Thermal plasma treatment of stormwater sediments: comparison between DC non-transferred and partially transferred arc plasma.

PubMed

Li, O L; Guo, Y; Chang, J S; Saito, N

2015-01-01

The disposal of enormous amount of stormwater sediments becomes an emerging worldwide problem. Stormwater sediments are contaminated by heavy metals, phosphorus, trace organic and hydrocarbons, and cannot be disposed without treatment. Thermal plasma decontamination technology offers a high decomposition rate in a wide range of toxic organic compound and immobilization of heavy metal. In this study, we compared the treatment results between two different modes of thermal plasma: (1) a non-transferred direct current (DC) mode and (2) a partial DC-transferred mode. The reductions of total organic carbon (TOC) were, respectively, 25% and 80% for non-transferred and partially transferred plasma, respectively. Most of the toxic organic compounds were converted majorly to CxHy. In the gaseous emission, the accumulated CxHy, CO, NO and H2S were significantly higher in partially transferred mode than in non-transferred mode. The solid analysis demonstrated that the concentrations of Ca and Fe were enriched by 500% and 40%, respectively. New chemical compositions such as KAlSi3O8, Fe3O4, NaCl and CaSO4 were formed after treatment in partially DC-transferred mode. The power inputs were 1 and 10 kW, respectively, for non-transferred DC mode and a partially DC-transferred mode. With a lower energy input, non-transferred plasma treatment can be used for decontamination of sediments with low TOC and metal concentration. Meanwhile, partially transferred thermal plasma with higher energy input is suitable for treating sediments with high TOC percentage and volatile metal concentration. The organic compounds are converted into valuable gaseous products which can be recycled as an energy source.

Thermal degradation study of silicon carbide threads developed for advanced flexible thermal protection systems

NASA Technical Reports Server (NTRS)

Tran, Huy Kim; Sawko, Paul M.

1992-01-01

Silicon carbide (SiC) fiber is a material that may be used in advanced thermal protection systems (TPS) for future aerospace vehicles. SiC fiber's mechanical properties depend greatly on the presence or absence of sizing and its microstructure. In this research, silicon dioxide is found to be present on the surface of the fiber. Electron Spectroscopy for Chemical Analysis (ESCA) and Scanning Electron Microscopy (SEM) show that a thin oxide layer (SiO2) exists on the as-received fibers, and the oxide thickness increases when the fibers are exposed to high temperature. ESCA also reveals no evidence of Si-C bonding on the fiber surface on both as-received and heat treated fibers. The silicon oxide layer is thought to signal the decomposition of SiC bonds and may be partially responsible for the degradation in the breaking strength observed at temperatures above 400 C. The variation in electrical resistivity of the fibers with increasing temperature indicates a transition to a higher band gap material at 350 to 600 C. This is consistent with a decomposition of SiC involving silicon oxide formation.

Laboratory Measurements of Gas Phase Pyrolysis Products from Southern Wildland Fuels using Infrared Spectroscopy

NASA Astrophysics Data System (ADS)

Scharko, N.; Safdari, S.; Danby, T. O.; Howarth, J.; Beiswenger, T. N.; Weise, D.; Myers, T. L.; Fletcher, T. H.; Johnson, T. J.

2017-12-01

Combustion is an oxidation reaction that occurs when there is less fuel available than oxidizers, while pyrolysis is a thermal decomposition process that occurs under "fuel rich" conditions where all of the available oxidizers are consumed leaving some fuel(s) either unreacted or partially reacted. Gas-phase combustion products from biomass burning experiments have been studied extensively; less is known, however, about pyrolysis processes and products. Pyrolysis is the initial reaction occurring in the burning process and generates products that are subsequently oxidized during combustion, yielding highly-oxidized chemicals. This laboratory study investigates the pyrolysis processes by using an FTIR spectrometer to detect and quantify the gas-phase products from thermal decomposition of intact understory fuels from forests in the southeastern United States. In particular, a laboratory flat-flame burner operating under fuel rich conditions (no oxygen) was used to heat individual leaves to cause decomposition. The gas-phase products were introduced to an 8 meter gas cell coupled to an infrared spectrometer were used to monitor the products. Trace gas emissions along with emission ratios, which are calculated by dividing the change in the amount of the trace gas by the change in the amount of CO, for the plant species, gallberry (Ilex glabra) and swampbay (Persea palustris) were determined. Preliminary measurements observed species such as CO2, CO, C2H2, C2H4, HCHO, CH3OH, isoprene, 1,3-butadiene, phenol and NH3 being produced as part of the thermal decomposition process. It is important to note that FTIR will not detect H2.

How to Compute the Partial Fraction Decomposition without Really Trying

ERIC Educational Resources Information Center

Brazier, Richard; Boman, Eugene

2007-01-01

For various reasons there has been a recent trend in college and high school calculus courses to de-emphasize teaching the Partial Fraction Decomposition (PFD) as an integration technique. This is regrettable because the Partial Fraction Decomposition is considerably more than an integration technique. It is, in fact, a general purpose tool which…

Thermal stability and haemolytic effects of depolymerized guar gum derivatives.

PubMed

Hussain, Majid; Zahoor, Tahir; Akhtar, Saeed; Ismail, Amir; Hameed, Aneela

2018-03-01

The purpose of current study was to purify and partially depolymerize guar gum by β-mannanase, HCl, Ba(OH) 2 actions and subjected to inspect compositional, thermogravimetric analysis (TGA) and haemolytic activity. Chemical composition revealed mannose and galactose ratio remained un-altered even after process of purification and hydrolysis. TGA thermograms affirmed initial and final decomposition temperature in various zones. Major decomposition stages apparently revealed partially hydrolyzed guar gum (PHGG) exhibited better heat stable properties having more zones of degradation than crude one. Furthermore, all guar fractions (2.5-250 mg/mL) were subjected to haemolysis to evaluate toxic effects during process of hydrolysis. The crude and hydrolyzed guar galactomannans exhibited minor haemolytic activity (1.9 ± 0.03-7.24 ± 0.02%) when compared to 0.1% Triton-X 100 (100% haemolysis) showing no toxic effects to human RBC's. Conclusively, hydrolyzed guar-galactomannans are safe and can be used in food products with improved heat stability.

Introducing the Improved Heaviside Approach to Partial Fraction Decomposition to Undergraduate Students: Results and Implications from a Pilot Study

ERIC Educational Resources Information Center

Man, Yiu-Kwong

2012-01-01

Partial fraction decomposition is a useful technique often taught at senior secondary or undergraduate levels to handle integrations, inverse Laplace transforms or linear ordinary differential equations, etc. In recent years, an improved Heaviside's approach to partial fraction decomposition was introduced and developed by the author. An important…

Effects of Potassium loading and thermal aging on K/Pt/Al2O3 high-temperature lean NOx trap catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luo, Jinyong; Gao, Feng; Kim, Do Heui

2014-03-31

The effects of K loading and thermal aging on the structural properties and high temperature performance of Pt/K/Al2O3 lean NOx trap (LNT) catalysts were investigated using in situ X-ray diffraction (XRD), temperature-programmed decomposition/desorption of NOx (NOx-TPD), transmission electron microscopy (TEM), NO oxidation and NOx storage tests. In situ XRD results demonstrate that KNO3 becomes extremely mobile on the Al2O3 surface, and experiences complex transformations between orthorhombic and rhombohedral structures, accompanied by sintering, melting and thermal decomposition upon heating. NOx storage results show an optimum K loading around 10% for the best performance at high temperatures. At lower K loadings wheremore » the majority of KNO3 stays as a surface layer, the strong interaction between KNO3 and Al2O3 promotes KNO3 decomposition and deteriorates high-temperature performance. At K loadings higher than 10%, the performance drop is not caused by NOx diffusion limitations as for the case of barium-based LNTs, but rather from the blocking of Pt sites by K species, which adversely affects NO oxidation. Thermal aging at 800 ºC severely deactivates the Pt/K/Al2O3 catalysts due to Pt sintering. However, in the presence of potassium, some Pt remains in a dispersed and oxidized form. These Pt species interact strongly with K and, therefore, do not sinter. After a reduction treatment, these Pt species remain finely dispersed, contributing to a partial recovery of NOx storage performance.« less

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

DTIC Science & Technology

2016-03-14

Journal Article 3. DATES COVERED (From - To) Feb 2015-May 2015 4. TITLE AND SUBTITLE Ab initio Kinetics and Thermal Decomposition Mechanism of 5a...tetrazole-free, nitrogen-rich, energetic compounds. For the first time, the thermal decomposition mechanisms of MNB and DNB have been investigated...potential energy surfaces for thermal decomposition of MNB and DNB were characterized at the RCCSD(T)/cc-pV∞Z//M06-2X/aug- cc-pVTZ level of theory

The thermal decomposition of fine-grained micrometeorites, observations from mid-IR spectroscopy

NASA Astrophysics Data System (ADS)

Suttle, Martin David; Genge, Matthew J.; Folco, Luigi; Russell, Sara S.

2017-06-01

We analysed 44 fine-grained and scoriaceous micrometeorites. A bulk mid-IR spectrum (8-13 μm) for each grain was collected and the entire micrometeorite population classified into 5 spectral groups, based on the positions of their absorption bands. Corresponding carbonaceous Raman spectra, textural observations from SEM-BSE and bulk geochemical data via EMPA were collected to aid in the interpretation of mid-IR spectra. The 5 spectral groups identified correspond to progressive thermal decomposition. Unheated hydrated chondritic matrix, composed predominantly of phyllosilicates, exhibit smooth, asymmetric spectra with a peak at ∼10 μm. Thermal decomposition of sheet silicates evolves through dehydration, dehydroxylation, annealing and finally by the onset of partial melting. Both CI-like and CM-like micrometeorites are shown to pass through the same decomposition stages and produce similar mid-IR spectra. Using known temperature thresholds for each decomposition stage it is possible to assign a peak temperature range to a given micrometeorite. Since the temperature thresholds for decomposition reactions are defined by the phyllosilicate species and the cation composition and that these variables are markedly different between CM and CI classes, atmospheric entry should bias the dust flux to favour the survival of CI-like grains, whilst preferentially melting most CM-like dust. However, this hypothesis is inconsistent with empirical observations and instead requires that the source ratio of CI:CM dust is heavily skewed in favour of CM material. In addition, a small population of anomalous grains are identified whose carbonaceous and petrographic characteristics suggest in-space heating and dehydroxylation have occurred. These grains may therefore represent regolith micrometeorites derived from the surface of C-type asteroids. Since the spectroscopic signatures of dehydroxylates are distinctive, i.e. characterised by a reflectance peak at 9.0-9.5 μm, and since the surfaces of C-type asteroids are expected to be heated via impact gardening, we suggest that future spectroscopic investigations should attempt to identify dehydroxylate signatures in the reflectance spectra of young carbonaceous asteroid families.

The decomposition of mixed oxide Ag2Cu2O3: Structural features and the catalytic properties in CO and C2H4 oxidation

NASA Astrophysics Data System (ADS)

Svintsitskiy, Dmitry A.; Kardash, Tatyana Yu.; Slavinskaya, Elena M.; Stonkus, Olga A.; Koscheev, Sergei V.; Boronin, Andrei I.

2018-01-01

The mixed silver-copper oxide Ag2Cu2O3 with a paramelaconite crystal structure is a promising material for catalytic applications. The as-prepared sample of Ag2Cu2O3 consisted of brick-like particles extended along the [001] direction. A combination of physicochemical techniques such as TEM, XPS and XRD was applied to investigate the structural features of this mixed silver-copper oxide. The thermal stability of Ag2Cu2O3 was investigated using in situ XRD under different reaction conditions, including a catalytic CO + O2 mixture. The first step of Ag2Cu2O3 decomposition was accompanied by the appearance of ensembles consisting of silver nanoparticles with sizes of 5-15 nm. Silver nanoparticles were strongly oriented to each other and to the surface of the initial Ag2Cu2O3 bricks. Based on the XRD data, it was shown that the release of silver occurred along the a and b axes of the paramelaconite structure. Partial decomposition of Ag2Cu2O3 accompanied by the formation of silver nanoparticles was observed during prolonged air storage under ambient conditions. The high reactivity is discussed as a reason for spontaneous decomposition during Ag2Cu2O3 storage. The full decomposition of the mixed oxide into metallic silver and copper (II) oxide took place at temperatures higher than 300 °C regardless of the nature of the reaction medium (helium, air, CO + O2). Catalytic properties of partially and fully decomposed samples of mixed silver-copper oxide were measured in low-temperature CO oxidation and C2H4 epoxidation reactions.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Glascoe, E A; Hsu, P C; Springer, H K

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 smallmore » 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.« less

Trigonometric Integrals via Partial Fractions

ERIC Educational Resources Information Center

Chen, H.; Fulford, M.

2005-01-01

Parametric differentiation is used to derive the partial fractions decompositions of certain rational functions. Those decompositions enable us to integrate some new combinations of trigonometric functions.

Origins of Magnetite Nanocrystals in Martian Meteorite ALH84001

NASA Technical Reports Server (NTRS)

Thomas-Keprta, Kathie L.; Clemett, Simon J.; Mckay, David S.; Gibson, Everett K.; Wentworth, Susan J.

2009-01-01

The Martian meteorite ALH84001 preserves evidence of interaction with aqueous fluids while on Mars in the form of microscopic carbonate disks. These carbonate disks are believed to have precipitated 3.9 Ga ago at beginning of the Noachian epoch on Mars during which both the oldest extant Martian surfaces were formed, and perhaps the earliest global oceans. Intimately associated within and throughout these carbonate disks are nanocrystal magnetites (Fe3O4) with unusual chemical and physical properties, whose origins have become the source of considerable debate. One group of hypotheses argues that these magnetites are the product of partial thermal decomposition of the host carbonate. Alternatively, the origins of mag- netite and carbonate may be unrelated; that is, from the perspective of the carbonate the magnetite is allochthonous. For example, the magnetites might have already been present in the aqueous fluids from which the carbonates were believed to have been deposited. We have sought to resolve between these hypotheses through the detailed characterized of the compo- sitional and structural relationships of the carbonate disks and associated magnetites with the orthopyroxene matrix in which they are embedded. Extensive use of focused ion beam milling techniques has been utilized for sample preparation. We then compared our observations with those from experimental thermal decomposition studies of sideritic carbonates under a range of plausible geological heating scenarios. We conclude that the vast majority of the nanocrystal magnetites present in the car- bonate disks could not have formed by any of the currently proposed thermal decomposition scenarios. Instead, we find there is considerable evidence in support of an alternative allochthonous origin for the magnetite unrelated to any shock or thermal processing of the carbonates.

Magnetic anisotropy and order parameter in nanostructured CoPt particles

NASA Astrophysics Data System (ADS)

Komogortsev, S. V.; Iskhakov, R. S.; Zimin, A. A.; Filatov, E. Yu.; Korenev, S. V.; Shubin, Yu. V.; Chizhik, N. A.; Yurkin, G. Yu.; Eremin, E. V.

2013-10-01

The correlation of magnetic anisotropy energy with order parameter in the crystallites of CoPt nanostructured particles prepared by thermal decomposition and further annealing has been studied by investigation of the approach magnetization to saturation curves and x-ray powder diffraction pattern profiles. It is shown that magnetic anisotropy energy value in partially ordered CoPt crystallite could be described as an intermediate case between two extremes, corresponding to either single or several c-domains of L10 phase in crystallite.

Mechanism of thermal decomposition of K2FeO4 and BaFeO4: A review

NASA Astrophysics Data System (ADS)

Sharma, Virender K.; Machala, Libor

2016-12-01

This paper presents thermal decomposition of potassium ferrate(VI) (K2FeO4) and barium ferrate(VI) (BaFeO4) in air and nitrogen atmosphere. Mössbauer spectroscopy and nuclear forward scattering (NFS) synchrotron radiation approaches are reviewed to advance understanding of electron-transfer processes involved in reduction of ferrate(VI) to Fe(III) phases. Direct evidences of Fe V and Fe IV as intermediate iron species using the applied techniques are given. Thermal decomposition of K2FeO4 involved Fe V, Fe IV, and K3FeO3 as intermediate species while BaFeO3 (i.e. Fe IV) was the only intermediate species during the decomposition of BaFeO4. Nature of ferrite species, formed as final Fe(III) species, of thermal decomposition of K2FeO4 and BaFeO4 under different conditions are evaluated. Steps of the mechanisms of thermal decomposition of ferrate(VI), which reasonably explained experimental observations of applied approaches in conjunction with thermal and surface techniques, are summarized.

Thermal Decomposition Mechanism of CL-20 at Different Temperatures by ReaxFF Reactive Molecular Dynamics Simulations.

