magnets. In addition, an unusual effect of “switching” of magnetization in a field of 10 kOe was found in the Fe{sub 3}Se{sub 4} nanoparticles below 280 K, which can be important for applications.

  16. 2-step purification of the Ku DNA repair protein expressed in Escherichia coli

    PubMed Central

    2007-01-01

    The Ku protein is involved in DNA double-strand break repair by non-homologous end-joining (NHEJ), which is crucial to the maintenance of genomic integrity in mammals. To study the role of Ku in NHEJ we developed a bicistronic E. coli expression system for the Ku70 and Ku80 subunits. Association of the Ku70 and Ku80 subunits buries a substantial amount of surface area (~9000Å2 [1]), which suggests that herterodimerization may be important for protein stability. N-terminally his6-tagged Ku80 was soluble in the presence, but not in the absence, of bicistronically expressed untagged Ku70. In a 2-step purification, metal chelating affinity chromatography was followed by step-gradient elution from heparin-agarose. Co-purification of equimolar amounts of his6-tagged Ku80 and untagged Ku70 was observed, which indicated heterodimerization. Recombinant Ku bound dsDNA, activated the catalytic subunit of the DNA-dependent kinase (DNA-PKcs) and functioned in NHEJ reactions in vitro. Our results demonstrate that while the heterodimeric interface of Ku is extensive it is nonetheless possible to produce biologically active Ku protein in E. coli. PMID:17110127

  17. Hydrazine decomposition and other reactions

    NASA Technical Reports Server (NTRS)

    Armstrong, Warren E. (Inventor); La France, Donald S. (Inventor); Voge, Hervey H. (Inventor)

    1978-01-01

    This invention relates to the catalytic decomposition of hydrazine, catalysts useful for this decomposition and other reactions, and to reactions in hydrogen atmospheres generally using carbon-containing catalysts.

  18. Reprocessed polylactide: studies of thermo-oxidative decomposition.

    PubMed

    Badia, J D; Santonja-Blasco, L; Martínez-Felipe, A; Ribes-Greus, A

    2012-06-01

    The combustion process of virgin and reprocessed polylactide (PLA) was simulated by multi-rate linear non-isothermal thermogravimetric experiments under O(2). A complete methodology that accounted on the thermal stability and emission of gases was thoroughly developed. A new model, Thermal Decomposition Behavior, and novel parameters, the Zero-Decomposition Temperatures, were used to test the thermal stability of the materials under any linear heating rate. The release of gases was monitored by Evolved Gas Analysis with in-line FT-IR analysis. In addition, a kinetic analysis methodology that accounted for variable activation parameters showed that the decomposition process could be driven by the formation of bubbles in the melt. It was found that the combustion technologies for virgin PLA could be transferred for the energetic valorization of its recyclates. Combustion was pointed out as appropriate for the energetic valorization of PLA submitted to more than three successive reprocessing cycles. PMID:22481003

  19. Multicriteria approximation through decomposition

    SciTech Connect

    Burch, C. |; Krumke, S.; Marathe, M.; Phillips, C.; Sundberg, E. |

    1997-12-01

    The authors propose a general technique called solution decomposition to devise approximation algorithms with provable performance guarantees. The technique is applicable to a large class of combinatorial optimization problems that can be formulated as integer linear programs. Two key ingredients of the technique involve finding a decomposition of a fractional solution into a convex combination of feasible integral solutions and devising generic approximation algorithms based on calls to such decompositions as oracles. The technique is closely related to randomized rounding. The method yields as corollaries unified solutions to a number of well studied problems and it provides the first approximation algorithms with provable guarantees for a number of new problems. The particular results obtained in this paper include the following: (1) The authors demonstrate how the technique can be used to provide more understanding of previous results and new algorithms for classical problems such as Multicriteria Spanning Trees, and Suitcase Packing. (2) They show how the ideas can be extended to apply to multicriteria optimization problems, in which they wish to minimize a certain objective function subject to one or more budget constraints. As corollaries they obtain first non-trivial multicriteria approximation algorithms for problems including the k-Hurdle and the Network Inhibition problems.

  20. Multicriteria approximation through decomposition

    SciTech Connect

    Burch, C.; Krumke, S.; Marathe, M.; Phillips, C.; Sundberg, E.

    1998-06-01

    The authors propose a general technique called solution decomposition to devise approximation algorithms with provable performance guarantees. The technique is applicable to a large class of combinatorial optimization problems that can be formulated as integer linear programs. Two key ingredients of their technique involve finding a decomposition of a fractional solution into a convex combination of feasible integral solutions and devising generic approximation algorithms based on calls to such decompositions as oracles. The technique is closely related to randomized rounding. Their method yields as corollaries unified solutions to a number of well studied problems and it provides the first approximation algorithms with provable guarantees for a number of new problems. The particular results obtained in this paper include the following: (1) the authors demonstrate how the technique can be used to provide more understanding of previous results and new algorithms for classical problems such as Multicriteria Spanning Trees, and Suitcase Packing; (2) they also show how the ideas can be extended to apply to multicriteria optimization problems, in which they wish to minimize a certain objective function subject to one or more budget constraints. As corollaries they obtain first non-trivial multicriteria approximation algorithms for problems including the k-Hurdle and the Network Inhibition problems.

  1. Formation, structure, and decomposition of lanthanide basic carbonates

    SciTech Connect

    Akinc, M.; Sordelet, D.J.; Munson, M. )

    1988-05-01

    Precipitation, crystal structure, and thermal decomposition behavior of the rare-earth basic carbonates were investigated. Precipitates were produced from hydrolysis of rare-earth cations in hot urea solutions. The light rare earths formed were crystalline with regular geometric shapes, whereas heavy rare earths produced amorphous, spherical monodisperse particles. Crystalline phases belong to ancylite-type orthorhombic symmetry. Unit-cell volume was related to interatomic distance. Thermal decomposition of the crystalline precipitates occurred in two major distinct steps to produce oxide, whereas heavy rare earths decomposed continuously with several distinct effects to produce oxide powder.