PubMed

Wang, Fuping; Chen, Lang; Geng, Deshen; Wu, Junying; Lu, Jianying; Wang, Chen

2018-04-26

Hexanitrohexaazaisowurtzitane (CL-20) has a high detonation velocity and pressure, but its sensitivity is also high, which somewhat limits its applications. Therefore, it is important to understand the mechanism and characteristics of thermal decomposition of CL-20. In this study, a ε-CL-20 supercell was constructed and ReaxFF-lg reactive molecular dynamics simulations were performed to investigate thermal decomposition of ε-CL-20 at various temperatures (2000, 2500, 2750, 3000, 3250, and 3500 K). The mechanism of thermal decomposition of CL-20 was analyzed from the aspects of potential energy evolution, the primary reactions, and the intermediate and final product species. The effect of temperature on thermal decomposition of CL-20 is also discussed. The initial reaction path of thermal decomposition of CL-20 is N-NO 2 cleavage to form NO 2 , followed by C-N cleavage, leading to the destruction of the cage structure. A small number of clusters appear in the early reactions and disappear at the end of the reactions. The initial reaction path of CL-20 decomposition is the same at different temperatures. However, as the temperature increases, the decomposition rate of CL-20 increases and the cage structure is destroyed earlier. The temperature greatly affects the rate constants of H 2 O and N 2 , but it has little effect on the rate constants of CO 2 and H 2 .

Origin of Magnetite Crystals in Martian Meteorite ALH84001 Carbonate Disks

NASA Technical Reports Server (NTRS)

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

2010-01-01

Martian meteorite ALH84001 preserves evidence of interaction with aqueous fluids while on Mars in the form of microscopic carbonate disks which are believed to have precipitated approx.3.9 Ga ago at beginning of the Noachian epoch. Intimately associated within and throughout these carbonate disks are nanocrystal magnetites (Fe3O4) with unusual chemical and physical properties, whose origins have become the source of considerable debate. One group of hypotheses argues that these Fe3O4 are the product of partial thermal decomposition of the host carbonate. Alternatively, the origins of Fe3O4 and carbonate may be unrelated; that is, from the perspective of the carbonate the magnetite is allochthonous. We have sought to resolve between these hypotheses through the detailed characterized of the compositional and structural relationships of the carbonate disks and associated magnetites with the orthopyroxene matrix in which they are embedded [1]. We focus this discussion on the composition of ALH84001 magnetites and then compare these observations with those from our thermal decomposition studies of sideritic carbonates under a range of plausible geological heating scenarios.

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

Treesearch

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

2012-01-01

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

Toward the Elucidation of the Competing Role of Evaporation and Thermal Decomposition in Ionic Liquids: A Multitechnique Study of the Vaporization Behavior of 1-Butyl-3-methylimidazolium Hexafluorophosphate under Effusion Conditions.

PubMed

Volpe, V; Brunetti, B; Gigli, G; Lapi, A; Vecchio Ciprioti, S; Ciccioli, A

2017-11-16

The evaporation/decomposition behavior of the imidazolium ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMImPF 6 ) was investigated in the overall temperature range 425-551 K by means of the molecular-effusion-based techniques Knudsen effusion mass loss (KEML) and Knudsen effusion mass spectrometry (KEMS), using effusion orifices of different size (from 0.2 to 3 mm in diameter). Specific effusion fluxes measured by KEML were found to depend markedly on the orifice size, suggesting the occurrence of a kinetically delayed evaporation/decomposition process. KEMS experiments revealed that other species are present in the vapor phase besides the intact ion pair BMImPF 6 (g) produced by the simple evaporation BMImPF 6 (l) = BMImPF 6 (g), with relative abundances depending on the orifice size-the larger the orifice, the larger the contribution of the BMImPF 6 (g) species. By combining KEML and KEMS results, the conclusion is drawn that in the investigated temperature range, when small effusion orifices are used, a significant part of the mass loss/volatility of BMImPF 6 is due to molecular products formed by decomposition/dissociation processes rather than to evaporated intact ion pairs. Additional experiments performed by nonisothermal thermogravimetry-differential thermal analysis (TG-DTA) further support the evidence of simultaneous evaporation/decomposition, although the conventional decomposition temperature derived from TG curves is much higher than the temperatures covered in effusion experiments. Partial pressures of the BMImPF 6 (g) species were derived from KEMS spectra and analyzed by second- and third-law methods giving a value of Δ evap H 298K ° = 145.3 ± 2.9 kJ·mol -1 for the standard evaporation enthalpy of BMImPF 6 . A comparison is done with the behavior of the 1-butyl-3-methylimidazolium bis(trifluoromethyl)sulfonylimide (BMImNTf 2 ) ionic liquid.

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).

Experimental and DFT simulation study of a novel felodipine cocrystal: Characterization, dissolving properties and thermal decomposition kinetics.

PubMed

Yang, Caiqin; Guo, Wei; Lin, Yulong; Lin, Qianqian; Wang, Jiaojiao; Wang, Jing; Zeng, Yanli

2018-05-30

In this study, a new cocrystal of felodipine (Fel) and glutaric acid (Glu) with a high dissolution rate was developed using the solvent ultrasonic method. The prepared cocrystal was characterized using X-ray powder diffraction, differential scanning calorimetry, thermogravimetric (TG) analysis, and infrared (IR) spectroscopy. To provide basic information about the optimization of pharmaceutical preparations of Fel-based cocrystals, this work investigated the thermal decomposition kinetics of the Fel-Glu cocrystal through non-isothermal thermogravimetry. Density functional theory (DFT) simulations were also performed on the Fel monomer and the trimolecular cocrystal compound for exploring the mechanisms underlying hydrogen bonding formation and thermal decomposition. Combined results of IR spectroscopy and DFT simulation verified that the Fel-Glu cocrystal formed via the NH⋯OC and CO⋯HO hydrogen bonds between Fel and Glu at the ratio of 1:2. The TG/derivative TG curves indicated that the thermal decomposition of the Fel-Glu cocrystal underwent a two-step process. The apparent activation energy (E a ) and pre-exponential factor (A) of the thermal decomposition for the first stage were 84.90 kJ mol -1 and 7.03 × 10 7  min -1 , respectively. The mechanism underlying thermal decomposition possibly involved nucleation and growth, with the integral mechanism function G(α) of α 3/2 . DFT calculation revealed that the hydrogen bonding between Fel and Glu weakened the terminal methoxyl, methyl, and ethyl groups in the Fel molecule. As a result, these groups were lost along with the Glu molecule in the first thermal decomposition. In conclusion, the formed cocrystal exhibited different thermal decomposition kinetics and showed different E a , A, and shelf life from the intact active pharmaceutical ingredient. Copyright © 2018 Elsevier B.V. All rights reserved.

On Partial Fraction Decompositions by Repeated Polynomial Divisions

ERIC Educational Resources Information Center

Man, Yiu-Kwong

2017-01-01

We present a method for finding partial fraction decompositions of rational functions with linear or quadratic factors in the denominators by means of repeated polynomial divisions. This method does not involve differentiation or solving linear equations for obtaining the unknown partial fraction coefficients, which is very suitable for either…

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.

Convective heat transfer for a gaseous slip flow in micropipe and parallel-plate microchannel with uniform wall heat flux: effect of axial heat conduction

NASA Astrophysics Data System (ADS)

Haddout, Y.; Essaghir, E.; Oubarra, A.; Lahjomri, J.

2017-12-01

Thermally developing laminar slip flow through a micropipe and a parallel plate microchannel, with axial heat conduction and uniform wall heat flux, is studied analytically by using a powerful method of self-adjoint formalism. This method results from a decomposition of the elliptic energy equation into a system of two first-order partial differential equations. The advantage of this method over other methods, resides in the fact that the decomposition procedure leads to a selfadjoint problem although the initial problem is apparently not a self-adjoint one. The solution is an extension of prior studies and considers a first order slip model boundary conditions at the fluid-wall interface. The analytical expressions for the developing temperature and local Nusselt number in the thermal entrance region are obtained in the general case. Therefore, the solution obtained could be extended easily to any hydrodynamically developed flow and arbitrary heat flux distribution. The analytical results obtained are compared for select simplified cases with available numerical calculations and they both agree. The results show that the heat transfer characteristics of flow in the thermal entrance region are strongly influenced by the axial heat conduction and rarefaction effects which are respectively characterized by Péclet and Knudsen numbers.

Convective heat transfer for a gaseous slip flow in micropipe and parallel-plate microchannel with uniform wall heat flux: effect of axial heat conduction

NASA Astrophysics Data System (ADS)

Haddout, Y.; Essaghir, E.; Oubarra, A.; Lahjomri, J.

2018-06-01

Thermally developing laminar slip flow through a micropipe and a parallel plate microchannel, with axial heat conduction and uniform wall heat flux, is studied analytically by using a powerful method of self-adjoint formalism. This method results from a decomposition of the elliptic energy equation into a system of two first-order partial differential equations. The advantage of this method over other methods, resides in the fact that the decomposition procedure leads to a selfadjoint problem although the initial problem is apparently not a self-adjoint one. The solution is an extension of prior studies and considers a first order slip model boundary conditions at the fluid-wall interface. The analytical expressions for the developing temperature and local Nusselt number in the thermal entrance region are obtained in the general case. Therefore, the solution obtained could be extended easily to any hydrodynamically developed flow and arbitrary heat flux distribution. The analytical results obtained are compared for select simplified cases with available numerical calculations and they both agree. The results show that the heat transfer characteristics of flow in the thermal entrance region are strongly influenced by the axial heat conduction and rarefaction effects which are respectively characterized by Péclet and Knudsen numbers.

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…

Applications of singular value analysis and partial-step algorithm for nonlinear orbit determination

NASA Technical Reports Server (NTRS)

Ryne, Mark S.; Wang, Tseng-Chan

1991-01-01

An adaptive method in which cruise and nonlinear orbit determination problems can be solved using a single program is presented. It involves singular value decomposition augmented with an extended partial step algorithm. The extended partial step algorithm constrains the size of the correction to the spacecraft state and other solve-for parameters. The correction is controlled by an a priori covariance and a user-supplied bounds parameter. The extended partial step method is an extension of the update portion of the singular value decomposition algorithm. It thus preserves the numerical stability of the singular value decomposition method, while extending the region over which it converges. In linear cases, this method reduces to the singular value decomposition algorithm with the full rank solution. Two examples are presented to illustrate the method's utility.

Thermal decomposition of cyanate ester resins

DOT National Transportation Integrated Search

2001-09-01

Polycyanurate networks were prepared by thermal polymerization of cyanate ester monomers containing two or more cyanate ester : (O-CN) functional groups. The thermal decomposition chemistry of nine different polycyanurates was studied by : ther...

The Composition of Intermediate Products of the Thermal Decomposition of (NH4)2ZrF6 to ZrO2 from Vibrational-Spectroscopy Data

NASA Astrophysics Data System (ADS)

Voit, E. I.; Didenko, N. A.; Gaivoronskaya, K. A.

2018-03-01

Thermal decomposition of (NH4)2ZrF6 resulting in ZrO2 formation within the temperature range of 20°-750°C has been investigated by means of thermal and X-ray diffraction analysis and IR and Raman spectroscopy. It has been established that thermolysis proceeds in six stages. The vibrational-spectroscopy data for the intermediate products of thermal decomposition have been obtained, systematized, and summarized.

Nanorods, nanospheres, nanocubes: Synthesis, characterization and catalytic activity of nanoferrites of Mn, Co, Ni, Part-89

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singh, Supriya; Srivastava, Pratibha; Singh, Gurdip, E-mail: gsingh4us@yahoo.com

2013-02-15

Graphical abstract: Prepared nanoferrites were characterized by FE-SEM and bright field TEM micrographs. The catalytic effect of these nanoferrites was evaluated on the thermal decomposition of ammonium perchlorate using TG and TG–DSC techniques. The kinetics of thermal decomposition of AP was evaluated using isothermal TG data by model fitting as well as isoconversional method. Display Omitted Highlights: ► Synthesis of ferrite nanostructures (∼20.0 nm) by wet-chemical method under different synthetic conditions. ► Characterization using XRD, FE-SEM, EDS, TEM, HRTEM and SAED pattern. ► Catalytic activity of ferrite nanostructures on AP thermal decomposition by thermal techniques. ► Burning rate measurements ofmore » CSPs with ferrite nanostructures. ► Kinetics of thermal decomposition of AP + nanoferrites. -- Abstract: In this paper, the nanoferrites of Mn, Co and Ni were synthesized by wet chemical method and characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy dispersive, X-ray spectra (EDS), transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HR-TEM). It is catalytic activity were investigated on the thermal decomposition of ammonium perchlorate (AP) and composite solid propellants (CSPs) using thermogravimetry (TG), TG coupled with differential scanning calorimetry (TG–DSC) and ignition delay measurements. Kinetics of thermal decomposition of AP + nanoferrites have also been investigated using isoconversional and model fitting approaches which have been applied to data for isothermal TG decomposition. The burning rate of CSPs was considerably enhanced by these nanoferrites. Addition of nanoferrites to AP led to shifting of the high temperature decomposition peak toward lower temperature. All these studies reveal that ferrite nanorods show the best catalytic activity superior to that of nanospheres and nanocubes.« less

Mössbauer study of the thermal decomposition of alkali tris(oxalato)ferrates(III)

NASA Astrophysics Data System (ADS)

Brar, A. S.; Randhawa, B. S.

1985-07-01

The thermal decomposition of alkali (Li,Na,K,Cs,NH 4) tris(oxalato)ferrates(III) has been studied at different temperatures up to 700°C using Mössbauer, infrared spectroscopy, and thermogravimetric techniques. The formation of different intermediates has been observed during thermal decomposition. The decomposition in these complexes starts at different temperatures, i.e., at 200°C in the case of lithium, cesium, and ammonium ferrate(III), 250°C in the case of sodium, and 270°C in the case of potassium tris(oxalato)ferrate(III). The intermediates, i.e., Fe 11C 2O 4, K 6Fe 112(ox) 5. and Cs 2Fe 11 (ox) 2(H 2O) 2, are formed during thermal decomposition of lithium, potassium, and cesium tris(oxalato)ferrates(III), respectively. In the case of sodium and ammonium tris(oxalato)ferrates(III), the decomposition occurs without reduction to the iron(II) state and leads directly to α-Fe 2O 3.

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

NASA Astrophysics Data System (ADS)

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

2017-03-01

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

THERMAL DECOMPOSITION OF PEROXYACETYL NITRATE AND REACTIONS OF ACETYL PEROXY RADICALS WITH NO AND NO2 OVER THE TEMPERATURE RANGE 283-313K

EPA Science Inventory

The thermal decomposition of peroxyacetyl nitrate (PAN) in NO-NO2-air (or N2) mixtures has been studied at 740 torr total pressure over the temperature range 283-313 K. he experimental data obtained yield a rate constant for the thermal decomposition of PAN of k3 = 2.52 x 1016 e-...

Review on Thermal Decomposition of Ammonium Nitrate

NASA Astrophysics Data System (ADS)

Chaturvedi, Shalini; Dave, Pragnesh N.

2013-01-01

In this review data from the literature on thermal decomposition of ammonium nitrate (AN) and the effect of additives to their thermal decomposition are summarized. The effect of additives like oxides, cations, inorganic acids, organic compounds, phase-stablized CuO, etc., is discussed. The effect of an additive mainly occurs at the exothermic peak of pure AN in a temperature range of 200°C to 140°C.

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.

[Ecological/hygienic and toxicological evaluation of combustion products of aviation kerosene and liquefied natural gas].

PubMed

Afanas'ev, R V; Berezin, G I; Raznoschikov, V V

2006-01-01

Products of kerosene combustion in the present-day aeroengines contain more than 200 compounds of incomplete combustion, partial oxidation, and thermal decomposition of fuel and oil. Most of these are strong toxicants for humans. Increase of temperature in the turbine engine combustion chamber led to production of very toxic nitrogen oxides. In search for the ecologically safe and less toxic alternative attention of fuel engineers was drawn to liquefied natural gas which compares well and even excels kerosene in ecological, economic and many other respects.

Focused Ion Beam Microscopy of ALH84001 Carbonate Disks

NASA Technical Reports Server (NTRS)

Thomas-Keprta, Kathie L.; Clemett, Simon J.; Bazylinski, Dennis A.; Kirschvink, Joseph L.; McKay, David S.; Vali, Hojatollah; Gibson, Everett K., Jr.; Romanek, Christopher S.

2005-01-01

Our aim is to understand the mechanism(s) of formation of carbonate assemblages in ALH84001. A prerequisite is that a detailed characterization of the chemical and physical properties of the carbonate be established. We present here analyses by transmission electron microscopy (TEM) of carbonate thin sections produced by both focused ion beam (FIB) sectioning and ultramicrotomy. Our results suggest that the formation of ALH84001 carbonate assemblages were produced by considerably more complex process(es) than simple aqueous precipitation followed by partial thermal decomposition as proposed by other investigators [e.g., 1-3].

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)

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.

Real-Time Optical Monitoring and Simulations of Gas Phase Kinetics in InN Vapor Phase Epitaxy at High Pressure

NASA Technical Reports Server (NTRS)

Dietz, Nikolaus; Woods, Vincent; McCall, Sonya D.; Bachmann, Klaus J.

2003-01-01

Understanding the kinetics of nucleation and coalescence of heteroepitaxial thin films is a crucial step in controlling a chemical vapor deposition process, since it defines the perfection of the heteroepitaxial film both in terms of extended defect formation and chemical integrity of the interface. The initial nucleation process also defines the film quality during the later stages of film growth. The growth of emerging new materials heterostructures such as InN or In-rich Ga(x)In(1-x)N require deposition methods operating at higher vapor densities due to the high thermal decomposition pressure in these materials. High nitrogen pressure has been demonstrated to suppress thermal decomposition of InN, but has not been applied yet in chemical vapor deposition or etching experiments. Because of the difficulty with maintaining stochiometry at elevated temperature, current knowledge regarding thermodynamic data for InN, e.g., its melting point, temperature-dependent heat capacity, heat and entropy of formation are known with far less accuracy than for InP, InAs and InSb. Also, no information exists regarding the partial pressures of nitrogen and phosphorus along the liquidus surfaces of mixed-anion alloys of InN, of which the InN(x)P(1-x) system is the most interesting option. A miscibility gap is expected for InN(x)P(1-x) pseudobinary solidus compositions, but its extent is not established at this point by experimental studies under near equilibrium conditions. The extension of chemical vapor deposition to elevated pressure is also necessary for retaining stoichiometric single phase surface composition for materials that are characterized by large thermal decomposition pressures at optimum processing temperatures.

Calvin Mukarakate | NREL

Science.gov Websites

for the Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Products. He is also a ;Unimolecular Thermal Decomposition of Dimethoxybenzenes," Journal of Chemical Physics (2014) "Real ," Green Chemistry (2014) "Biomass Pyrolysis: Thermal Decomposition Mechanisms of Furfural and

Controlled thermal decomposition of NaSi to derive silicon clathrate compounds

NASA Astrophysics Data System (ADS)

Horie, Hiro-omi; Kikudome, Takashi; Teramura, Kyosuke; Yamanaka, Shoji

2009-01-01

Formation conditions of two types of sodium containing silicon clathrate compounds were determined by the controlled thermal decomposition of sodium monosilicide NaSi under vacuum. The decomposition began at 360 °C. Much higher decomposition temperatures and the presence of sodium metal vapor were favorable for the formation of type I clathrate compound Na 8Si 46. Type II clathrate compound Na xSi 136 was obtained as a single phase at a decomposition temperature <440 °C under the condition without sodium metal vapor. The type I clathrate compound was decomposed to crystalline Si above 520 °C. The type II clathrate compound was thermally more stable, and retained at least up to 550 °C in vacuum.

Gd Ba Cu O bulk superconductors fabricated by a seeded infiltration growth technique under reduced oxygen partial pressure

NASA Astrophysics Data System (ADS)

Iida, K.; Babu, N. H.; Shi, Y. H.; Cardwell, D. A.; Murakami, M.

2006-06-01

Single-grain Gd-Ba-Cu-O (GdBCO) bulk superconductors have been grown by a seeded infiltration and growth (SIG) technique under a 1% O2+N2 atmosphere using a generic MgO-doped Nd-Ba-Cu-O (MgO-NdBCO) seed placed on the sample surface at room temperature (the so-called the cold-seeding method). Partial melting of the MgO-NdBCO seeds fabricated in air under notionally identical thermal processing conditions, however, limited the reliability of this bulk GdBCO single-grain process. The observed seed decomposition is attributed to the dependence of the peritectic temperature Tp of MgO-doped Nd1+xBa2-xCu3Oy solid solution (MgO-doped Nd-123ss, where ss indicates solid solution) compounds on both oxygen partial pressure during the melt process and the level of solid solution (x). The peritectic decomposition temperature of MgO-doped Nd-123ss, with x ranging from 0 to 0.5 under p(O2) = 1.00 atm, was observed to remain constant at 1120 °C. Tp was observed to decrease linearly as a function of solid solution level, on the other hand, under oxygen partial pressures of both p(O2) = 0.21 and 0.01 atm. Based on these results, MgO-doped NdBCO seed crystals should be grown under reduced oxygen partial pressure in order to obtain a stable MgO-doped NdBCO seed crystal suitable for cold-seeding processes of large-grain (RE)BCO bulk superconductors (where RE is a rare earth element).

Sensory irritation and incapacitation evoked by thermal decomposition products of polymers and comparisons with known sensory irritants.

PubMed

Barrow, C S; Alarie, Y; Stock, M F

1978-01-01

A decrease in respiratory rate in mice during exposure to irritating airborne chemicals has been utilized as a response parameter to characterize the degree of upper respiratory tract irritation (sensory irritation) to the thermal decomposition products of various polymers. These included polystyrene, polyvinyl chloride, flexible polyurethane foam, polytetrafluorethylene, a fiber glass reinforced polyester resin, and Douglas Fir. Each of the materials was thermally decomposed in a low-mass vertical furnace in an air atmosphere at a programmed heating rate of 20 degrees C/min. Mice, in groups of four, were exposed to graded concentrations of the thermal decomposition products of each of the above materials. Dose-response curves were obtained by utilizing the maximum percent decrease in respiratory rate as the response parameter during each exposure. Comparison of these dose-response curves with other sensory irritants such as chlorine, ammonia, hydrogen chloride, sulfur dioxide, and toluene diisocyanate gave an indication of the sensory irrtation potential of the thermal decomposition products of these various polymers versus that of well-known single airborne chemical irritants. Total stress and incapacitation of the organism during exposure to sensory irritants such as from the thermal decomposition products of synthetic polymers is discussed.

Thermo-Chemical Conversion of Microwave Activated Biomass Mixtures

NASA Astrophysics Data System (ADS)

Barmina, I.; Kolmickovs, A.; Valdmanis, R.; Vostrikovs, S.; Zake, M.

2018-05-01

Thermo-chemical conversion of microwave activated wheat straw mixtures with wood or peat pellets is studied experimentally with the aim to provide more effective application of wheat straw for heat energy production. Microwave pre-processing of straw pellets is used to provide a partial decomposition of the main constituents of straw and to activate the thermo-chemical conversion of wheat straw mixtures with wood or peat pellets. The experimental study includes complex measurements of the elemental composition of biomass pellets (wheat straw, wood, peat), DTG analysis of their thermal degradation, FTIR analysis of the composition of combustible volatiles entering the combustor, the flame temperature, the heat output of the device and composition of the products by comparing these characteristics for mixtures with unprocessed and mw pre-treated straw pellets. The results of experimental study confirm that mw pre-processing of straw activates the thermal decomposition of mixtures providing enhanced formation of combustible volatiles. This leads to improvement of the combustion conditions in the flame reaction zone, completing thus the combustion of volatiles, increasing the flame temperature, the heat output from the device, the produced heat energy per mass of burned mixture and decreasing at the same time the mass fraction of unburned volatiles in the products.

Thermal decomposition characteristics of microwave liquefied rape straw residues using thermogravimetric analysis

Treesearch

Xingyan Huang; Cornelis F. De Hoop; Jiulong Xie; Chung-Yun Hse; Jinqiu Qi; Yuzhu Chen; Feng Li

2017-01-01

The thermal decomposition characteristics of microwave liquefied rape straw residues with respect to liquefaction condition and pyrolysis conversion were investigated using a thermogravimetric (TG) analyzer at the heating rates of 5, 20, 50 °C min-1. The hemicellulose decomposition peak was absent at the derivative thermogravimetric analysis (DTG...

Thermal Decomposition of Condensed-Phase Nitromethane from Molecular Dynamics from ReaxFF Reactive Dynamics

DTIC Science & Technology

2011-05-04

pubs.acs.org/JPCB Thermal Decomposition of Condensed-Phase Nitromethane from Molecular Dynamics from ReaxFF Reactive Dynamics Si-ping Han,†,‡ Adri C. T. van...ABSTRACT: We studied the thermal decomposition and subsequent reaction of the energetic material nitromethane (CH3NO2) using molec- ular dynamics...with ReaxFF, a first principles-based reactive force field. We characterize the chemistry of liquid and solid nitromethane at high temperatures (2000

Cycling Performance of a Columnar-Structured Complex Perovskite in a Temperature Gradient Test

NASA Astrophysics Data System (ADS)

Schlegel, N.; Sebold, D.; Sohn, Y. J.; Mauer, G.; Vaßen, R.

2015-10-01

To increase the efficiency of turbines for the power generation and the aircraft industry, advanced thermal barrier coatings (TBCs) are required. They need to be long-term stable at temperatures higher than 1200 °C. Nowadays, yttria partially stabilized zirconia (YSZ) is applied as standard TBC material. But its long-term application at temperatures higher than 1200 °C leads to detrimental phase changes and sintering effects. Therefore, new materials have to be investigated, for example, complex perovskites. They provide high melting points, high thermal expansion coefficients and thermal conductivities of approx. 2.0 W/(m K). In this work, the complex perovskite La(Al1/4Mg1/2Ta1/4)O3 (LAMT) was investigated. It was deposited by the suspension plasma spraying (SPS) process, resulting in a columnar microstructure of the coating. The coatings were tested in thermal cycling gradient tests and they show excellent results, even though some phase decomposition was found.

Enhanced Thermal Decomposition Properties of CL-20 through Space-Confining in Three-Dimensional Hierarchically Ordered Porous Carbon.

PubMed

Chen, Jin; He, Simin; Huang, Bing; Wu, Peng; Qiao, Zhiqiang; Wang, Jun; Zhang, Liyuan; Yang, Guangcheng; Huang, Hui

2017-03-29

High energy and low signature properties are the future trend of solid propellant development. As a new and promising oxidizer, hexanitrohexaazaisowurtzitane (CL-20) is expected to replace the conventional oxidizer ammonium perchlorate to reach above goals. However, the high pressure exponent of CL-20 hinders its application in solid propellants so that the development of effective catalysts to improve the thermal decomposition properties of CL-20 still remains challenging. Here, 3D hierarchically ordered porous carbon (3D HOPC) is presented as a catalyst for the thermal decomposition of CL-20 via synthesizing a series of nanostructured CL-20/HOPC composites. In these nanocomposites, CL-20 is homogeneously space-confined into the 3D HOPC scaffold as nanocrystals 9.2-26.5 nm in diameter. The effect of the pore textural parameters and surface modification of 3D HOPC as well as CL-20 loading amount on the thermal decomposition of CL-20 is discussed. A significant improvement of the thermal decomposition properties of CL-20 is achieved with remarkable decrease in decomposition peak temperature (from 247.0 to 174.8 °C) and activation energy (from 165.5 to 115.3 kJ/mol). The exceptional performance of 3D HOPC could be attributed to its well-connected 3D hierarchically ordered porous structure, high surface area, and the confined CL-20 nanocrystals. This work clearly demonstrates that 3D HOPC is a superior catalyst for CL-20 thermal decomposition and opens new potential for further applications of CL-20 in solid propellants.

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

PubMed Central

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

2015-01-01

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 a widely used NEP, 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

Development of Novel Decontamination and Inerting Techniques for Explosives Contaminated Facilities. Phase 1. Identification and Evaluation of Novel Decontamination Concepts. Volume 1

DTIC Science & Technology

1983-07-01

the decomposition reaction (Leider, 1981; Kageyama, 1973; Wolfrom, 1956), 2) Hydrolysis of linkages between glucose units (Urbanski, 1964), 3... dehydration ), 2) Acceleration period (to 50 percent decomposition ), 3) First order reaction rate period. The products of thermal decomposition of...simple mechanism to clean an entire building at once. o Depending on the contaminant, thermal decomposition and or hydrolysis may occur. o May be

Integrated control/structure optimization by multilevel decomposition

NASA Technical Reports Server (NTRS)

Zeiler, Thomas A.; Gilbert, Michael G.

1990-01-01

A method for integrated control/structure optimization by multilevel decomposition is presented. It is shown that several previously reported methods were actually partial decompositions wherein only the control was decomposed into a subsystem design. One of these partially decomposed problems was selected as a benchmark example for comparison. The system is fully decomposed into structural and control subsystem designs and an improved design is produced. Theory, implementation, and results for the method are presented and compared with the benchmark example.

Investigation on an ammonia supply system for flue gas denitrification of low-speed marine diesel

PubMed Central

Yuan, Han; Zhao, Jian; Mei, Ning

2017-01-01

Low-speed marine diesel flue gas denitrification is in great demand in the ship transport industry. This research proposes an ammonia supply system which can be used for flue gas denitrification of low-speed marine diesel. In this proposed ammonia supply system, ammonium bicarbonate is selected as the ammonia carrier to produce ammonia and carbon dioxide by thermal decomposition. The diesel engine exhaust heat is used as the heating source for ammonium bicarbonate decomposition and ammonia gas desorption. As the ammonium bicarbonate decomposition is critical to the proper operation of this system, effects have been observed to reveal the performance of the thermal decomposition chamber in this paper. A visualization experiment for determination of the single-tube heat transfer coefficient and simulation of flow and heat transfer in two structures is conducted; the decomposition of ammonium bicarbonate is simulated by ASPEN PLUS. The results show that the single-tube heat transfer coefficient is 1052 W m2 °C−1; the thermal decomposition chamber fork-type structure gets a higher heat transfer compared with the row-type. With regard to the simulation of ammonium bicarbonate thermal decomposition, the ammonia production is significantly affected by the reaction temperature and the mass flow rate of the ammonium bicarbonate input. PMID:29308269

Stabilization of the Thermal Decomposition of Poly(Propylene Carbonate) Through Copper Ion Incorporation and Use in Self-Patterning

NASA Astrophysics Data System (ADS)

Spencer, Todd J.; Chen, Yu-Chun; Saha, Rajarshi; Kohl, Paul A.

2011-06-01

Incorporation of copper ions into poly(propylene carbonate) (PPC) films cast from γ-butyrolactone (GBL), trichloroethylene (TCE) or methylene chloride (MeCl) solutions containing a photo-acid generator is shown to stabilize the PPC from thermal decomposition. Copper ions were introduced into the PPC mixtures by bringing the polymer mixture into contact with copper metal. The metal was oxidized and dissolved into the PPC mixture. The dissolved copper interferes with the decomposition mechanism of PPC, raising its decomposition temperature. Thermogravimetric analysis shows that copper ions make PPC more stable by up to 50°C. Spectroscopic analysis indicates that copper ions may stabilize terminal carboxylic acid groups, inhibiting PPC decomposition. The change in thermal stability based on PPC exposure to patterned copper substrates was used to provide a self-aligned patterning method for PPC on copper traces without the need for an additional photopatterning registration step. Thermal decomposition of PPC is then used to create air isolation regions around the copper traces. The spatial resolution of the self-patterning PPC process is limited by the lateral diffusion of the copper ions within the PPC. The concentration profiles of copper within the PPC, patterning resolution, and temperature effects on the PPC decomposition have been studied.

Investigation on an ammonia supply system for flue gas denitrification of low-speed marine diesel

NASA Astrophysics Data System (ADS)

Huang, Xiankun; Yuan, Han; Zhao, Jian; Mei, Ning

2017-12-01

Low-speed marine diesel flue gas denitrification is in great demand in the ship transport industry. This research proposes an ammonia supply system which can be used for flue gas denitrification of low-speed marine diesel. In this proposed ammonia supply system, ammonium bicarbonate is selected as the ammonia carrier to produce ammonia and carbon dioxide by thermal decomposition. The diesel engine exhaust heat is used as the heating source for ammonium bicarbonate decomposition and ammonia gas desorption. As the ammonium bicarbonate decomposition is critical to the proper operation of this system, effects have been observed to reveal the performance of the thermal decomposition chamber in this paper. A visualization experiment for determination of the single-tube heat transfer coefficient and simulation of flow and heat transfer in two structures is conducted; the decomposition of ammonium bicarbonate is simulated by ASPEN PLUS. The results show that the single-tube heat transfer coefficient is 1052 W m2 °C-1; the thermal decomposition chamber fork-type structure gets a higher heat transfer compared with the row-type. With regard to the simulation of ammonium bicarbonate thermal decomposition, the ammonia production is significantly affected by the reaction temperature and the mass flow rate of the ammonium bicarbonate input.