  2. Decomposition of ethylene on small Pd particles

    NASA Technical Reports Server (NTRS)

    Durrer, W. G.; Poppa, H.; Dickinson, J. T.; Park, C.

    1985-01-01

    New results have been obtained which contribute to the understanding of hydrocarbon reactions on the surface of highly dispersed metal systems. Small particle of Pd were grown by electron beam evaporation on cleavage planes of high purity natural mica under ultrahigh vacuum conditions. Samples were subsequently characterized by transmission electron microscopy. Average particle sizes ranged from about 1 to 10 nm diameter. The chemisoption and decomposition of C2H4 on the Pd particles was studied using Auger electron spectroscopy and flash thermal desorption. It is shown that (a) C2H4 decomposes on Pd particles at room temperature, (b) specific surface sites are causing decomposition, and (c) the proportion of such active sites is significantly greater for the smaller metal particles. This enhanced reactivity may be due to an increase in the density of step, corner, and edge sites with a decrease in particle size.

  3. Pressure Dependent Decomposition Kinetics of the Energetic Material HMX up to 3.6 GPa

    SciTech Connect

    Glascoe, E A; Zaug, J M; Burnham, A K

    2009-05-29

    The effect of pressure on the thermal decomposition rate of the energetic material HMX was studied. HMX was precompressed in a diamond anvil cell (DAC) and heated at various rates. The parent species population was monitored as a function of time and temperature using Fourier transform infrared (FTIR) spectroscopy. Decomposition rates were determined by fitting the fraction reacted to the extended-Prout-Tompkins nucleation-growth model and the Friedman isoconversional method. The results of these experiments and analysis indicate that pressure accelerates the decomposition at low to moderate pressures (i.e. between ambient pressure and 1 GPa) and decelerates the decomposition at higher pressures. The decomposition acceleration is attributed to pressure enhanced autocatalysis whereas the deceleration at high pressures is attributed pressure inhibiting bond homolysis step(s), which would result in an increase in volume. These results indicate that both {beta} and {delta} phase HMX are sensitive to pressure in the thermally induced decomposition kinetics.

  4. In situ analysis of Titan's tholins by Laser 2 steps Desorption Ionisation

    NASA Astrophysics Data System (ADS)

    Benilan, Y.; Carrasco, N.; Cernogora, G.; Gazeau, M.; Mahjoub, A.; Szopa, C.; Schwell, M.

    2013-12-01

    The main objective of the whole project developed in collaboration (LISA/LATMOS) is to provide a better understanding of the chemical composition of Titan aerosols laboratory analogs, called tholins, and thereby of their formation pathways. The tholins are produced in the PAMPRE reactor (French acronyme for Aerosols Microgravity Production by Reactives Plasmas) developed at LATMOS. These tholins are generated in levitation (wall effects are thus limited) in a low pressure radiofrequency plasma. Up to now, the determination of the physical and chemical properties of these tholins was achieved after their collection and ex-situ analysis by several methods. Their bulk composition was then determined but their insoluble part is still unknown. Other studies were performed after the transfer of the soluble part of the aerosols to different analytical instruments. Therefore, possible artifacts could have influenced the results. We present the SMARD (a French acronym for Mass Spectrometry of Aerosols by InfraRed Laser Desorption) program. A challenging issue of our work is to perform the soluble and unsoluble parts of PAMPRE tholins' analysis in real time and in situ. The coupling of the PAMPRE reactor to a unique instrument (Single Particle Laser Ablation Mass Spectrometry) developed at LISA should allow determining in real time and in situ the characteristics (chemical composition together with granulometry) of the nanometric aerosols. The later are introduced in the analytical instrument using an aerodynamic lens device. Their detection and aerodynamic diameter are determined using two continuous diode lasers operating at λ = 403 nm. Then, the L2DI (Laser 2 steps Desorption Ionisation) technique is used in order to access to the chemical composition of individual particles: they are vaporized using a 10 μm CO2 pulsed laser and the gas produced is then ionized by a 248 nm KrF Excimer laser. Finally, the molecular ions are analyzed by a 1 m linear time-of-flight mass

  5. Fulvenallene decomposition kinetics.

    PubMed

    Polino, Daniela; Cavallotti, Carlo

    2011-09-22

    While the decomposition kinetics of the benzyl radical has been studied in depth both from the experimental and the theoretical standpoint, much less is known about the reactivity of what is likely to be its main decomposition product, fulvenallene. In this work the high temperature reactivity of fulvenallene was investigated on a Potential Energy Surface (PES) consisting of 10 wells interconnected through 11 transition states using a 1 D Master Equation (ME). Rate constants were calculated using RRKM theory and the ME was integrated using a stochastic kinetic Monte Carlo code. It was found that two main decomposition channels are possible, the first is active on the singlet PES and leads to the formation of the fulvenallenyl radical and atomic hydrogen. The second requires intersystem crossing to the triplet PES and leads to acetylene and cyclopentadienylidene. ME simulations were performed calculating the microcanonical intersystem crossing frequency using Landau-Zener theory convoluting the crossing probability with RRKM rates evaluated at the conical intersection. It was found that the reaction channel leading to the cyclopentadienylidene diradical is only slightly faster than that leading to the fulvenallenyl radical, so that it can be concluded that both reactions are likely to be active in the investigated temperature (1500-2000 K) and pressure (0.05-50 bar) ranges. However, the simulations show that intersystem crossing is rate limiting for the first reaction channel, as the removal of this barrier leads to an increase of the rate constant by a factor of 2-3. Channel specific rate constants are reported as a function of temperature and pressure. PMID:21819060

  6. Hydrogen peroxide catalytic decomposition

    NASA Technical Reports Server (NTRS)

    Parrish, Clyde F. (Inventor)

    2010-01-01

    Nitric oxide in a gaseous stream is converted to nitrogen dioxide using oxidizing species generated through the use of concentrated hydrogen peroxide fed as a monopropellant into a catalyzed thruster assembly. The hydrogen peroxide is preferably stored at stable concentration levels, i.e., approximately 50%-70% by volume, and may be increased in concentration in a continuous process preceding decomposition in the thruster assembly. The exhaust of the thruster assembly, rich in hydroxyl and/or hydroperoxy radicals, may be fed into a stream containing oxidizable components, such as nitric oxide, to facilitate their oxidation.