Thermophysical Properties and Corrosion Characterization of Low Cost Lithium Containing Nitrate Salts Produced in Northern Chile for Thermal Energy Storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fernandez, Angel G.; Gomez, Judith C.; Galleguillos, Hector

In recent years, lithium containing salts have been studied for thermal energy storage (TES) systems applications, because of their optimal thermophysical properties. In solar power plants, lithium is seen as a way to improve the properties of molten salts used today. Lithium nitrate is a good candidate for sensible heat storage, due to its ability to increase the salt mixture's working temperature range. In the present research, thermophysical properties characterization of lithium nitrate containing salts, produced in Chile, have been carried out. Corrosion evaluations of carbon and low chromium steels were performed at 390 degrees C for 1000 hours. Thermophysicalmore » properties of the salt mixtures, such as thermal stability and heat capacity, were measured before and after corrosion tests. Chemical composition of the salts was also determined and an estimation of Chilean production costs is reported. Results showed that purity, thermal stability and heat capacity of the salts were reduced, caused by partial thermal decomposition and incorporation of corrosion products from the steel.« less

Designing and Thermal Analysis of Safe Lithium Ion Cathode Materials for High Energy Applications

NASA Astrophysics Data System (ADS)

Hu, Enyuan

Safety is one of the most critical issues facing lithium-ion battery application in vehicles. Addressing this issue requires the integration of several aspects, especially the material chemistry and the battery thermal management. First, thermal stability investigation was carried out on an attractive high energy density material LiNi0.5Mn1.5O4. New findings on the thermal-stability and thermal-decomposition-pathways related to the oxygen-release are discovered for the high-voltage spinel Li xNi0.5Mn1.5O4 (LNMO) with ordered (o-) and disordered (d-) structures at fully delithiated (charged) state using a combination of in situ time-resolved x-ray diffraction (TR-XRD) coupled with mass spectroscopy (MS) and x-ray absorption spectroscopy (XAS). Both fully charged o--LixNi0.5Mn1.5O 4 and d-LixNi0.5Mn1.5O 4 start oxygen-releasing structural changes at temperatures below 300 °C, which is in sharp contrast to the good thermal stability of the 4V-spinel LixMn2O4 with no oxygen being released up to 375 °C. This is mainly caused by the presence of Ni4+ in LNMO, which undergoes dramatic reduction during the thermal decomposition. In addition, charged o-LNMO shows better thermal stability than the d-LNMO counterpart, due to the Ni/Mn ordering and smaller amount of the rock-salt impurity phase in o-LNMO. Newly identified two thermal-decomposition-pathways from the initial LixNi0.5Mn1.5O 4 spinel to the final NiMn2O4-type spinel structure with and without the intermediate phases (NiMnO3 and alpha-Mn 2O3) are found to play key roles in thermal stability and oxygen release of LNMO during thermal decomposition. In addressing the safety issue associated with LNMO, Fe is selected to partially substitute Ni and Mn simultaneously utilizing the electrochemical activity and structure-stabilizing high spin Fe3+. The synthesized LiNi1/3Mn4/3Fe1/3O4 showed superior thermal stability and satisfactory electrochemical performance. At charged state, it is able to withstand the temperature as high as 500°C without observable oxygen release. It shows comparable cyclability performance to the LNMO material with better rate capability. The undiminished high voltage capacity is due to the electrochemical activity of Fe in the system. Fe also plays the key role of stabilizing the system at Fe3O4 type spinel phase against further phase transformation to the rock salt phase, accounting for the superior thermal stability of LiNi1/3Mn 4/3Fe1/3O4. Thermal analysis of the lithium-ion battery indicates the key role of electric current in contributing to a thermal runaway. FLUENT simulation on a 10-cell battery shows that under fast discharging conditions, the temperature level can easily reach the threshold of malfunction and the battery temperature features a large distribution of 18°C. Simple air cooling is not effective enough in addressing the problem. Designed air cooling or liquid cooling is required for the normal operation of lithium-ion batteries in vehicles.

Thermal decomposition of ammonium hexachloroosmate.

PubMed

Asanova, T I; Kantor, I; Asanov, I P; Korenev, S V; Yusenko, K V

2016-12-07

Structural changes of (NH 4 ) 2 [OsCl 6 ] occurring during thermal decomposition in a reduction atmosphere have been studied in situ using combined energy-dispersive X-ray absorption spectroscopy (ED-XAFS) and powder X-ray diffraction (PXRD). According to PXRD, (NH 4 ) 2 [OsCl 6 ] transforms directly to metallic Os without the formation of any crystalline intermediates but through a plateau where no reactions occur. XANES and EXAFS data by means of Multivariate Curve Resolution (MCR) analysis show that thermal decomposition occurs with the formation of an amorphous intermediate {OsCl 4 } x with a possible polymeric structure. Being revealed for the first time the intermediate was subjected to determine the local atomic structure around osmium. The thermal decomposition of hexachloroosmate is much more complex and occurs within a minimum two-step process, which has never been observed before.

Integrated control/structure optimization by multilevel decomposition

NASA Technical Reports Server (NTRS)

Zeiler, Thomas A.; Gilbert, Michael G.

1990-01-01

A method for integrated control/structure optimization by multilevel decomposition is presented. It is shown that several previously reported methods were actually partial decompositions wherein only the control was decomposed into a subsystem design. One of these partially decomposed problems was selected as a benchmark example for comparison. The present paper fully decomposes the system into structural and control subsystem designs and produces an improved design. Theory, implementation, and results for the method are presented and compared with the benchmark example.

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}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Jin-jian; Yancheng Teachers College, Yancheng 224002; Liu, Zu-Liang, E-mail: liuzl@mail.njust.edu.cn

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 decompositionmore » 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.« less

Effects of magnesium-based hydrogen storage materials on the thermal decomposition, burning rate, and explosive heat of ammonium perchlorate-based composite solid propellant.

PubMed

Liu, Leili; Li, Jie; Zhang, Lingyao; Tian, Siyu

2018-01-15

MgH 2 , Mg 2 NiH 4 , and Mg 2 CuH 3 were prepared, and their structure and hydrogen storage properties were determined through X-ray photoelectron spectroscopy and thermal analyzer. The effects of MgH 2 , Mg 2 NiH 4 , and Mg 2 CuH 3 on the thermal decomposition, burning rate, and explosive heat of ammonium perchlorate-based composite solid propellant were subsequently studied. Results indicated that MgH 2 , Mg 2 NiH 4 , and Mg 2 CuH 3 can decrease the thermal decomposition peak temperature and increase the total released heat of decomposition. These compounds can improve the effect of thermal decomposition of the propellant. The burning rates of the propellant increased using Mg-based hydrogen storage materials as promoter. The burning rates of the propellant also increased using MgH 2 instead of Al in the propellant, but its explosive heat was not enlarged. Nonetheless, the combustion heat of MgH 2 was higher than that of Al. A possible mechanism was thus proposed. Copyright © 2017. Published by Elsevier B.V.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Nano or micro? A mechanism on thermal decomposition of ammonium perchlorate catalyzed by cobalt oxalate.

PubMed

Zou, Min; Jiang, Xiaohong; Lu, Lude; Wang, Xin

2012-07-30

Micrometer-sized cobalt oxalates with different morphologies have been prepared in the presence of surfactants. The effect of catalysts morphology on the thermal decomposition of ammonium perchlorate (AP) was evaluated by differential thermal analysis (DSC). Remarkably, contrary to the well-accepted concepts, no direct relationship between the morphologies of catalysts and their activities has been observed. Based on the structural and morphological variation of the catalysts during the reaction, a catalytic mechanism on thermal decomposition of ammonium perchlorate catalyzed by cobalt oxalate is proposed. We believe that it is the "self-crushing and self-distributed" occurred within the reaction that really works for the improvement of the overall catalytic activities. In this process, both catalysts and reactants have been crashed and distributed uniformly in an automatic way. This work provides an in-depth insight into the thermal decomposition mechanism of AP as catalyzed by oxalates. Copyright © 2012 Elsevier B.V. All rights reserved.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Keedy, Ryan Michael; Harrison, Kale Warren; Cordaro, Joseph Gabriel

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

Secret Sharing and Shared Information

NASA Astrophysics Data System (ADS)

Rauh, Johannes

2017-11-01

Secret sharing is a cryptographic discipline in which the goal is to distribute information about a secret over a set of participants in such a way that only specific authorized combinations of participants together can reconstruct the secret. Thus, secret sharing schemes are systems of variables in which it is very clearly specified which subsets have information about the secret. As such, they provide perfect model systems for information decompositions. However, following this intuition too far leads to an information decomposition with negative partial information terms, which are difficult to interpret. One possible explanation is that the partial information lattice proposed by Williams and Beer is incomplete and has to be extended to incorporate terms corresponding to higher order redundancy. These results put bounds on information decompositions that follow the partial information framework, and they hint at where the partial information lattice needs to be improved.

POTENTIAL EMISSIONS OF HAZARDOUS ORGANIC COMPOUNDS FROM SEWAGE SLUDGE INCINERATION

EPA Science Inventory

Laboratory thermal decomposition studies were undertaken to evaluate potential organic emissions from sewage sludge incinerators. Precisely controlled thermal decomposition experiments were conducted on sludge spiked with mixtures of hazardous organic compounds, on the mixtures o...

Thermal Decomposition of RP-2 with Stabilizing Additives

DTIC Science & Technology

2010-04-01

was analyzed by gas chromatography . The increase in a suite of light decomposition products was used to monitor the extent of decomposition. The...approximate initial pressure of 34.5 MPa (5000 psi). After each reaction, the thermally stressed liquid phase was analyzed by gas chromatography . The...and operational specifications for these fluids and facilitate new applications. 14,15 The thermophysical properties that are being measured include

Controlled thermal decomposition of NaSi to derive silicon clathrate compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Horie, Hiro-omi; Kikudome, Takashi; Teramura, Kyosuke

Formation conditions of two types of sodium containing silicon clathrate compounds were determined by the controlled thermal decomposition of sodium monosilicide NaSi under vacuum. The decomposition began at 360 deg. C. Much higher decomposition temperatures and the presence of sodium metal vapor were favorable for the formation of type I clathrate compound Na{sub 8}Si{sub 46}. Type II clathrate compound Na{sub x}Si{sub 136} was obtained as a single phase at a decomposition temperature <440 deg. C under the condition without sodium metal vapor. The type I clathrate compound was decomposed to crystalline Si above 520 deg. C. The type II clathratemore » compound was thermally more stable, and retained at least up to 550 deg. C in vacuum. - Graphical Abstract: The optimal condition to prepare type II silicon clathrate Na{sub x}Si{sub 136} with minimal contamination of the type I phase is proposed. The starting NaSi should be thermally decomposed below 440 deg. C, and the rapid removal of Na vapor evolved is essentially important.« less

Thermal decomposition kinetics of hydrazinium cerium 2,3-Pyrazinedicarboxylate hydrate: a new precursor for CeO2.

PubMed

Premkumar, Thathan; Govindarajan, Subbiah; Coles, Andrew E; Wight, Charles A

2005-04-07

The thermal decomposition kinetics of N(2)H(5)[Ce(pyrazine-2,3-dicarboxylate)(2)(H(2)O)] (Ce-P) have been studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), for the first time; TGA analysis reveals an oxidative decomposition process yielding CeO(2) as the final product with an activation energy of approximately 160 kJ mol(-1). This complex may be used as a precursor to fine particle cerium oxides due to its low temperature of decomposition.

On the Possibility of Studying the Reactions of the Thermal Decomposition of Energy Substances by the Methods of High-Resolution Terahertz Spectroscopy

NASA Astrophysics Data System (ADS)

Vaks, V. L.; Domracheva, E. G.; Chernyaeva, M. B.; Pripolzin, S. I.; Revin, L. S.; Tretyakov, I. V.; Anfertyev, V. A.; Yablokov, A. A.; Lukyanenko, I. A.; Sheikov, Yu. V.

2018-02-01

We show prospects for using the method of high-resolution terahertz spectroscopy for a continuous analysis of the decomposition products of energy substances in the gas phase (including short-lived ones) in a wide temperature range. The experimental setup, which includes a terahertz spectrometer for studying the thermal decomposition reactions, is described. The results of analysis of the gaseous decomposition products of energy substances by the example of ammonium nitrate heated from room temperature to 167°C are presented.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maharrey, Sean; Wiese-Smith, Deneille; Highley, Aaron M.

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 formore » a delayed, more violent release.« less

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 of (NO2 + H2O) to be the major decomposition path. Furthermore, we provide fundamental interpretations for the experimental results of Klapötke et al. [Combust. Flame 139, 358-366 (2004)] regarding the thermal stability of MNB and DNB, and their decomposition products. Notably, a fundamental understanding of fuel stability, decomposition mechanism, and key reactions leading to ignition is essential in the design and manipulation of molecular systems for the development of new energetic materials for advanced propulsion applications.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 foundmore » 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 of (NO2 + H2O) to be the major decomposition path. Furthermore, we provide fundamental interpretations for the experimental results of Klapötke et al. [Combust. Flame 139, 358–366 (2004)] regarding the thermal stability of MNB and DNB, and their decomposition products. Notably, a fundamental understanding of fuel stability, decomposition mechanism, and key reactions leading to ignition is essential in the design and manipulation of molecular systems for the development of new energetic materials for advanced propulsion applications.« less

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 of (NO2 + H2O) to be the major decomposition path. Furthermore, we provide fundamental interpretations for the experimental results of Klapötke et al. [Combust. Flame 139, 358-366 (2004)] regarding the thermal stability of MNB and DNB, and their decomposition products. Notably, a fundamental understanding of fuel stability, decomposition mechanism, and key reactions leading to ignition is essential in the design and manipulation of molecular systems for the development of new energetic materials for advanced propulsion applications.

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

PubMed

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

2017-09-05

In order to analyze the thermal decomposition characteristics of ammonium nitrate (AN), its thermal behavior and stability under different conditions are studied, including different atmospheres, heating rates and gas flow rates. The evolved decomposition gases of AN in air and nitrogen are analyzed with a quadrupole mass spectrometer. Thermal stability of AN at different heating rates and gas flow rates are studied by differential scanning calorimetry, thermogravimetric analysis, paired comparison method and safety parameter evaluation. Experimental results show that the major evolved decomposition gases in air are H 2 O, NH 3 , N 2 O, NO, NO 2 and HNO 3 , while in nitrogen, H 2 O, NH 3 , NO and HNO 3 are major components. Compared with nitrogen atmosphere, lower initial and end temperatures, higher heat flux and broader reaction temperature range are obtained in air. Meanwhile, higher air gas flow rate tends to achieve lower reaction temperature and to reduce thermal stability of AN. Self-accelerating decomposition temperature of AN in air is much lower than that in nitrogen. It is considered that thermostability of AN is influenced by atmosphere, heating rate and gas flow rate, thus changes of boundary conditions will influence its thermostability, which is helpful to its safe production, storage, transportation and utilization. Copyright © 2017 Elsevier B.V. All rights reserved.

Does increasing pressure always accelerate the condensed material decay initiated through bimolecular reactions? A case of the thermal decomposition of TKX-50 at high pressures.

PubMed

Lu, Zhipeng; Zeng, Qun; Xue, Xianggui; Zhang, Zengming; Nie, Fude; Zhang, Chaoyang

2017-08-30

Performances and behaviors under high temperature-high pressure conditions are fundamentals for many materials. We study in the present work the pressure effect on the thermal decomposition of a new energetic ionic salt (EIS), TKX-50, by confining samples in a diamond anvil cell, using Raman spectroscopy measurements and ab initio simulations. As a result, we find a quadratic increase in decomposition temperature (T d ) of TKX-50 with increasing pressure (P) (T d = 6.28P 2 + 12.94P + 493.33, T d and P in K and GPa, respectively, and R 2 = 0.995) and the decomposition under various pressures initiated by an intermolecular H-transfer reaction (a bimolecular reaction). Surprisingly, this finding is contrary to a general observation about the pressure effect on the decomposition of common energetic materials (EMs) composed of neutral molecules: increasing pressure will impede the decomposition if it starts from a bimolecular reaction. Our results also demonstrate that increasing pressure impedes the H-transfer via the enhanced long-range electrostatic repulsion of H +δ H +δ of neighboring NH 3 OH + , with blue shifts of the intermolecular H-bonds. And the subsequent decomposition of the H-transferred intermediates is also suppressed, because the decomposition proceeds from a bimolecular reaction to a unimolecular one, which is generally prevented by compression. These two factors are the basic root for which the decomposition retarded with increasing pressure of TKX-50. Therefore, our finding breaks through the previously proposed concept that, for the condensed materials, increasing pressure will accelerate the thermal decomposition initiated by bimolecular reactions, and reveals a distinct mechanism of the pressure effect on thermal decomposition. That is to say, increasing pressure does not always promote the condensed material decay initiated through bimolecular reactions. Moreover, such a mechanism may be feasible to other EISs due to the similar intermolecular interactions.

Premelting, Melting, and Degradation Properties of Molten Alkali Nitrates: LiNO3, NaNO3, KNO3, and Binary NaNO3-KNO3

NASA Astrophysics Data System (ADS)

Mohammad, Mehedi Bin; Brooks, Geoffrey Alan; Rhamdhani, Muhammad Akbar

2018-02-01

A simultaneous thermal analyzer (STA) was used to observe the transition and degradation events of LiNO3, NaNO3, KNO3, and binary NaNO3-KNO3 salts for potential use as phase change materials (PCMs) and heat transfer fluid (HTF). Samples were heated from 50 °C to 800 °C at 10 °C/min scanning rate in three atmospheres (argon, air, and oxygen) using an STA to observe decomposition behavior. Thermal stability increased for all salts at high partial pressure of O2 ( P_{{{O}2 }} = 1.0) compared to inert argon ( P_{{{O}2 }} = 0). O2, N2, NO, N2O, and NO2 were main evolved gases during nitrate decomposition. NO and O2 started to evolve at approximately the same temperature after melting, indicating that primary and secondary decomposition reactions were concurrent and overlapping. The solid-solid transition, liquidus and solidus temperatures, heat of transition, heat of melting, and heat of solidification were obtained at various heating-cooling rates (1, 2, 4, 5, 6, 8, 10, and 15 °C/min) using an STA. At all heating-cooling rates, a small gap exists between liquidus and solidus temperatures for all samples due to the salts exhibiting supercooling phenomena. This study showed that the degradation point depends on the blanket atmosphere top of the molten salts and that heating rates have a minor effect on transition events (peaks height, peaks width, and transition enthalpies).

Premelting, Melting, and Degradation Properties of Molten Alkali Nitrates: LiNO3, NaNO3, KNO3, and Binary NaNO3-KNO3

NASA Astrophysics Data System (ADS)

Mohammad, Mehedi Bin; Brooks, Geoffrey Alan; Rhamdhani, Muhammad Akbar

2018-06-01

A simultaneous thermal analyzer (STA) was used to observe the transition and degradation events of LiNO3, NaNO3, KNO3, and binary NaNO3-KNO3 salts for potential use as phase change materials (PCMs) and heat transfer fluid (HTF). Samples were heated from 50 °C to 800 °C at 10 °C/min scanning rate in three atmospheres (argon, air, and oxygen) using an STA to observe decomposition behavior. Thermal stability increased for all salts at high partial pressure of O2 ( P_{{{O}2 }} = 1.0) compared to inert argon ( P_{{{O}2 }} = 0). O2, N2, NO, N2O, and NO2 were main evolved gases during nitrate decomposition. NO and O2 started to evolve at approximately the same temperature after melting, indicating that primary and secondary decomposition reactions were concurrent and overlapping. The solid-solid transition, liquidus and solidus temperatures, heat of transition, heat of melting, and heat of solidification were obtained at various heating-cooling rates (1, 2, 4, 5, 6, 8, 10, and 15 °C/min) using an STA. At all heating-cooling rates, a small gap exists between liquidus and solidus temperatures for all samples due to the salts exhibiting supercooling phenomena. This study showed that the degradation point depends on the blanket atmosphere top of the molten salts and that heating rates have a minor effect on transition events (peaks height, peaks width, and transition enthalpies).

Computing the Partial Fraction Decomposition of Rational Functions with Irreducible Quadratic Factors in the Denominators

ERIC Educational Resources Information Center

Man, Yiu-Kwong

2012-01-01

In this note, a new method for computing the partial fraction decomposition of rational functions with irreducible quadratic factors in the denominators is presented. This method involves polynomial divisions and substitutions only, without having to solve for the complex roots of the irreducible quadratic polynomial or to solve a system of linear…

Lipid oxidation. Part. 1. Effect of free carboxyl group on the decomposition of lipid hydroperoxide.

PubMed

Pokorný, J; Rzepa, J; Janícek, G

1976-01-01

Hydroperoxido butyl oleate was decomposed by heating in excess palmitic acid at 60-120 degrees C. The decomposition followed the kinetics of a first order reaction with formation of both monomeric and oligomeric secondary products. The proportions of oligomers slightly increased with increasing reaction temperature and decreased with increasing concentration of hydroperoxide. The activation energy was 70.4 kJ/mol +/- 4.7 kJ/mol. The decomposition of hydroperoxides proceeded partially by monomolecular cleavage, partially by formation of esters with palmitic acid.

Assessment of a new method for the analysis of decomposition gases of polymers by a combining thermogravimetric solid-phase extraction and thermal desorption gas chromatography mass spectrometry.

PubMed

Duemichen, E; Braun, U; Senz, R; Fabian, G; Sturm, H

2014-08-08

For analysis of the gaseous thermal decomposition products of polymers, the common techniques are thermogravimetry, combined with Fourier transformed infrared spectroscopy (TGA-FTIR) and mass spectrometry (TGA-MS). These methods offer a simple approach to the decomposition mechanism, especially for small decomposition molecules. Complex spectra of gaseous mixtures are very often hard to identify because of overlapping signals. In this paper a new method is described to adsorb the decomposition products during controlled conditions in TGA on solid-phase extraction (SPE) material: twisters. Subsequently the twisters were analysed with thermal desorption gas chromatography mass spectrometry (TDS-GC-MS), which allows the decomposition products to be separated and identified using an MS library. The thermoplastics polyamide 66 (PA 66) and polybutylene terephthalate (PBT) were used as example polymers. The influence of the sample mass and of the purge gas flow during the decomposition process was investigated in TGA. The advantages and limitations of the method were presented in comparison to the common analysis techniques, TGA-FTIR and TGA-MS. Copyright © 2014 Elsevier B.V. All rights reserved.

A procedure for the assessment of the toxicity of intermediates and products formed during the accidental thermal decomposition of a chemical species.

PubMed

Di Somma, Ilaria; Pollio, Antonino; Pinto, Gabriele; De Falco, Maria; Pizzo, Elio; Andreozzi, Roberto

2010-04-15

The knowledge of the substances which form when a molecule undergoes chemical reactions under unusual conditions is required by European legislation to evaluate the risks associated with an industrial chemical process. A thermal decomposition is often the result of a loss of control of the process which leads to the formation of many substances in some cases not easily predictable. The evaluation of the change of an overall toxicity passing from the parent compound to the mixture of its thermal decomposition products has been already proposed as a practical approach to this problem when preliminary indications about the temperature range in which the molecule decomposes are available. A new procedure is proposed in this work for the obtainment of the mixtures of thermal decomposition products also when there is no previous information about the thermal behaviour of investigated molecules. A scanning calorimetric run that is aimed to identify the onset temperature of the decomposition process is coupled to an isoperibolic one in order to obtain and collect the products. An algal strain is adopted for toxicological assessments of chemical compounds and mixtures. An extension of toxicological investigations to human cells is also attempted. 2009 Elsevier B.V. All rights reserved.

Thermal decomposition of europium sulfates Eu2(SO4)3·8H2O and EuSO4

NASA Astrophysics Data System (ADS)

Denisenko, Yu. G.; Khritokhin, N. A.; Andreev, O. V.; Basova, S. A.; Sal'nikova, E. I.; Polkovnikov, A. A.

2017-11-01

Reactions of europium sulfates Eu2(SO4)3·8H2O and EuSO4 complete decomposition were studied by Simultaneous Thermal Analysis. It was revealed that one-step dehydratation of Eu2(SO4)3·8H2O crystallohydrate is accompanied by the formation of amorphous anhydrous europium sulfate Eu2(SO4)3. Crystallization of amorphous europium (III) sulfate occurs at 381.1 °C (in argon) and 391.3 °C (in air). The average enthalpy values for dehydratation reaction of Eu2(SO4)3·8H2O (ΔH° = 141.1 kJ/mol), decomposition reactions of Eu2(SO4)3 (ΔH = 463.1 kJ/mol), Eu2O2SO4 (ΔH = 378.4 kJ/mol) and EuSO4 (ΔH = 124.1 kJ/mol) were determined. The step process mechanisms of thermal decomposition of europium (III) sulfate in air and europium (II) sulfate in inert atmosphere were established and justified. The kinetic parameters of complete thermal decomposition of europium (III) sulfate octahydrate were calculated by Kissinger model. The standard enthalpies of compound formation were calculated using thermal effects and formation enthalpy data for binary compounds.

Thermal decomposition and isomerization of cis-permethrin and beta-cypermethrin in the solid phase.

PubMed

González Audino, Paola; Licastro, Susana A; Zerba, Eduardo

2002-02-01

The stability to heart of cis-permethrin and beta-cypermethrin in the solid phase was studied and the decomposition products identified. Samples heated at 210 degrees C in an oven in the dark showed that, in the absence of potassium chlorate (the salt present in smoke-generating formulations of these pyrethroids), cis-permethrin was not isomerized, although in the presence of that salt, decomposition was greater and thermal isomerization occurred. Other salts of the type KXO3 or NaXO3, with X being halogen or nitrogen, also led to a considerable thermal isomerization. Heating the insecticides in solution in the presence of potassium chlorate did not produce isomerization in any of the solvents assayed. Salt-catalysed thermal cis-trans isomerization was also found for other pyrethroids derived from permethrinic or deltamethrinic acid but not for those derived from chrysanthemic acid. The main thermal degradation processes of cis-permethrin and beta-cypermethrin decomposition when potassium chlorate was present were cyclopropane isomerization, ester cleavage and subsequent oxidation of the resulting products. Permethrinic acid, 3-phenoxybenzyle chloride, alcohol, aldehyde and acid were identified in both cases, as well as 3-phenoxybenzyl cyanide from beta-cypermethrin. A similar decomposition pattern occurred after combustion of pyrethroid fumigant formulations.

Determination of the thermal stability of perfluoropolyalkyl ethers by tensimetry

NASA Technical Reports Server (NTRS)

Helmick, Larry A.; Jones, William R., Jr.

1992-01-01

The thermal decomposition temperatures of several perfluoropolyalkyl ether fluids were determined with a computerized tensimeter. In general, the decomposition temperatures of the commercial fluids were all similar and significantly higher than those for noncommercial fluids. Correlation of the decomposition temperatures with the molecular structures of the primary components of the commercial fluids revealed that the stability of the fluids was not affected by carbon chain length, branching, or adjacent difluoroformal groups. Instead, stability was limited by the presence of small quantities of thermally unstable material and/or chlorine-containing material arising from the use of chlorine containing solvents during synthesis. Finally, correlation of decomposition temperatures with molecular weights for two fluids supports a chain cleavage reaction mechanism for one and an unzipping reaction mechanism for the other.

Pursuing reliable thermal analysis techniques for energetic materials: decomposition kinetics and thermal stability of dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50).

PubMed

Muravyev, Nikita V; Monogarov, Konstantin A; Asachenko, Andrey F; Nechaev, Mikhail S; Ananyev, Ivan V; Fomenkov, Igor V; Kiselev, Vitaly G; Pivkina, Alla N

2016-12-21

Thermal decomposition of a novel promising high-performance explosive dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50) was studied using a number of thermal analysis techniques (thermogravimetry, differential scanning calorimetry, and accelerating rate calorimetry, ARC). To obtain more comprehensive insight into the kinetics and mechanism of TKX-50 decomposition, a variety of complementary thermoanalytical experiments were performed under various conditions. Non-isothermal and isothermal kinetics were obtained at both atmospheric and low (up to 0.3 Torr) pressures. The gas products of thermolysis were detected in situ using IR spectroscopy, and the structure of solid-state decomposition products was determined by X-ray diffraction and scanning electron microscopy. Diammonium 5,5'-bistetrazole-1,1'-diolate (ABTOX) was directly identified to be the most important intermediate of the decomposition process. The important role of bistetrazole diol (BTO) in the mechanism of TKX-50 decomposition was also rationalized by thermolysis experiments with mixtures of TKX-50 and BTO. Several widely used thermoanalytical data processing techniques (Kissinger, isoconversional, formal kinetic approaches, etc.) were independently benchmarked against the ARC data, which are more germane to the real storage and application conditions of energetic materials. Our study revealed that none of the Arrhenius parameters reported before can properly describe the complex two-stage decomposition process of TKX-50. In contrast, we showed the superior performance of the isoconversional methods combined with isothermal measurements, which yielded the most reliable kinetic parameters of TKX-50 thermolysis. In contrast with the existing reports, the thermal stability of TKX-50 was determined in the ARC experiments to be lower than that of hexogen, but close to that of hexanitrohexaazaisowurtzitane (CL-20).

A review of plutonium oxalate decomposition reactions and effects of decomposition temperature on the surface area of the plutonium dioxide product

NASA Astrophysics Data System (ADS)

Orr, R. M.; Sims, H. E.; Taylor, R. J.

2015-10-01

Plutonium (IV) and (III) ions in nitric acid solution readily form insoluble precipitates with oxalic acid. The plutonium oxalates are then easily thermally decomposed to form plutonium dioxide powder. This simple process forms the basis of current industrial conversion or 'finishing' processes that are used in commercial scale reprocessing plants. It is also widely used in analytical or laboratory scale operations and for waste residues treatment. However, the mechanisms of the thermal decompositions in both air and inert atmospheres have been the subject of various studies over several decades. The nature of intermediate phases is of fundamental interest whilst understanding the evolution of gases at different temperatures is relevant to process control. The thermal decomposition is also used to control a number of powder properties of the PuO2 product that are important to either long term storage or mixed oxide fuel manufacturing. These properties are the surface area, residual carbon impurities and adsorbed volatile species whereas the morphology and particle size distribution are functions of the precipitation process. Available data and experience regarding the thermal and radiation-induced decompositions of plutonium oxalate to oxide are reviewed. The mechanisms of the thermal decompositions are considered with a particular focus on the likely redox chemistry involved. Also, whilst it is well known that the surface area is dependent on calcination temperature, there is a wide variation in the published data and so new correlations have been derived. Better understanding of plutonium (III) and (IV) oxalate decompositions will assist the development of more proliferation resistant actinide co-conversion processes that are needed for advanced reprocessing in future closed nuclear fuel cycles.

Mechanism of the Thermal Decomposition of Ethanethiol and Dimethylsulfide

NASA Astrophysics Data System (ADS)

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

2016-06-01

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

Adsorption of thiophene on silica-supported Mo clusters

NASA Astrophysics Data System (ADS)

Komarneni, M.; Kadossov, E.; Justin, J.; Lu, M.; Burghaus, U.

2010-07-01

The adsorption/decomposition kinetics/dynamics of thiophene has been studied on silica-supported Mo and MoS x clusters. Two-dimensional cluster formation at small Mo exposures and three-dimensional cluster growth at larger exposures would be consistent with the Auger electron spectroscopy (AES) data. Thermal desorption spectroscopy (TDS) indicates two reaction pathways. H 4C 4S desorbs molecularly at 190-400 K. Two TDS features were evident and could be assigned to molecularly on Mo sites, and S sites adsorbed thiophene. Assuming a standard preexponential factor (ν = 1 × 10 13/s) for first-order kinetics, the binding energies for adsorption on Mo (sulfur) sites amount to 90 (65) kJ/mol for 0.4 ML Mo exposure and 76 (63) kJ/mol for 2 ML Mo. Thus, smaller clusters are more reactive than larger clusters for molecular adsorption of H 4C 4S. The second reaction pathway, the decomposition of thiophene, starts at 250 K. Utilizing multimass TDS, H 2, H 2S, and mostly alkynes are detected in the gas phase as decomposition products. H 4C 4S bond activation results in partially sulfided Mo clusters as well as S and C residuals on the surface. S and C poison the catalyst. As a result, with an increasing number of H 4C 4S adsorption/desorption cycles, the uptake of molecular thiophene decreases as well as the H 2 and H 2S production ceases. Thus, silica-supported sulfided Mo clusters are less reactive than metallic clusters. The poisoned catalyst can be partially reactivated by annealing in O 2. However, Mo oxides also appear to form, which passivate the catalyst further. On the other hand, while annealing a used catalyst in H/H 2, it is poisoned even more (i.e., the S AES signal increases). By means of adsorption transients, the initial adsorption probability, S0, of C 4H 4S has been determined. At thermal impact energies ( Ei = 0.04 eV), S0 for molecular adsorption amounts to 0.43 ± 0.03 for a surface temperature of 200 K. S0 increases with Mo cluster size, obeying the capture zone model. The temperature dependence of S0( Ts) consists of two regions consistent with molecular adsorption of thiophene at low temperatures and its decomposition above 250 K. Fitting S0( Ts) curves allows one to determine the bond activation energy for the first elementary decomposition step of C 4H 4S, which amounts to (79 ± 2) kJ/mol and (52 ± 4) kJ/mol for small and large Mo clusters, respectively. Thus, larger clusters are more active for decomposing C 4H 4S than are smaller clusters.

Viscosity effects on the thermal decomposition of bis(perfluoro-2-N-propoxypropionyl) peroxide in dense carbon dioxide and fluorinated solvents.

PubMed

Bunyard, W C; Kadla, J F; DeYoung, J; DeSimone, J M

2001-08-01

The thermal decomposition of the free-radical initiator bis(perfluoro-2-N-propoxyprionyl) peroxide (BPPP) was studied in dense carbon dioxide and a series of fluorinated solvents. For the fluorinated solvents, the observed first-order decomposition rate constants, k(obs), increased with decreasing solvent viscosity, suggesting a single-bond decomposition mechanism. The k(obs) values are comparatively larger in dense carbon dioxide and similar to the "zero-viscosity" rate constants extrapolated from the decomposition kinetics in the fluorinated solvents. The decomposition activation parameters demonstrate a compensation behavior of the activation enthalpy with the activation entropy upon change in solvent viscosity. Comparison of the change in activation parameter values upon change in solvent viscosity for BPPP with two additional initiators, acetyl peroxide (AP) and trifluoroacetyl peroxide (TFAP), further suggests that carbon dioxide exerts a very minimal influence on the decomposition mechanism of these initiators through solvent-cage effects.