  7. Mode decomposition evolution equations

    PubMed Central

    Wang, Yang; Wei, Guo-Wei; Yang, Siyang

    2011-01-01

    Partial differential equation (PDE) based methods have become some of the most powerful tools for exploring the fundamental problems in signal processing, image processing, computer vision, machine vision and artificial intelligence in the past two decades. The advantages of PDE based approaches are that they can be made fully automatic, robust for the analysis of images, videos and high dimensional data. A fundamental question is whether one can use PDEs to perform all the basic tasks in the image processing. If one can devise PDEs to perform full-scale mode decomposition for signals and images, the modes thus generated would be very useful for secondary processing to meet the needs in various types of signal and image processing. Despite of great progress in PDE based image analysis in the past two decades, the basic roles of PDEs in image/signal analysis are only limited to PDE based low-pass filters, and their applications to noise removal, edge detection, segmentation, etc. At present, it is not clear how to construct PDE based methods for full-scale mode decomposition. The above-mentioned limitation of most current PDE based image/signal processing methods is addressed in the proposed work, in which we introduce a family of mode decomposition evolution equations (MoDEEs) for a vast variety of applications. The MoDEEs are constructed as an extension of a PDE based high-pass filter (Europhys. Lett., 59(6): 814, 2002) by using arbitrarily high order PDE based low-pass filters introduced by Wei (IEEE Signal Process. Lett., 6(7): 165, 1999). The use of arbitrarily high order PDEs is essential to the frequency localization in the mode decomposition. Similar to the wavelet transform, the present MoDEEs have a controllable time-frequency localization and allow a perfect reconstruction of the original function. Therefore, the MoDEE operation is also called a PDE transform. However, modes generated from the present approach are in the spatial or time domain and can be

  8. Hydrogen iodide decomposition

    DOEpatents

    O'Keefe, Dennis R.; Norman, John H.

    1983-01-01

    Liquid hydrogen iodide is decomposed to form hydrogen and iodine in the presence of water using a soluble catalyst. Decomposition is carried out at a temperature between about 350.degree. K. and about 525.degree. K. and at a corresponding pressure between about 25 and about 300 atmospheres in the presence of an aqueous solution which acts as a carrier for the homogeneous catalyst. Various halides of the platinum group metals, particularly Pd, Rh and Pt, are used, particularly the chlorides and iodides which exhibit good solubility. After separation of the H.sub.2, the stream from the decomposer is countercurrently extracted with nearly dry HI to remove I.sub.2. The wet phase contains most of the catalyst and is recycled directly to the decomposition step. The catalyst in the remaining almost dry HI-I.sub.2 phase is then extracted into a wet phase which is also recycled. The catalyst-free HI-I.sub.2 phase is finally distilled to separate the HI and I.sub.2. The HI is recycled to the reactor; the I.sub.2 is returned to a reactor operating in accordance with the Bunsen equation to create more HI.

  9. Coxeter decompositions of hyperbolic simplexes

    SciTech Connect

    Felikson, A A

    2002-12-31

    A Coxeter decomposition of a polyhedron in a hyperbolic space H{sup n} is a decomposition of it into finitely many Coxeter polyhedra such that any two tiles having a common facet are symmetric with respect to it. The classification of Coxeter decompositions is closely related to the problem of the classification of finite-index subgroups generated by reflections in discrete hyperbolic groups generated by reflections. All Coxeter decompositions of simplexes in the hyperbolic spaces H{sup n} with n>3 are described in this paper.

  10. Method for improved decomposition of metal nitrate solutions

    DOEpatents

    Haas, Paul A.; Stines, William B.

    1983-10-11

    A method for co-conversion of aqueous solutions of one or more heavy metal nitrates wherein thermal decomposition within a temperature range of about 300.degree. to 800.degree. C. is carried out in the presence of about 50 to 500% molar concentration of ammonium nitrate to total metal.

  11. Method for improved decomposition of metal nitrate solutions

    DOEpatents

    Haas, P.A.; Stines, W.B.

    1981-01-21

    A method for co-conversion of aqueous solutions of one or more heavy metal nitrates is described, wherein thermal decomposition within a temperature range of about 300 to 800/sup 0/C is carried out in the presence of about 50 to 500% molar concentration of ammonium nitrate to total metal.

  12. Art of spin decomposition

    SciTech Connect

    Chen Xiangsong; Sun Weimin; Wang Fan; Goldman, T.

    2011-04-01

    We analyze the problem of spin decomposition for an interacting system from a natural perspective of constructing angular-momentum eigenstates. We split, from the total angular-momentum operator, a proper part which can be separately conserved for a stationary state. This part commutes with the total Hamiltonian and thus specifies the quantum angular momentum. We first show how this can be done in a gauge-dependent way, by seeking a specific gauge in which part of the total angular-momentum operator vanishes identically. We then construct a gauge-invariant operator with the desired property. Our analysis clarifies what is the most pertinent choice among the various proposals for decomposing the nucleon spin. A similar analysis is performed for extracting a proper part from the total Hamiltonian to construct energy eigenstates.