The processing of aluminum gasarites via thermal decomposition of interstitial hydrides

NASA Astrophysics Data System (ADS)

Licavoli, Joseph J.

Gasarite structures are a unique type of metallic foam containing tubular pores. The original methods for their production limited them to laboratory study despite appealing foam properties. Thermal decomposition processing of gasarites holds the potential to increase the application of gasarite foams in engineering design by removing several barriers to their industrial scale production. The following study characterized thermal decomposition gasarite processing both experimentally and theoretically. It was found that significant variation was inherent to this process therefore several modifications were necessary to produce gasarites using this method. Conventional means to increase porosity and enhance pore morphology were studied. Pore morphology was determined to be more easily replicated if pores were stabilized by alumina additions and powders were dispersed evenly. In order to better characterize processing, high temperature and high ramp rate thermal decomposition data were gathered. It was found that the high ramp rate thermal decomposition behavior of several hydrides was more rapid than hydride kinetics at low ramp rates. This data was then used to estimate the contribution of several pore formation mechanisms to the development of pore structure. It was found that gas-metal eutectic growth can only be a viable pore formation mode if non-equilibrium conditions persist. Bubble capture cannot be a dominant pore growth mode due to high bubble terminal velocities. Direct gas evolution appears to be the most likely pore formation mode due to high gas evolution rate from the decomposing particulate and microstructural pore growth trends. The overall process was evaluated for its economic viability. It was found that thermal decomposition has potential for industrialization, but further refinements are necessary in order for the process to be viable.

Evaporation Study of an Ionic Liquid with a Double-Charged Cation.

PubMed

Chilingarov, Norbert S; Zhirov, Maksim S; Shmykova, Anna M; Martynova, Ekaterina A; Glukhov, Lev M; Chernikova, Elena A; Kustov, Leonid M; Markov, Vitaliy Yu; Ioutsi, Vitaliy A; Sidorov, Lev N

2018-05-07

The evaporation of a dicationic ionic liquid, 1,3-bis(3-methylimidazolium-1-yl)propane bis(trifluoromethanesulfonyl)amide ([C 3 (MIm) 2 2+ ][Tf 2 N - ] 2 ), was studied by Knudsen effusion mass spectrometry. Its evaporation is accompanied by a partial thermal decomposition producing monocationic ionic liquids, 1,3-dimethylimidazolium and 1-(2-propenyl)-3-methylimidazolium bis(trifluoromethanesulfonyl)amides, as volatile products. This decomposition does not affect the vaporization characteristics of [C 3 (MIm) 2 2+ ][Tf 2 N - ] 2 , which were established to be as follows. The vaporization enthalpy (550 K) is equal to (155.5 ± 3.2) kJ·mol -1 ; the saturated vapor pressure is described by the equation ln( p/Pa) = -(18699 ± 381)/( T/K) + (30.21 ± 0.82) in the range of 508-583 K. 1,3-Bis(3-methylimidazolium-1-yl)propane bis(trifluoromethanesulfonyl)amide is the first dicationic ionic liquid, the vaporization characteristics of which were determined with an acceptable accuracy.

Process for remediation of plastic waste

DOEpatents

Pol, Vilas G [Westmont, IL; Thiyagarajan, Pappannan [Germantown, MD

2012-04-10

A single step process for degrading plastic waste by converting the plastic waste into carbonaceous products via thermal decomposition of the plastic waste by placing the plastic waste into a reactor, heating the plastic waste under an inert or air atmosphere until the temperature of 700.degree. C. is achieved, allowing the reactor to cool down, and recovering the resulting decomposition products therefrom. The decomposition products that this process yields are carbonaceous materials, and more specifically egg-shaped and spherical-shaped solid carbons. Additionally, in the presence of a transition metal compound, this thermal decomposition process produces multi-walled carbon nanotubes.

Contribution to the identification of pyrolysis byproducts in fluidized bed soot and in pyrocarbon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wolfrum, E.; Rottmann, J.; Bueker, I.

1973-01-15

In order to develop improved fuel particles, pyrohysis byproducts of both the pyrocarbon separated in fluidized beds and the resulting soot were studied. The aim was to study the separation mechanism of pyrocarbon on fuel kernels during the thermal decomposition of low hydrocarbons. This study referred to pyrolysis products of acetylene and propylene. The extraction was performed with various methods. The extracts were separated gas- chromatographically and mass-spectrometrically; the single components were partially identified. 21 polycyclic and aromatic hydrocarbons were clearly identified in soot. Beyond that, pyrocarbon contains still higher molecular pohycyclic compounds. (18 figures, 12 tables, 34 references) (auth)

Further insights into the kinetics of thermal decomposition during continuous cooling.

PubMed

Liavitskaya, Tatsiana; Guigo, Nathanaël; Sbirrazzuoli, Nicolas; Vyazovkin, Sergey

2017-07-26

Following the previous work (Phys. Chem. Chem. Phys., 2016, 18, 32021), this study continues to investigate the intriguing phenomenon of thermal decomposition during continuous cooling. The phenomenon can be detected and its kinetics can be measured by means of thermogravimetric analysis (TGA). The kinetics of the thermal decomposition of ammonium nitrate (NH 4 NO 3 ), nickel oxalate (NiC 2 O 4 ), and lithium sulfate monohydrate (Li 2 SO 4 ·H 2 O) have been measured upon heating and cooling and analyzed by means of the isoconversional methodology. The results have confirmed the hypothesis that the respective kinetics should be similar for single-step processes (NH 4 NO 3 decomposition) but different for multi-step ones (NiC 2 O 4 decomposition and Li 2 SO 4 ·H 2 O dehydration). It has been discovered that the differences in the kinetics can be either quantitative or qualitative. Physical insights into the nature of the differences have been proposed.

Pollutant content in marine debris and characterization by thermal decomposition.

PubMed

Iñiguez, M E; Conesa, J A; Fullana, A

2017-04-15

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

Microscopic observations of X-ray and gamma-ray induced decomposition of ammonium perchlorate crystals

NASA Technical Reports Server (NTRS)

Herley, P. J.; Levy, P. W.

1972-01-01

The X-ray and gamma-ray induced decomposition of ammonium perchlorate was studied by optical, transmission, and scanning electron microscopy. This material is a commonly used oxidizer in solid propellents which could be employed in deep-space probes, and where they will be subjected to a variety of radiations for as long as ten years. In some respects the radiation-induced damage closely resembles the effects produced by thermal decomposition, but in other respects the results differ markedly. Similar radiation and thermal effects include the following: (1) irregular or ill-defined circular etch pits are formed in both cases; (2) approximately the same size pits are produced; (3) the pit density is similar; (4) the c face is considerably more reactive than the m face; and (5) most importantly, many of the etch pits are aligned in crystallographic directions which are the same for thermal or radiolytic decomposition. Thus, dislocations play an important role in the radiolytic decomposition process.

Kinetics of Thermal Decomposition of Ammonium Perchlorate by TG/DSC-MS-FTIR

NASA Astrophysics Data System (ADS)

Zhu, Yan-Li; Huang, Hao; Ren, Hui; Jiao, Qing-Jie

2014-01-01

The method of thermogravimetry/differential scanning calorimetry-mass spectrometry-Fourier transform infrared (TG/DSC-MS-FTIR) simultaneous analysis has been used to study thermal decomposition of ammonium perchlorate (AP). The processing of nonisothermal data at various heating rates was performed using NETZSCH Thermokinetics. The MS-FTIR spectra showed that N2O and NO2 were the main gaseous products of the thermal decomposition of AP, and there was a competition between the formation reaction of N2O and that of NO2 during the process with an iso-concentration point of N2O and NO2. The dependence of the activation energy calculated by Friedman's iso-conversional method on the degree of conversion indicated that the AP decomposition process can be divided into three stages, which are autocatalytic, low-temperature diffusion and high-temperature, stable-phase reaction. The corresponding kinetic parameters were determined by multivariate nonlinear regression and the mechanism of the AP decomposition process was proposed.

Rate of warming affects temperature sensitivity of anaerobic peat decomposition and greenhouse gas production.

PubMed

Sihi, Debjani; Inglett, Patrick W; Gerber, Stefan; Inglett, Kanika S

2018-01-01

Temperature sensitivity of anaerobic carbon mineralization in wetlands remains poorly represented in most climate models and is especially unconstrained for warmer subtropical and tropical systems which account for a large proportion of global methane emissions. Several studies of experimental warming have documented thermal acclimation of soil respiration involving adjustments in microbial physiology or carbon use efficiency (CUE), with an initial decline in CUE with warming followed by a partial recovery in CUE at a later stage. The variable CUE implies that the rate of warming may impact microbial acclimation and the rate of carbon-dioxide (CO 2 ) and methane (CH 4 ) production. Here, we assessed the effects of warming rate on the decomposition of subtropical peats, by applying either a large single-step (10°C within a day) or a slow ramping (0.1°C/day for 100 days) temperature increase. The extent of thermal acclimation was tested by monitoring CO 2 and CH 4 production, CUE, and microbial biomass. Total gaseous C loss, CUE, and MBC were greater in the slow (ramp) warming treatment. However, greater values of CH 4 -C:CO 2 -C ratios lead to a greater global warming potential in the fast (step) warming treatment. The effect of gradual warming on decomposition was more pronounced in recalcitrant and nutrient-limited soils. Stable carbon isotopes of CH 4 and CO 2 further indicated the possibility of different carbon processing pathways under the contrasting warming rates. Different responses in fast vs. slow warming treatment combined with different endpoints may indicate alternate pathways with long-term consequences. Incorporations of experimental results into organic matter decomposition models suggest that parameter uncertainties in CUE and CH 4 -C:CO 2 -C ratios have a larger impact on long-term soil organic carbon and global warming potential than uncertainty in model structure, and shows that particular rates of warming are central to understand the response of wetland soils to global climate change. © 2017 John Wiley & Sons Ltd.

Spectral and thermal studies of MgI2·8H2O

NASA Astrophysics Data System (ADS)

Koleva, Violeta; Stefov, Viktor; Najdoski, Metodija; Ilievski, Zlatko; Cahil, Adnan

2017-10-01

In the present contribution special attention is paid to the spectroscopic and thermal characterization of MgI2·8H2O which is the stable hydrated form at room temperature. The infrared spectra of MgI2·8H2O and its deuterated analogues recorded at room and liquid nitrogen temperature are presented and interpreted. In the low-temperature diference infrared spectrum of the slightly deuterated analogue (≈5% D) at least four bands are found out of the expected five (at 2595, 2550, 2538 and 2495 cm-1) as a result of the uncoupled O-D oscillators in the isotopically isolated HOD molecules. Multiple bands are observed in the water bending region and only two bands of the HOH librational modes are found. For more precise and deep description of the processes occurring upon heating of MgI2·8H2O we have applied simultaneous TG/DTA/Mass spectrometry technique identifying the gases evolved during the thermal transformations. We have established that the thermal decomposition of MgI2·8H2O is a complex process that takes place in two main stages. In the first stage (between 120 and 275 °C) the salt undergoes a partial stepwise dehydration to MgI2·2H2O followed by a hydrolytic decomposition with formation of magnesium hydroxyiodide Mg(OH)1.44I0.56 accompanied with simultaneous release of H2O and HI. In the second stage Mg(OH)1.44I0.56 is completely decomposed to MgO with elimination of gaseous H2O, HI, I2 and H2. Infrared spectra of the annealed samples heated between 190 and 270 °C confirmed the formation of magnesium hydroxyiodide.

Mössbauer study on the thermal decomposition of potassium tris (oxalato) ferrate(III) trihydrate and bis (oxalato) ferrate(II) dihydrate

NASA Astrophysics Data System (ADS)

Ladriere, J.

1992-04-01

The thermal decompositions of K3Fe(ox)3 3 H2O and K2Fe(ox)2 2 H2O in nitrogen have been studied using Mössbauer spectroscopy, X-ray diffraction and thermal analysis methods in order to determine the nature of the solid residues obtained after each stage of decomposition. Particularly, after dehydration at 113°C, the ferric complex is reduced into a ferrous compound, with a quadrupole splitting of 3.89 mm/s, which corresponds to the anhydrous form of K2Fe(ox)2 2 H2O.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Hongyan, E-mail: hongyan.sun1@gmail.com, E-mail: ghanshyam.vaghjiani@us.af.mil; Vaghjiani, Ghanshyam L., E-mail: hongyan.sun1@gmail.com, E-mail: ghanshyam.vaghjiani@us.af.mil

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 foundmore » 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 reveal the formation of (NO{sub 2} + H{sub 2}O) to be the major decomposition path. Furthermore, we provide fundamental interpretations for the experimental results of Klapötke et al. [Combust. Flame 139, 358–366 (2004)] regarding the thermal stability of MNB and DNB, and their decomposition products. Notably, a fundamental understanding of fuel stability, decomposition mechanism, and key reactions leading to ignition is essential in the design and manipulation of molecular systems for the development of new energetic materials for advanced propulsion applications.« less

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

USDA-ARS?s Scientific Manuscript database

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

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. Copyright © 2014 Elsevier B.V. All rights reserved.

Thermal explosion analysis of methyl ethyl ketone peroxide by non-isothermal and isothermal calorimetric applications.

PubMed

Chi, Jen-Hao; Wu, Sheng-Hung; Shu, Chi-Min

2009-11-15

In the past, process incidents attributed to organic peroxides (OPs) that involved near misses, over-pressures, runaway reactions, and thermal explosions occurred because of poor training, human error, incorrect kinetic assumptions, insufficient change management, and inadequate chemical knowledge in the manufacturing process. Calorimetric applications were employed broadly to test organic peroxides on a small-scale because of their thermal hazards, such as exothermic behavior and self-accelerating decomposition in the laboratory. In essence, methyl ethyl ketone peroxide (MEKPO) is highly reactive and exothermically unstable. In recent years, it has undergone many thermal explosions and runaway reaction incidents in the manufacturing process. Differential scanning calorimetry (DSC), vent sizing package 2 (VSP2), and thermal activity monitor (TAM) were employed to analyze thermokinetic parameters and safety index. The intent of the analyses was to facilitate the use of various auto-alarm equipments to detect over-pressure, over-temperature, and hazardous materials leaks for a wide spectrum of operations. Results indicated that MEKPO decomposition is detected at low temperatures (30-40 degrees C), and the rate of decomposition was shown to exponentially increase with temperature and pressure. Determining time to maximum rate (TMR), self-accelerating decomposition temperature (SADT), maximum temperature (T(max)), exothermic onset temperature (T(0)), and heat of decomposition (DeltaH(d)) was essential for identifying early-stage runaway reactions effectively for industries.

Effect of Isomorphous Substitution on the Thermal Decomposition Mechanism of Hydrotalcites

PubMed Central

Crosby, Sergio; Tran, Doanh; Cocke, David; Duraia, El-Shazly M.; Beall, Gary W.

2014-01-01

Hydrotalcites have many important applications in catalysis, wastewater treatment, gene delivery and polymer stabilization, all depending on preparation history and treatment scenarios. In catalysis and polymer stabilization, thermal decomposition is of great importance. Hydrotalcites form easily with atmospheric carbon dioxide and often interfere with the study of other anion containing systems, particularly if formed at room temperature. The dehydroxylation and decomposition of carbonate occurs simultaneously, making it difficult to distinguish the dehydroxylation mechanisms directly. To date, the majority of work on understanding the decomposition mechanism has utilized hydrotalcite precipitated at room temperature. In this study, evolved gas analysis combined with thermal analysis has been used to show that CO2 contamination is problematic in materials being formed at RT that are poorly crystalline. This has led to some dispute as to the nature of the dehydroxylation mechanism. In this paper, data for the thermal decomposition of the chloride form of hydrotalcite are reported. In addition, carbonate-free hydrotalcites have been synthesized with different charge densities and at different growth temperatures. This combination of parameters has allowed a better understanding of the mechanism of dehydroxylation and the role that isomorphous substitution plays in these mechanisms to be delineated. In addition, the effect of anion type on thermal stability is also reported. A stepwise dehydroxylation model is proposed that is mediated by the level of aluminum substitution. PMID:28788231

Decomposition of nitrous oxide and chloromethanes absorbed on particulate matter

NASA Technical Reports Server (NTRS)

Rebbert, R. E.; Ausloos, P. J.

1978-01-01

The effect of pressure on the heterogeneous thermal and pyrolytic decomposition of nitrous oxides adsorbed on sand was studied. Results indicate that N20 adsorbed on certain sand surfaces can be decomposed by photons which nitrous oxide cannot absorb in the gas phase. There is also a thermal heterogeneous decomposition of nitrous oxide which also produces nitrogen. The photolysis of CC14, CFC13, CF2C12 adsorbed on fused quartz and on different types of sand was also investigated. There was no thermal heterogeneous reaction with any of these chloromethanes. Apparently the larger bond energy of approximately 74 kcal for the C-C1 bond compared to approximately 40 kcal for the N-O bond in N2O makes the thermal reaction inoperative for the chloromethanes.

Teaching a New Method of Partial Fraction Decomposition to Senior Secondary Students: Results and Analysis from a Pilot Study

ERIC Educational Resources Information Center

Man, Yiu-Kwong; Leung, Allen

2012-01-01

In this paper, we introduce a new approach to compute the partial fraction decompositions of rational functions and describe the results of its trials at three secondary schools in Hong Kong. The data were collected via quizzes, questionnaire and interviews. In general, according to the responses from the teachers and students concerned, this new…

Inhalation toxicology. V., Evaluation of relative toxicity to rats of thermal decomposition products from two aircraft seat fire-blocking materials.

DOT National Transportation Integrated Search

1985-11-01

Two fire-blocking layer (FBL) materials, designed to delay the thermal decomposition of polyurethane foam seat cushions during an aircraft cabin fire, were evaluated for the relative toxicity of their gaseous combustion products. Each materials was t...

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)

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.

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.

Investigation of MIS-sensor sensitivity to vapor of unsymmetrical dimethylgydrazine in air

NASA Astrophysics Data System (ADS)

Filipchuk, D. V.; Litvinov, A. V.; Etrekova, M. O.; Nozdrya, D. A.

2018-01-01

The sensitivity of MIS-sensor to the products of thermal decomposition of unsymmetrical dimethylhydrazine was investigated. It is shown that MIS sensor is able to detect the concentrations of the test substance by the means of the certain products of its thermal decomposition (ammonia and nitric dioxide).

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 signal found in the traditional compound elution time period reveals higher correlations with AMS hydrocarbon-like OA (HOA) combined with the fraction of OOA that is less oxygenated. Potential to quantify nitrate and sulfate aerosol mass concentrations using the TAG system is explored through analysis of ammonium sulfate and ammonium nitrate standards. While chemical standards display a linear response in the TAG system, re-desorptions of the CTD cell following ambient sample analysis shows some signal carryover on sulfate and organics, and new desorption methods should be developed to improve throughput. Future standards should be composed of complex organic/inorganic mixtures, similar to what is found in the atmosphere, and perhaps will more accurately account for any aerosol mixture effects on compositional quantification.

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) component. TAG signal found in the traditional compound elution time period reveals higher correlations with AMS hydrocarbon-like OA (HOA) combined with the fraction of OOA that is less oxygenated. Potential to quantify nitrate and sulfate aerosol mass concentrations using the TAG system is explored through analysis of ammonium sulfate and ammonium nitrate standards. While chemical standards display a linear response in the TAG system, redesorptions of the CTD cell following ambient sample analysis show some signal carryover on sulfate and organics, and new desorption methods should be developed to improve throughput. Future standards should be composed of complex organic/inorganic mixtures, similar to what is found in the atmosphere, and perhaps will more accurately account for any aerosol mixture effects on compositional quantification.

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

DOE PAGES

Williams, Brent J.; Zhang, Yaping; Zuo, Xiaochen; ...

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), NO 2 + ( m/z 46), SO + ( m/z 48), and SO 2 + ( m/z 64), derived from either inorganic or organic particle-phase nitrate and sulfate. CO 2 + ( 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 signal found in the traditional compound elution time period reveals higher correlations with AMS hydrocarbon-like OA (HOA) combined with the fraction of OOA that is less oxygenated. Potential to quantify nitrate and sulfate aerosol mass concentrations using the TAG system is explored through analysis of ammonium sulfate and ammonium nitrate standards. While chemical standards display a linear response in the TAG system, redesorptions of the CTD cell following ambient sample analysis show some signal carryover on sulfate and organics, and new desorption methods should be developed to improve throughput. Future standards should be composed of complex organic/inorganic mixtures, similar to what is found in the atmosphere, and perhaps will more accurately account for any aerosol mixture effects on compositional quantification.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Glascoe, E A; Zaug, J M; Burnham, A K

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.more » 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.« less

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.

Determination of the thermal stability of perfluoroalkylethers

NASA Technical Reports Server (NTRS)

Helmick, Larry S.; Jones, William R., Jr.

1990-01-01

The thermal decomposition temperatures of several commercial and custom synthesized perfluoroalkylether fluids were determined with a computerized tensimeter. In general, the decomposition temperatures of the commercial fluids were all similar and significantly higher than those for custom synthesized fluids. Correlation of the decomposition temperatures with the molecular structures of the primary components of the commercial fluids revealed that the stability of the fluids is not affected by intrinsic factors such as carbon chain length, branching, or cumulated difluoroformal groups. Instead, correlation with extrinsic factors revealed that the stability may be limited by the presence of small quantities of thermally unstable material and/or chlorine-containing material arising from the use of chlorine-containing solvents during synthesis. Finally, correlation of decomposition temperatures with molecular weights for Demnum and Krytox fluids supports a chain cleavage reaction mechanism for Demnum fluids and an unzipping reaction mechanism for Krytox fluids.

Some aspects of the thermodynamic behaviour of the lead-doped Bi-2223 system

NASA Astrophysics Data System (ADS)

Tetenbaum, M.; Maroni, V. A.

1996-02-01

A thermodynamic assessment of lead-doped Bi-2223 with emphasis on compositions and oxygen partial pressures within the homogeneity region prior to solid-state decomposition is presented. Equations for the variation of oxygen partial pressure with composition and temperature have been derived from our EMF measurements. Long-term metastability was indicated during cycling over a temperature range of ∼ 700-815°C of a lead-doped Bi-2223 sample having an oxygen-deficient stoichiometry of 9.64 prior to solid-state decomposition corresponding to the diphasic CuOCu 2O system. A trend of increasing negative values of the partial molar enthalpy Δ overlineH( O 2) and entropy Δ overlineS( O2 with increasing oxygen deficiency of the condensed phase indicated an increase in ordering of the cuprate structure prior to solid-state decomposition.

Pressure-dependent decomposition kinetics of the energetic material HMX up to 3.6 GPa.

PubMed

Glascoe, Elizabeth A; Zaug, Joseph M; Burnham, Alan K

2009-12-03

The effect of pressure on the global 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. Global 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 0.1 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 to pressure-inhibiting bond homolysis step(s), which would result in an increase in volume. These results indicate that both the beta- and delta-polymorphs of HMX are sensitive to pressure in the thermally induced decomposition kinetics.

Synthesis and characterization of nanoscale molybdenum sulfide catalysts by controlled gas phase decomposition of Mo(CO){sub 6} and H{sub 2}S

DOE Office of Scientific and Technical Information (OSTI.GOV)

Close, M.R.; Petersen, J.L.; Kugler, E.L.

1999-04-05

Molybdenum sulfide catalysts with surface areas ranging from 16 to 120 m{sup 2}/g were prepared by the thermal decomposition of Mo(CO){sub 6} and H{sub 2}S vapors in a specially designed tubular reactor system. The gas phase decomposition (GPD) reactions performed at 500--1100 C produced only MoS{sub 2} when excess H{sub 2}S was used. The optimum temperature range for the high-yield production of MoS{sub 2} was from 500 to 700 C. By controlling the decomposition temperature, the Mo(CO){sub 6} partial pressure, or the inert gas flow rate, the surface area, oxidation state, chemical composition, and the grain size of the molybdenummore » sulfide product(s) were modified. At reactor temperatures between 300 and 400 C, lower valent molybdenum sulfide materials, which were sulfur deficient relative to MoS{sub 2}, were obtained with formal molybdenum oxidation states intermediate to those found for Chevrel phase compounds, M{prime}Mo{sub 6}S{sub 8} (M{prime} = Fe, Ni, Co) and MoS{sub 2}. By lowering the H{sub 2}S flow rate used for the GPD reaction at 1000 C, mixtures containing variable amounts of MoS{sub 2} and Mo{sub 2}S{sub 3} were produced. Thus, through the modification of critical reactor parameters used for these GPD reactions, fundamental material properties were controlled.« less

Thermal decomposition of pyrazole to vinylcarbene + N 2: A first principles/RRKM study

NASA Astrophysics Data System (ADS)

da Silva, Gabriel

2009-05-01

Thermal decomposition of pyrazole, a five-membered nitrogen-containing heterocycle, has been studied using ab initio G3X theory and RRKM rate theory. The decomposition mechanism involves an intramolecular hydrogen shift to 3 H-pyrazole, followed by ring opening to 3-diazo-1-propene and dissociation to vinylcarbene (CH 2CHCH) + N 2. At 1 atm the calculated rate equation k [s -1] = 1.26 × 10 50T-10.699e -41200/T is obtained, which agrees with the results of flash vacuum pyrolysis experiments. The pyrazole decomposition product vinylcarbene is expected to rearrange to propyne, making pyrazole decomposition essentially thermoneutral. It is hypothesized that at high concentrations vinylcarbene could undergo a self-reaction to 1,3- and 1,4-cyclohexadiene.

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

NASA Astrophysics Data System (ADS)

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

2016-02-01

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

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

PubMed Central

2017-01-01

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

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

USDA-ARS?s Scientific Manuscript database

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...

Thermal characterization and model free kinetics of aged epoxies and foams using TGA and DSC methods.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cordaro, Joseph Gabriel; Kruizenga, Alan Michael; Nissen, April

2013-10-01

Two classes of materials, poly(methylene diphenyl diisocyanate) or PMDI foam, and cross-linked epoxy resins, were characterized using thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC), to help understand the effects of aging and %E2%80%9Cbake-out%E2%80%9D. The materials were evaluated for mass loss and the onset of decomposition. In some experiments, volatile materials released during heating were analyzed via mass spectroscopy. In all, over twenty materials were evaluated to compare the mass loss and onset temperature for decomposition. Model free kinetic (MFK) measurements, acquired using variable heating rate TGA experiments, were used to calculate the apparent activation energy of thermal decomposition.more » From these compiled data the effects of aging, bake-out, and sample history on the thermal stability of materials were compared. No significant differences between aged and unaged materials were detected. Bake-out did slightly affect the onset temperature of decomposition but only at the highest bake-out temperatures. Finally, some recommendations for future handling are made.« less

Preparation, non-isothermal decomposition kinetics, heat capacity and adiabatic time-to-explosion of NTOxDNAZ.

PubMed

Ma, Haixia; Yan, Biao; Li, Zhaona; Guan, Yulei; Song, Jirong; Xu, Kangzhen; Hu, Rongzu

2009-09-30

NTOxDNAZ was prepared by mixing 3,3-dinitroazetidine (DNAZ) and 3-nitro-1,2,4-triazol-5-one (NTO) in ethanol solution. The thermal behavior of the title compound was studied under a non-isothermal condition by DSC and TG/DTG methods. The kinetic parameters were obtained from analysis of the DSC and TG/DTG curves by Kissinger method, Ozawa method, the differential method and the integral method. The main exothermic decomposition reaction mechanism of NTOxDNAZ is classified as chemical reaction, and the kinetic parameters of the reaction are E(a)=149.68 kJ mol(-1) and A=10(15.81)s(-1). The specific heat capacity of the title compound was determined with continuous C(p) mode of microcalorimeter. The standard mole specific heat capacity of NTOxDNAZ was 352.56 J mol(-1)K(-1) in 298.15K. Using the relationship between C(p) and T and the thermal decomposition parameters, the time of the thermal decomposition from initialization to thermal explosion (adiabatic time-to-explosion) was obtained.

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

NASA Astrophysics Data System (ADS)

Patel, Vinay Kumar; Bhattacharya, Shantanu

2017-09-01

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

Resolving Some Paradoxes in the Thermal Decomposition Mechanism of Acetaldehyde

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sivaramakrishnan, Raghu; Michael, Joe V.; Harding, Lawrence B.

2015-07-16

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

Structure and thermal decomposition of sulfated β-cyclodextrin intercalated in a layered double hydroxide

NASA Astrophysics Data System (ADS)

Wang, Ji; Wei, Min; Rao, Guoying; Evans, David G.; Duan, Xue

2004-01-01

The sodium salt of hexasulfated β-cyclodextrin has been synthesized and intercalated into a magnesium-aluminum layered double hydroxide by ion exchange. The structure, composition and thermal decomposition behavior of the intercalated material have been studied by variable temperature X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), inductively coupled plasma emission spectroscopy (ICP), and thermal analysis (TG-DTA) and a model for the structure has been proposed. The thermal stability of the intercalated sulfated β-cyclodextrin is significantly enhanced compared with the pure form before intercalation.

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

PubMed

Tan, Linghua; Xu, Jianhua; Li, Shiying; Li, Dongnan; Dai, Yuming; Kou, Bo; Chen, Yu

2017-05-02

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 bymore » 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.« less

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

PubMed

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

2015-08-15

Elemental analyzer systems generate N(2) and CO(2) for elemental composition and isotope ratio measurements. As quantitative conversion of nitrogen in some materials (i.e., nitrate salts and nitro-organic compounds) is difficult, this study tests a recently published method - thermal decomposition without the addition of O(2) - for the analysis of these materials. Elemental analyzer/isotope ratio mass spectrometry (EA/IRMS) was used to compare the traditional combustion method (CM) and the thermal decomposition method (TDM), where additional O(2) is eliminated from the reaction. The comparisons used organic and inorganic materials with oxidized and/or reduced nitrogen and included ureas, nitrate salts, ammonium sulfate, nitro esters, and nitramines. Previous TDM applications were limited to nitrate salts and ammonium sulfate. The measurement precision and accuracy were compared to determine the effectiveness of converting materials containing different fractions of oxidized nitrogen into N(2). The δ(13) C(VPDB) values were not meaningfully different when measured via CM or TDM, allowing for the analysis of multiple elements in one sample. For materials containing oxidized nitrogen, (15) N measurements made using thermal decomposition were more precise than those made using combustion. The precision was similar between the methods for materials containing reduced nitrogen. The %N values were closer to theoretical when measured by TDM than by CM. The δ(15) N(AIR) values of purchased nitrate salts and ureas were nearer to the known values when analyzed using thermal decomposition than using combustion. The thermal decomposition method addresses insufficient recovery of nitrogen during elemental analysis in a variety of organic and inorganic materials. Its implementation requires relatively few changes to the elemental analyzer. Using TDM, it is possible to directly calibrate certain organic materials to international nitrate isotope reference materials without off-line preparation. Copyright © 2015 John Wiley & Sons, Ltd.

Thermal decomposition of sodium amide, NaNH2, and sodium amide hydroxide composites, NaNH2-NaOH.

PubMed

Jepsen, Lars H; Wang, Peikun; Wu, Guotao; Xiong, Zhitao; Besenbacher, Flemming; Chen, Ping; Jensen, Torben R

2016-09-14

Sodium amide, NaNH 2 , has recently been shown to be a useful catalyst to decompose NH 3 into H 2 and N 2 , however, sodium hydroxide is omnipresent and commercially available NaNH 2 usually contains impurities of NaOH (<2%). The thermal decomposition of NaNH 2 and NaNH 2 -NaOH composites is systematically investigated and discussed. NaNH 2 is partially dissolved in NaOH at T > 100 °C, forming a non-stoichiometric solid solution of Na(OH) 1-x (NH 2 ) x (0 < x < ∼0.30), which crystallizes in an orthorhombic unit cell with the space group P2 1 2 1 2 1 determined by synchrotron powder X-ray diffraction. The composite xNaNH 2 -(1 - x)NaOH (∼0.70 < x < 0.72) shows a lowered melting point, ∼160 °C, compared to 200 and 318 °C for neat NaNH 2 and NaOH, respectively. We report that 0.36 mol of NH 3 per mol of NaNH 2 is released below 400 °C during heating in an argon atmosphere, initiated at its melting point, T = 200 °C, possibly due to the formation of the mixed sodium amide imide solid solution. Furthermore, NaOH reacts with NaNH 2 at elevated temperatures and provides the release of additional NH 3 .

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vasiliou, AnGayle; National Renewable Energy Laboratory, 1617 Cole Blvd., Golden, Colorado 80401; Piech, Krzysztof M.