  13. Decomposition of Rare Earth Loaded Resin Particles

    SciTech Connect

    Voit, Stewart L; Rawn, Claudia J

    2010-09-01

    resin is made of sulfonic acid functional groups attached to a styrene divinylbenzene copolymer lattice (long chained hydrocarbon). The metal cation binds to the sulfur group, then during thermal decomposition in air the hydrocarbons will form gaseous species leaving behind a spherical metal-oxide particle. Process development for resin applications with radioactive materials is typically performed using surrogates. For americium and curium, a trivalent metal like neodymium can be used. Thermal decomposition of Nd-loaded resin in air has been studied by Hale. Process conditions were established for resin decomposition and the formation of Nd{sub 2}O{sub 3} particles. The intermediate product compounds were described using x-ray diffraction (XRD) and wet chemistry. Leskela and Niinisto studied the decomposition of rare earth (RE) elements and found results consistent with Hale. Picart et al. demonstrated the viability of using a resin loading process for the fabrication of uranium-actinide mixed oxide microspheres for transmutation of minor actinides in a fast reactor. For effective transmutation of actinides, it will be desirable to extend the in-reactor burnup and minimize the number of recycles of used actinide materials. Longer burn times increases the chance of Fuel Clad Chemical or Mechanical Interaction (FCCI, FCMI). Sulfur is suspected of contributing to Irradiation Assisted Stress Corrosion Cracking (IASCC) thus it is necessary to maximize the removal of sulfur during decomposition of the resin. The present effort extends the previous work by quantifying the removal of sulfur during the decomposition process. Neodymium was selected as a surrogate for trivalent actinide metal cations. As described above Nd was dissolved in nitric acid solution then contacted with the AG-50W resin column. After washing the column, the Nd-resin particles are removed and dried. The Nd-resin, seen in Figure 1 prior to decomposition, is ready to be converted to Nd oxide microspheres.

  14. Direct Sum Decomposition of Groups

    ERIC Educational Resources Information Center

    Thaheem, A. B.

    2005-01-01

    Direct sum decomposition of Abelian groups appears in almost all textbooks on algebra for undergraduate students. This concept plays an important role in group theory. One simple example of this decomposition is obtained by using the kernel and range of a projection map on an Abelian group. The aim in this pedagogical note is to establish a direct…

  15. Mutual effect of thermochemical surface decomposition and viscous interaction during hypersonic flow past a sharp cone

    NASA Technical Reports Server (NTRS)

    Limanskiy, A. V.; Timoshenko, V. I.

    1986-01-01

    Numerical results on the hypersonic gas flow in viscous interaction regime past sharp circular cones with thermally destructible Teflon surface are presented. Characteristics of the mutual influence between the thermochemical decomposition of the surface and the viscous interaction are revealed.

  16. Modeling Decomposition of Unconfined Rigid Polyurethane Foam

    SciTech Connect

    CHU,TZE YAO; ERICKSON,KENNETH L.; HOBBS,MICHAEL L.

    1999-11-01

    The decomposition of unconfined rigid polyurethane foam has been modeled by a kinetic bond-breaking scheme describing degradation of a primary polymer and formation of a thermally stable secondary polymer. The bond-breaking scheme is resolved using percolation theory to describe evolving polymer fragments. The polymer fragments vaporize according to individual vapor pressures. Kinetic parameters for the model were obtained from Thermal Gravimetric Analysis (TGA). The chemical structure of the foam was determined from the preparation techniques and ingredients used to synthesize the foam. Scale-up effects were investigated by simulating the response of an incident heat flux of 25 W/cm{sup 2} on a partially confined 8.8-cm diameter by 15-cm long right circular cylinder of foam which contained an encapsulated component. Predictions of center, midradial, and component temperatures, as well as regression of the foam surface, were in agreement with measurements using thermocouples and X-ray imaging.

  17. Two decoupling methods for non-isothermal DSC results of AIBN decomposition.

    PubMed

    Zhang, Cai-Xing; Lu, Gui-Bin; Chen, Li-Ping; Chen, Wang-Hua; Peng, Min-Jun; Lv, Jia-Yu

    2015-03-21

    During thermal decomposition of azobisisobutyronitrile (AIBN), the endothermic process of phase transition disturbed exothermic decomposition, which brought deformation in its thermal graphs. Therefore, exact kinetic parameters of the decomposition could not be obtained by the existing kinetics analytic models, and the accurate enthalpy data of the decomposition and phase transition were not available. Two methods, i.e., a solvent method and a mathematical method, were introduced in this paper to resolve the coupling phenomenon. In the former method, AIBN was dissolved into aniline to eliminate the endothermic process and obtain curves of the liquid-state decomposition. In the latter method, MATLAB software was employed to get the "pure" exothermic decomposition curve without the influence of phase transition by fitting coupling curves within the section after the transition point and extrapolating to the initial stage of decomposition. Moreover, the kinetic parameters of the "pure" exothermic decomposition of AIBN obtained by the mathematical fitting agreed with the results from the solvent method, verifying the accuracy of the decoupling. The research is of great significance for comprehending the exact characteristics of thermal behaviors and safety parameters of AIBN. It also provides a great help to determine the safe operating temperature and alarm temperature for processes in industry. PMID:25479145

  18. Decomposition in northern Minnesota peatlands

    SciTech Connect

    Farrish, K.W.

    1985-01-01

    Decomposition in peatlands was investigated in northern Minnesota. Four sites, an ombrotrophic raised bog, an ombrotrophic perched bog and two groundwater minerotrophic fens, were studied. Decomposition rates of peat and paper were estimated using mass-loss techniques. Environmental and substrate factors that were most likely to be responsible for limiting decomposition were monitored. Laboratory incubation experiments complemented the field work. Mass-loss over one year in one of the bogs, ranged from 11 percent in the upper 10 cm of hummocks to 1 percent at 60 to 100 cm depth in hollows. Regression analysis of the data for that bog predicted no mass-loss below 87 cm. Decomposition estimates on an area basis were 2720 and 6460 km/ha yr for the two bogs; 17,000 and 5900 kg/ha yr for the two fens. Environmental factors found to limit decomposition in these peatlands were reducing/anaerobic conditions below the water table and cool peat temperatures. Substrate factors found to limit decomposition were low pH, high content of resistant organics such as lignin, and shortages of available N and K. Greater groundwater influence was found to favor decomposition through raising the pH and perhaps by introducing limited amounts of dissolved oxygen.

  19. Structural optimization by multilevel decomposition

    NASA Technical Reports Server (NTRS)

    Sobieszczanski-Sobieski, J.; James, B.; Dovi, A.

    1983-01-01

    A method is described for decomposing an optimization problem into a set of subproblems and a coordination problem which preserves coupling between the subproblems. The method is introduced as a special case of multilevel, multidisciplinary system optimization and its algorithm is fully described for two level optimization for structures assembled of finite elements of arbitrary type. Numerical results are given for an example of a framework to show that the decomposition method converges and yields results comparable to those obtained without decomposition. It is pointed out that optimization by decomposition should reduce the design time by allowing groups of engineers, using different computers to work concurrently on the same large problem.

  20. Autonomous Gaussian Decomposition

    NASA Astrophysics Data System (ADS)

    Lindner, Robert R.; Vera-Ciro, Carlos; Murray, Claire E.; Stanimirović, Snežana; Babler, Brian; Heiles, Carl; Hennebelle, Patrick; Goss, W. M.; Dickey, John

    2015-04-01

    We present a new algorithm, named Autonomous Gaussian Decomposition (AGD), for automatically decomposing spectra into Gaussian components. AGD uses derivative spectroscopy and machine learning to provide optimized guesses for the number of Gaussian components in the data, and also their locations, widths, and amplitudes. We test AGD and find that it produces results comparable to human-derived solutions on 21 cm absorption spectra from the 21 cm SPectral line Observations of Neutral Gas with the EVLA (21-SPONGE) survey. We use AGD with Monte Carlo methods to derive the H i line completeness as a function of peak optical depth and velocity width for the 21-SPONGE data, and also show that the results of AGD are stable against varying observational noise intensity. The autonomy and computational efficiency of the method over traditional manual Gaussian fits allow for truly unbiased comparisons between observations and simulations, and for the ability to scale up and interpret the very large data volumes from the upcoming Square Kilometer Array and pathfinder telescopes.

  1. The bipyridine adducts of N-phenyldithiocarbamato complexes of Zn(II) and Cd(II); synthesis, spectral, thermal decomposition studies and use as precursors for ZnS and CdS nanoparticles

    NASA Astrophysics Data System (ADS)

    Onwudiwe, Damian C.; Strydom, Christien A.

    2015-01-01

    Bipyridine adducts of N-phenyldithiocarbamato complexes, [ML12L2] (M = Cd(II), Zn(II); L1 = N-phenyldithiocarbamate, L2 = 2,2‧ bipyridine), have been synthesized and characterised. The decomposition of these complexes to metal sulphides has been investigated by thermogravimetric analysis (TGA). The complexes were used as single-source precursors to synthesize MS (M = Zn, Cd) nanoparticles (NPs) passivated by hexadecyl amine (HDA). The growth of the nanoparticles was carried out at two different temperatures: 180 and 220 °C, and the optical and structural properties of the nanoparticles were studied using UV-Vis spectroscopy, photoluminescence spectroscopy (PL), transmission emission microscopy (TEM) and powdered X-ray diffraction (p-XRD). Nanoparticles, whose average diameters are 2.90 and 3.54 nm for ZnS, and 8.96 and 9.76 nm for CdS grown at 180 and 220 °C respectively, were obtained.

  2. Towards automated on-line adaptation of 2-Step IMRT plans: QUASIMODO phantom and prostate cancer cases

    PubMed Central

    2013-01-01

    Background The standard clinical protocol of image-guided IMRT for prostate carcinoma introduces isocenter relocation to restore the conformity of the multi-leaf collimator (MLC) segments to the target as seen in the cone-beam CT on the day of treatment. The large interfractional deformations of the clinical target volume (CTV) still require introduction of safety margins which leads to undesirably high rectum toxicity. Here we present further results from the 2-Step IMRT method which generates adaptable prostate IMRT plans using Beam Eye View (BEV) and 3D information. Methods Intermediate/high-risk prostate carcinoma cases are treated using Simultaneous Integrated Boost at the Universitätsklinkum Würzburg (UKW). Based on the planning CT a CTV is defined as the prostate and the base of seminal vesicles. The CTV is expanded by 10 mm resulting in the PTV; the posterior margin is limited to 7 mm. The Boost is obtained by expanding the CTV by 5 mm, overlap with rectum is not allowed. Prescription doses to PTV and Boost are 60.1 and 74 Gy respectively given in 33 fractions. We analyse the geometry of the structures of interest (SOIs): PTV, Boost, and rectum, and generate 2-Step IMRT plans to deliver three fluence steps: conformal to the target SOIs (S0), sparing the rectum (S1), and narrow segments compensating the underdosage in the target SOIs due to the rectum sparing (S2). The width of S2 segments is calculated for every MLC leaf pair based on the target and rectum geometry in the corresponding CT layer to have best target coverage. The resulting segments are then fed into the DMPO optimizer of the Pinnacle treatment planning system for weight optimization and fine-tuning of the form, prior to final dose calculation using the collapsed cone algorithm. We adapt 2-Step IMRT plans to changed geometry whilst simultaneously preserving the number of initially planned Monitor Units (MU). The adaptation adds three further steps to the previous isocenter relocation: 1

  3. Lignocellulose decomposition by microbial secretions

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Carbon storage in terrestrial ecosystems is contingent upon the natural resistance of plant cell wall polymers to rapid biological degradation. Nevertheless, certain microorganisms have evolved remarkable means to overcome this natural resistance. Lignocellulose decomposition by microorganisms com...

  4. Some nonlinear space decomposition algorithms

    SciTech Connect

    Tai, Xue-Cheng; Espedal, M.

    1996-12-31

    Convergence of a space decomposition method is proved for a general convex programming problem. The space decomposition refers to methods that decompose a space into sums of subspaces, which could be a domain decomposition or a multigrid method for partial differential equations. Two algorithms are proposed. Both can be used for linear as well as nonlinear elliptic problems and they reduce to the standard additive and multiplicative Schwarz methods for linear elliptic problems. Two {open_quotes}hybrid{close_quotes} algorithms are also presented. They converge faster than the additive one and have better parallelism than the multiplicative method. Numerical tests with a two level domain decomposition for linear, nonlinear and interface elliptic problems are presented for the proposed algorithms.

  5. Optimization by nonhierarchical asynchronous decomposition

    NASA Technical Reports Server (NTRS)

    Shankar, Jayashree; Ribbens, Calvin J.; Haftka, Raphael T.; Watson, Layne T.

    1992-01-01

    Large scale optimization problems are tractable only if they are somehow decomposed. Hierarchical decompositions are inappropriate for some types of problems and do not parallelize well. Sobieszczanski-Sobieski has proposed a nonhierarchical decomposition strategy for nonlinear constrained optimization that is naturally parallel. Despite some successes on engineering problems, the algorithm as originally proposed fails on simple two dimensional quadratic programs. The algorithm is carefully analyzed for quadratic programs, and a number of modifications are suggested to improve its robustness.

  6. Nontraditional tensor decompositions and applications.

    SciTech Connect

    Bader, Brett William

    2010-07-01

    This presentation will discuss two tensor decompositions that are not as well known as PARAFAC (parallel factors) and Tucker, but have proven useful in informatics applications. Three-way DEDICOM (decomposition into directional components) is an algebraic model for the analysis of 3-way arrays with nonsymmetric slices. PARAFAC2 is a related model that is less constrained than PARAFAC and allows for different objects in one mode. Applications of both models to informatics problems will be shown.

  7. Decomposition of indwelling EMG signals

    PubMed Central

    Nawab, S. Hamid; Wotiz, Robert P.; De Luca, Carlo J.

    2008-01-01

    Decomposition of indwelling electromyographic (EMG) signals is challenging in view of the complex and often unpredictable behaviors and interactions of the action potential trains of different motor units that constitute the indwelling EMG signal. These phenomena create a myriad of problem situations that a decomposition technique needs to address to attain completeness and accuracy levels required for various scientific and clinical applications. Starting with the maximum a posteriori probability classifier adapted from the original precision decomposition system (PD I) of LeFever and De Luca (25, 26), an artificial intelligence approach has been used to develop a multiclassifier system (PD II) for addressing some of the experimentally identified problem situations. On a database of indwelling EMG signals reflecting such conditions, the fully automatic PD II system is found to achieve a decomposition accuracy of 86.0% despite the fact that its results include low-amplitude action potential trains that are not decomposable at all via systems such as PD I. Accuracy was established by comparing the decompositions of indwelling EMG signals obtained from two sensors. At the end of the automatic PD II decomposition procedure, the accuracy may be enhanced to nearly 100% via an interactive editor, a particularly significant fact for the previously indecomposable trains. PMID:18483170

  8. Nuclear driven water decomposition plant for hydrogen production

    NASA Technical Reports Server (NTRS)

    Parker, G. H.; Brecher, L. E.; Farbman, G. H.

    1976-01-01

    The conceptual design of a hydrogen production plant using a very-high-temperature nuclear reactor (VHTR) to energize a hybrid electrolytic-thermochemical system for water decomposition has been prepared. A graphite-moderated helium-cooled VHTR is used to produce 1850 F gas for electric power generation and 1600 F process heat for the water-decomposition process which uses sulfur compounds and promises performance superior to normal water electrolysis or other published thermochemical processes. The combined cycle operates at an overall thermal efficiency in excess of 45%, and the overall economics of hydrogen production by this plant have been evaluated predicated on a consistent set of economic ground rules. The conceptual design and evaluation efforts have indicated that development of this type of nuclear-driven water-decomposition plant will permit large-scale economic generation of hydrogen in the 1990s.

  9. Catalytic decomposition of petroleum into natural gas

    SciTech Connect

    Mango, F.D.; Hightower, J.

    1997-12-01

    Petroleum is believed to be unstable in the earth, decomposing to lighter hydrocarbons at temperatures > 150{degrees}C. Oil and gas deposits support this view: gas/oil ratios and methane concentrations tend to increase with depth above 150{degrees}C. Although oil cracking is suggested and receives wide support, laboratory pyrolysis does not give products resembling natural gas. Moreover, it is doubtful that the light hydrocarbons in wet gas (C{sub 2}-C{sub 4}) could decompose over geologic time to dry gas (>95% methane) without catalytic assistance. We now report the catalytic decomposition of crude oil to a gas indistinguishable from natural gas. Like natural gas in deep basins, it becomes progressively enriched in methane: initially 90% (wet gas) to a final composition of 100% methane (dry gas). To our knowledge, the reaction is unprecedented and unexpectedly robust (conversion of oil to gas is 100% in days, 175{degrees}C) with significant implications regarding the stability of petroleum in sedimentary basins. The existence or nonexistence of oil in the deep subsurface may not depend on the thermal stability of hydrocarbons as currently thought. The critical factor could be the presence of transition metal catalysts which destabilize hydrocarbons and promote their decomposition to natural gas.

  10. Physico-Geometrical Kinetics of Solid-State Reactions in an Undergraduate Thermal Analysis Laboratory

    ERIC Educational Resources Information Center

    Koga, Nobuyoshi; Goshi, Yuri; Yoshikawa, Masahiro; Tatsuoka, Tomoyuki

    2014-01-01

    An undergraduate kinetic experiment of the thermal decomposition of solids by microscopic observation and thermal analysis was developed by investigating a suitable reaction, applicable techniques of thermal analysis and microscopic observation, and a reliable kinetic calculation method. The thermal decomposition of sodium hydrogen carbonate is…

  11. Inter-year repeatability study of volatile organic compounds from surface decomposition of human analogues.

    PubMed

    Stadler, Sonja; Desaulniers, Jean-Paul; Forbes, Shari L

    2015-05-01

    Decomposition odour and volatile organic compounds (VOCs) have gained considerable attention recently due to their use by insects and scent detection canines to locate remains. However, a comprehensive and accurate profile of decomposition odour is yet to be confirmed. This is, in part, due to the geographical diversity in the studies conducted and the variation in the methodology and compounds being reported. To date, no repeatability studies of decomposition odour have been conducted in the same environment. In order to address this current gap in the scientific literature, this study conducted three replicate trials in order to evaluate the inter-year repeatability of the decomposition VOC profile in a southern Canadian environment. Surface decomposition trials were conducted during the spring and summer months and the VOCs were analysed by thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS). This study was able to demonstrate that decomposition VOCs are produced consistently during their characteristic stages and that this relationship is maintained under varying environmental factors which influence the rate of decomposition. This consistent production of decomposition VOCs can lead to a better understanding of the mechanisms of soft tissue decomposition and their sources of variation, and it could potentially lead to improved applications of these compounds for the detection of decomposed remains. PMID:24867182

  12. A multiobjective interval programming model for wind-hydrothermal power system dispatching using 2-step optimization algorithm.

    PubMed

    Ren, Kun; Jihong, Qu

    2014-01-01

    Wind-hydrothermal power system dispatching has received intensive attention in recent years because it can help develop various reasonable plans to schedule the power generation efficiency. But future data such as wind power output and power load would not be accurately predicted and the nonlinear nature involved in the complex multiobjective scheduling model; therefore, to achieve accurate solution to such complex problem is a very difficult task. This paper presents an interval programming model with 2-step optimization algorithm to solve multiobjective dispatching. Initially, we represented the future data into interval numbers and simplified the object function to a linear programming problem to search the feasible and preliminary solutions to construct the Pareto set. Then the simulated annealing method was used to search the optimal solution of initial model. Thorough experimental results suggest that the proposed method performed reasonably well in terms of both operating efficiency and precision. PMID:24895663

  13. A Multiobjective Interval Programming Model for Wind-Hydrothermal Power System Dispatching Using 2-Step Optimization Algorithm

    PubMed Central

    Jihong, Qu

    2014-01-01

    Wind-hydrothermal power system dispatching has received intensive attention in recent years because it can help develop various reasonable plans to schedule the power generation efficiency. But future data such as wind power output and power load would not be accurately predicted and the nonlinear nature involved in the complex multiobjective scheduling model; therefore, to achieve accurate solution to such complex problem is a very difficult task. This paper presents an interval programming model with 2-step optimization algorithm to solve multiobjective dispatching. Initially, we represented the future data into interval numbers and simplified the object function to a linear programming problem to search the feasible and preliminary solutions to construct the Pareto set. Then the simulated annealing method was used to search the optimal solution of initial model. Thorough experimental results suggest that the proposed method performed reasonably well in terms of both operating efficiency and precision. PMID:24895663

  14. Structural characterization of a fusion glycoprotein from a retrovirus that undergoes a hybrid 2-step entry mechanism.

    PubMed

    Aydin, Halil; Smrke, Brianna M; Lee, Jeffrey E

    2013-12-01

    Entry of enveloped viruses into host cells is mediated by their surface envelope glycoproteins (Env). On the surface of the virus, Env is in a metastable, prefusion state, primed to catalyze the fusion of the viral and host membranes. An external trigger is needed to promote the drastic conformational changes necessary for the fusion subunit to fold into the low-energy, 6-helix bundle. These triggers typically facilitate pH-independent entry at the plasma membrane or pH-dependent entry in a low-pH endosomal compartment. The α-retrovirus avian sarcoma leukosis virus (ASLV) has a rare, 2-step entry mechanism with both pH-dependent and pH-independent features. Here, we present the 2.0-Å-resolution crystal structure of the ASLV transmembrane (TM) fusion protein. Our structural and biophysical studies indicated that unlike other pH-dependent or pH-independent viral TMs, the ASLV fusion subunit is stable irrespective of pH. Two histidine residues (His490 and His492) in the chain reversal region confer stability at low pH. A structural comparison of class I viral fusion proteins suggests that the presence of a positive charge, either a histidine or arginine amino acid, stabilizes a helical dipole moment and is a signature of fusion proteins active at low pH. The structure now reveals key residues and features that explain its 2-step mechanism, and we discuss the implications of the ASLV TM structure in the context of general mechanisms required for membrane fusion. PMID:24036886

  15. Updating the singular value decomposition

    NASA Astrophysics Data System (ADS)

    Davies, Philip I.; Smith, M. I. Matthew I.

    2004-09-01

    The spectral decomposition of a symmetric matrix A with small off-diagonal and distinct diagonal elements can be approximated using a direct scheme of R. Davies and Modi (Linear Algebra Appl. 77 (1986) 61). In this paper a generalization of this method for computing the singular value decomposition of close-to-diagonal is presented. When A has repeated or "close" singular values it is possible to apply the direct method to split the problem in two with one part containing the well-separated singular values and one requiring the computation of the "close" singular values.

  16. COMPARISON OF ORGANIC EMISSIONS FROM LABORATORY AND FULL-SCALE THERMAL DEGRADATION OF SEWAGE SLUDGE

    EPA Science Inventory

    Samples of sewage sludge burned at one fluidized-bed and three multiple-hearth incinerators were subjected to laboratory flow reactor thermal decomposition testing under both pyrolytic and oxidative atmospheres. he laboratory test results indicated that biomass decomposition prod...

  17. Thermodynamic anomaly in magnesium hydroxide decomposition

    SciTech Connect

    Reis, T.A.

    1983-08-01

    The Origin of the discrepancy in the equilibrium water vapor pressure measurements for the reaction Mg(OH)/sub 2/(s) = MgO(s) + H/sub 2/O(g) when determined by Knudsen effusion and static manometry at the same temperature was investigated. For this reaction undergoing continuous thermal decomposition in Knudsen cells, Kay and Gregory observed that by extrapolating the steady-state apparent equilibrium vapor pressure measurements to zero-orifice, the vapor pressure was approx. 10/sup -4/ of that previously established by Giauque and Archibald as the true thermodynamic equilibrium vapor pressure using statistical mechanical entropy calculations for the entropy of water vapor. This large difference in vapor pressures suggests the possibility of the formation in a Knudsen cell of a higher energy MgO that is thermodynamically metastable by about 48 kJ / mole. It has been shown here that experimental results are qualitatively independent of the type of Mg(OH)/sub 2/ used as a starting material, which confirms the inferences of Kay and Gregory. Thus, most forms of Mg(OH)/sub 2/ are considered to be the stable thermodynamic equilibrium form. X-ray diffraction results show that during the course of the reaction only the equilibrium NaCl-type MgO is formed, and no different phases result from samples prepared in Knudsen cells. Surface area data indicate that the MgO molar surface area remains constant throughout the course of the reaction at low decomposition temperatures, and no significant annealing occurs at less than 400/sup 0/C. Scanning electron microscope photographs show no change in particle size or particle surface morphology. Solution calorimetric measurements indicate no inherent hgher energy content in the MgO from the solid produced in Knudsen cells. The Knudsen cell vapor pressure discrepancy may reflect the formation of a transient metastable MgO or Mg(OH)/sub 2/-MgO solid solution during continuous thermal decomposition in Knudsen cells.

  18. Decomposition of silane on tungsten or other materials

    DOEpatents

    Wiesmann, H.J.

    This invention relates to hydrogenated amorphous silicon produced by thermally decomposing silane (SiH/sub 4/) or other gases comprising H and Si, from a W or foil heated to a temperature of about 1400 to 1600/sup 0/C, in a vacuum of about 10-/sup 6/ to 10-/sup 4/ torr. A gaseous mixture is formed of atomic hydrogen and atomic silicon. The gaseous mixture is deposited onto a substrate independent of and outside the source of thermal decomposition. Hydrogenated amorphous silicon is formed. The presence of an ammonia atmosphere in the vacuum chamber enhances the photoconductivity of the hydrogenated amorphous silicon film.

  19. Cadaver decomposition in terrestrial ecosystems

    NASA Astrophysics Data System (ADS)

    Carter, David O.; Yellowlees, David; Tibbett, Mark

    2007-01-01

    A dead mammal (i.e. cadaver) is a high quality resource (narrow carbon:nitrogen ratio, high water content) that releases an intense, localised pulse of carbon and nutrients into the soil upon decomposition. Despite the fact that as much as 5,000 kg of cadaver can be introduced to a square kilometre of terrestrial ecosystem each year, cadaver decomposition remains a neglected microsere. Here we review the processes associated with the introduction of cadaver-derived carbon and nutrients into soil from forensic and ecological settings to show that cadaver decomposition can have a greater, albeit localised, effect on belowground ecology than plant and faecal resources. Cadaveric materials are rapidly introduced to belowground floral and faunal communities, which results in the formation of a highly concentrated island of fertility, or cadaver decomposition island (CDI). CDIs are associated with increased soil microbial biomass, microbial activity (C mineralisation) and nematode abundance. Each CDI is an ephemeral natural disturbance that, in addition to releasing energy and nutrients to the wider ecosystem, acts as a hub by receiving these materials in the form of dead insects, exuvia and puparia, faecal matter (from scavengers, grazers and predators) and feathers (from avian scavengers and predators). As such, CDIs contribute to landscape heterogeneity. Furthermore, CDIs are a specialised habitat for a number of flies, beetles and pioneer vegetation, which enhances biodiversity in terrestrial ecosystems.

  20. An analysis of scatter decomposition

    NASA Technical Reports Server (NTRS)

    Nicol, David M.; Saltz, Joel H.

    1990-01-01

    A formal analysis of a powerful mapping technique known as scatter decomposition is presented. Scatter decomposition divides an irregular computational domain into a large number of equal sized pieces, and distributes them modularly among processors. A probabilistic model of workload in one dimension is used to formally explain why, and when scatter decomposition works. The first result is that if correlation in workload is a convex function of distance, then scattering a more finely decomposed domain yields a lower average processor workload variance. The second result shows that if the workload process is stationary Gaussian and the correlation function decreases linearly in distance until becoming zero and then remains zero, scattering a more finely decomposed domain yields a lower expected maximum processor workload. Finally it is shown that if the correlation function decreases linearly across the entire domain, then among all mappings that assign an equal number of domain pieces to each processor, scatter decomposition minimizes the average processor workload variance. The dependence of these results on the assumption of decreasing correlation is illustrated with situations where a coarser granularity actually achieves better load balance.