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 productsmore » 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.« less

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

PubMed

Zhou, Rong; Basile, Franco

2017-09-05

A method based on plasmon surface resonance absorption and heating was developed to perform a rapid on-surface protein thermal decomposition and digestion suitable for imaging mass spectrometry (MS) and/or profiling. This photothermal process or plasmonic thermal decomposition/digestion (plasmonic-TDD) method incorporates a continuous wave (CW) laser excitation and gold nanoparticles (Au-NPs) to induce known thermal decomposition reactions that cleave peptides and proteins specifically at the C-terminus of aspartic acid and at the N-terminus of cysteine. These thermal decomposition reactions are induced by heating a solid protein sample to temperatures between 200 and 270 °C for a short period of time (10-50 s per 200 μm segment) and are reagentless and solventless, and thus are devoid of sample product delocalization. In the plasmonic-TDD setup the sample is coated with Au-NPs and irradiated with 532 nm laser radiation to induce thermoplasmonic heating and bring about site-specific thermal decomposition on solid peptide/protein samples. In this manner the Au-NPs act as nanoheaters that result in a highly localized thermal decomposition and digestion of the protein sample that is independent of the absorption properties of the protein, making the method universally applicable to all types of proteinaceous samples (e.g., tissues or protein arrays). Several experimental variables were optimized to maximize product yield, and they include heating time, laser intensity, size of Au-NPs, and surface coverage of Au-NPs. Using optimized parameters, proof-of-principle experiments confirmed the ability of the plasmonic-TDD method to induce both C-cleavage and D-cleavage on several peptide standards and the protein lysozyme by detecting their thermal decomposition products with matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). The high spatial specificity of the plasmonic-TDD method was demonstrated by using a mask to digest designated sections of the sample surface with the heating laser and MALDI-MS imaging to map the resulting products. The solventless nature of the plasmonic-TDD method enabled the nonenzymatic on-surface digestion of proteins to proceed with undetectable delocalization of the resulting products from their precursor protein location. The advantages of this novel plasmonic-TDD method include short reaction times (<30 s/200 μm), compatibility with MALDI, universal sample compatibility, high spatial specificity, and localization of the digestion products. These advantages point to potential applications of this method for on-tissue protein digestion and MS-imaging/profiling for the identification of proteins, high-fidelity MS imaging of high molecular weight (>30 kDa) proteins, and the rapid analysis of formalin-fixed paraffin-embedded (FFPE) tissue samples.

Pointwise Partial Information Decomposition Using the Specificity and Ambiguity Lattices

NASA Astrophysics Data System (ADS)

Finn, Conor; Lizier, Joseph

2018-04-01

What are the distinct ways in which a set of predictor variables can provide information about a target variable? When does a variable provide unique information, when do variables share redundant information, and when do variables combine synergistically to provide complementary information? The redundancy lattice from the partial information decomposition of Williams and Beer provided a promising glimpse at the answer to these questions. However, this structure was constructed using a much criticised measure of redundant information, and despite sustained research, no completely satisfactory replacement measure has been proposed. In this paper, we take a different approach, applying the axiomatic derivation of the redundancy lattice to a single realisation from a set of discrete variables. To overcome the difficulty associated with signed pointwise mutual information, we apply this decomposition separately to the unsigned entropic components of pointwise mutual information which we refer to as the specificity and ambiguity. This yields a separate redundancy lattice for each component. Then based upon an operational interpretation of redundancy, we define measures of redundant specificity and ambiguity enabling us to evaluate the partial information atoms in each lattice. These atoms can be recombined to yield the sought-after multivariate information decomposition. We apply this framework to canonical examples from the literature and discuss the results and the various properties of the decomposition. In particular, the pointwise decomposition using specificity and ambiguity satisfies a chain rule over target variables, which provides new insights into the so-called two-bit-copy example.

Reactor cell assembly for use in spectroscopy and microscopy applications

DOEpatents

Grindstaff, Quirinus; Stowe, Ashley Clinton; Smyrl, Norm; Powell, Louis; McLane, Sam

2015-08-04

The present disclosure provides a reactor cell assembly that utilizes a novel design and that is wholly or partially manufactured from Aluminum, such that reactions involving Hydrogen, for example, including solid-gas reactions and thermal decomposition reactions, are not affected by any degree of Hydrogen outgassing. This reactor cell assembly can be utilized in a wide range of optical and laser spectroscopy applications, as well as optical microscopy applications, including high-temperature and high-pressure applications. The result is that the elucidation of the role of Hydrogen in the reactions studied can be achieved. Various window assemblies can be utilized, such that high temperatures and high pressures can be accommodated and the signals obtained can be optimized.

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

NASA Astrophysics Data System (ADS)

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

2017-09-01

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

Thermophysical properties of low cost lithium nitrate salts produced in northern Chile for thermal energy storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fernández, Ángel G.; Gomez-Vidal, Judith C.

In recent years, lithium containing salts have been studied for thermal energy storage (TES) applications because of their excellent thermophysical properties. In solar power plants, lithium is seen as a way to improve the properties of state-of-the art molten salts used today. Lithium nitrate is a good candidate for sensible heat storage, because of its ability to increase the salt mixture's working temperature range. In the present research, thermophysical properties characterization of lithium nitrate containing salts, produced in Chile, have been carried out. Corrosion evaluations at 390° and 565 °C for 1000 h were performed for low chromium steel T22more » and stainless steels (AISI 430 and AISI 316), respectively. Chemical composition of the salts including identification of corrosion products and impurities was determined and an estimation of the Chilean production costs is reported. The study shows a loss of thermal properties after the corrosion tests. The heat capacity was reduced, possibly caused by the formation of oxides at high temperatures. As a result, the partial thermal decomposition of the salt was probably produced by the incorporation of corrosion products from the steel.« less

Growth, stability and decomposition of Mg2Si ultra-thin films on Si (100)

NASA Astrophysics Data System (ADS)

Sarpi, B.; Zirmi, R.; Putero, M.; Bouslama, M.; Hemeryck, A.; Vizzini, S.

2018-01-01

Using Auger Electron Spectroscopy (AES), Scanning Tunneling Microscopy/Spectroscopy (STM/STS) and Low Energy Electron Diffraction (LEED), we report an in-situ study of amorphous magnesium silicide (Mg2Si) ultra-thin films grown by thermally enhanced solid-phase reaction of few Mg monolayers deposited at room temperature (RT) on a Si(100) surface. Silicidation of magnesium films can be achieved in the nanometric thickness range with high chemical purity and a high thermal stability after annealing at 150 °C, before reaching a regime of magnesium desorption for temperatures higher than 350 °C. The thermally enhanced reaction of one Mg monolayer (ML) results in the appearance of Mg2Si nanometric crystallites leaving the silicon surface partially uncovered. For thicker Mg deposition nevertheless, continuous 2D silicide films are formed with a volcano shape surface topography characteristic up to 4 Mg MLs. Due to high reactivity between magnesium and oxygen species, the thermal oxidation process in which a thin Mg2Si film is fully decomposed (0.75 eV band gap) into a magnesium oxide layer (6-8 eV band gap) is also reported.

Thermophysical properties of low cost lithium nitrate salts produced in northern Chile for thermal energy storage

DOE PAGES

Fernández, Ángel G.; Gomez-Vidal, Judith C.

2016-09-01

In recent years, lithium containing salts have been studied for thermal energy storage (TES) applications because of their excellent thermophysical properties. In solar power plants, lithium is seen as a way to improve the properties of state-of-the art molten salts used today. Lithium nitrate is a good candidate for sensible heat storage, because of its ability to increase the salt mixture's working temperature range. In the present research, thermophysical properties characterization of lithium nitrate containing salts, produced in Chile, have been carried out. Corrosion evaluations at 390° and 565 °C for 1000 h were performed for low chromium steel T22more » and stainless steels (AISI 430 and AISI 316), respectively. Chemical composition of the salts including identification of corrosion products and impurities was determined and an estimation of the Chilean production costs is reported. The study shows a loss of thermal properties after the corrosion tests. The heat capacity was reduced, possibly caused by the formation of oxides at high temperatures. As a result, the partial thermal decomposition of the salt was probably produced by the incorporation of corrosion products from the steel.« less

Pyrolysis and Matrix-Isolation FTIR of Acetoin

NASA Astrophysics Data System (ADS)

Cole, Sarah; Ellis, Martha; Sowards, John; McCunn, Laura R.

2017-06-01

Acetoin, CH_3C(O)CH(OH)CH_3, is an additive used in foods and cigarettes as well as a common component of biomass pyrolysate during the production of biofuels, yet little is known about its thermal decomposition mechanism. In order to identify thermal decomposition products of acetoin, a gas-phase mixture of approximately 0.3% acetoin in argon was subject to pyrolysis in a resistively heated SiC microtubular reactor at 1100-1500 K. Matrix-isolation FTIR spectroscopy was used to identify pyrolysis products. Many products were observed in analysis of the spectra, including acetylene, propyne, ethylene, and vinyl alcohol. These results provide clues to the overall mechanism of thermal decomposition and are important for predicting emissions from many industrial and residential processes.

Thermal Decomposition Behaviors and Burning Characteristics of Composite Propellants Prepared Using Combined Ammonium Perchlorate/Ammonium Nitrate Particles

NASA Astrophysics Data System (ADS)

Kohga, Makoto; Handa, Saori

2018-01-01

The thermal decomposition behaviors and burning characteristics of propellants prepared with combined ammonium perchlorate (AP)/ammonium nitrate (AN) particles greatly depended on the AN content (χ) of the AP/AN sample. The thermal decomposition behaviors of the propellants prepared with the combined samples almost matched those of the propellants prepared by physically mixing AP and AN particles, while their burning characteristics differed. The use of combined AP/AN particles decreased the heterogeneity of the combustion waves of the AP/AN propellants because of the difference in the combustion wave structure. In contrast, the addition of Fe2O3 caused unsteady combustion of the propellants prepared using samples with χ values lower than 8.1%.

Molecular dynamics simulations of methane hydrate decomposition.

PubMed

Myshakin, Evgeniy M; Jiang, Hao; Warzinski, Robert P; Jordan, Kenneth D

2009-03-12

Molecular dynamics simulations have been carried out to study decomposition of methane hydrate at different cage occupancies. The decomposition rate is found to depend sensitively on the hydration number. The rate of the destruction of the cages displays Arrhenius behavior, consistent with an activated mechanism. During the simulations, reversible formation of partial water cages around methane molecules in the liquid was observed at the interface at temperatures above the computed hydrate decomposition temperature.

Shape-dependence of the thermal and photochemical reactions of methanol on nanocrystalline anatase TiO2

NASA Astrophysics Data System (ADS)

Bennett, David A.; Cargnello, Matteo; Diroll, Benjamin T.; Murray, Christopher B.; Vohs, John M.

2016-12-01

Structure-activity relationships and the influence of particle size and shape on the partial- and photo-oxidation of methanol on nanocrystalline anatase TiO2 were investigated using temperature-programmed desorption. The study employed two distinct nanoparticle morphologies: truncated bipyramids exposing primarily {101} facets, and flatter platelets exposing primarily {001} surfaces, whose nominal sizes ranged from 10 to 25 nm. The platelets were found to be more active for thermally-driven reactions, such as coupling of methoxide groups to produce dimethyl ether, and deoxygenation to produce methane. A dependence of the reactivity of {001} facets for the coupling of methoxide groups to produce dimethyl ether on facet size was also observed. In contrast to the thermally-driven reactions, the bipyramidal nanoparticles were observed to be more active for a range of photochemical reactions, including oxidation and coupling to produce methyl formate, and photo-decomposition of surface methoxide species. This study also shows how well-defined nanocrystals can be used to help bridge the materials gap between studies of single crystal model catalysts and their high surface area industrial analogs.

Impact of cycling at low temperatures on the safety behavior of 18650-type lithium ion cells: Combined study of mechanical and thermal abuse testing accompanied by post-mortem analysis

NASA Astrophysics Data System (ADS)

Friesen, Alex; Horsthemke, Fabian; Mönnighoff, Xaver; Brunklaus, Gunther; Krafft, Roman; Börner, Markus; Risthaus, Tim; Winter, Martin; Schappacher, Falko M.

2016-12-01

The impact of cycling at low temperatures on the thermal and mechanical abuse behavior of commercial 18650-type lithium ion cells was compared to fresh cells. Post-mortem analyses revealed a deposition of high surface area lithium (HSAL) metal on the graphite surface accompanied by severe electrolyte decomposition. Heat wait search (HWS) tests in an accelerating rate calorimeter (ARC) were performed to investigate the thermal abuse behavior of aged and fresh cells under quasi-adiabatic conditions, showing a strong shift of the onset temperature for exothermic reactions. HSAL deposition promotes the reduction of the carbonate based electrolyte due to the high reactivity of lithium metal with high surface area, leading to a thermally induced decomposition of the electrolyte to produce volatile gaseous products. Nail penetration tests showed a change in the thermal runaway (TR) behavior affected by the decomposition reaction. This study indicates a greater thermal hazard for LIB cells at higher SOC and experiencing aging at low temperature.

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

NASA Astrophysics Data System (ADS)

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

2017-03-01

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

Ab initio kinetics of gas phase decomposition reactions.

PubMed

Sharia, Onise; Kuklja, Maija M

2010-12-09

The thermal and kinetic aspects of gas phase decomposition reactions can be extremely complex due to a large number of parameters, a variety of possible intermediates, and an overlap in thermal decomposition traces. The experimental determination of the activation energies is particularly difficult when several possible reaction pathways coexist in the thermal decomposition. Ab initio calculations intended to provide an interpretation of the experiment are often of little help if they produce only the activation barriers and ignore the kinetics of the decomposition process. To overcome this ambiguity, a theoretical study of a complete picture of gas phase thermo-decomposition, including reaction energies, activation barriers, and reaction rates, is illustrated with the example of the β-octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) molecule by means of quantum-chemical calculations. We study three types of major decomposition reactions characteristic of nitramines: the HONO elimination, the NONO rearrangement, and the N-NO(2) homolysis. The reaction rates were determined using the conventional transition state theory for the HONO and NONO decompositions and the variational transition state theory for the N-NO(2) homolysis. Our calculations show that the HMX decomposition process is more complex than it was previously believed to be and is defined by a combination of reactions at any given temperature. At all temperatures, the direct N-NO(2) homolysis prevails with the activation barrier at 38.1 kcal/mol. The nitro-nitrite isomerization and the HONO elimination, with the activation barriers at 46.3 and 39.4 kcal/mol, respectively, are slow reactions at all temperatures. The obtained conclusions provide a consistent interpretation for the reported experimental data.

Ab initio molecular dynamics study on the initial chemical events in nitramines: thermal decomposition of CL-20.

PubMed

Isayev, Olexandr; Gorb, Leonid; Qasim, Mo; Leszczynski, Jerzy

2008-09-04

CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane or HNIW) is a high-energy nitramine explosive. To improve atomistic understanding of the thermal decomposition of CL-20 gas and solid phases, we performed a series of ab initio molecular dynamics simulations. We found that during unimolecular decomposition, unlike other nitramines (e.g., RDX, HMX), CL-20 has only one distinct initial reaction channelhomolysis of the N-NO2 bond. We did not observe any HONO elimination reaction during unimolecular decomposition, whereas the ring-breaking reaction was followed by NO 2 fission. Therefore, in spite of limited sampling, that provides a mostly qualitative picture, we proposed here a scheme of unimolecular decomposition of CL-20. The averaged product population over all trajectories was estimated at four HCN, two to four NO2, two to four NO, one CO, and one OH molecule per one CL-20 molecule. Our simulations provide a detailed description of the chemical processes in the initial stages of thermal decomposition of condensed CL-20, allowing elucidation of key features of such processes as composition of primary reaction products, reaction timing, and Arrhenius behavior of the system. The primary reactions leading to NO2, NO, N 2O, and N2 occur at very early stages. We also estimated potential activation barriers for the formation of NO2, which essentially determines overall decomposition kinetics and effective rate constants for NO2 and N2. The calculated solid-phase decomposition pathways correlate with available condensed-phase experimental data.

Synthesis, characterization, thermal and explosive properties of potassium salts of trinitrophloroglucinol.

PubMed

Wang, Liqiong; Chen, Hongyan; Zhang, Tonglai; Zhang, Jianguo; Yang, Li

2007-08-17

Three different substituted potassium salts of trinitrophloroglucinol (H(3)TNPG) were prepared and characterized. The salts are all hydrates, and thermogravimetric analysis (TG) and elemental analysis confirmed that these salts contain crystal H2O and that the amount crystal H2O in potassium salts of H3TNPG is 1.0 hydrate for mono-substituted potassium salts of H3TNPG [K(H2TNPG)] and di-substituted potassium salt of H3TNPG [K2(HTNPG)], and 2.0 hydrate for tri-substituted potassium salt of H3TNPG [K3(TNPG)]. Their thermal decomposition mechanisms and kinetic parameters from 50 to 500 degrees C were studied under a linear heating rate by differential scanning calorimetry (DSC). Their thermal decomposition mechanisms undergo dehydration stage and intensive exothermic decomposition stage. FT-IR and TG studies verify that their final residua of decomposition are potassium cyanide or potassium carbonate. According to the onset temperature of the first exothermic decomposition process of dehydrated salts, the order of the thermal stability from low to high is from K(H2TNPG) and K2(HTNPG) to K3(TNPG), which is conform to the results of apparent activation energy calculated by Kissinger's and Ozawa-Doyle's method. Sensitivity test results showed that potassium salts of H3TNPG demonstrated higher sensitivity properties and had greater explosive probabilities.

A study of photothermal laser ablation of various polymers on microsecond time scales.

PubMed

Kappes, Ralf S; Schönfeld, Friedhelm; Li, Chen; Golriz, Ali A; Nagel, Matthias; Lippert, Thomas; Butt, Hans-Jürgen; Gutmann, Jochen S

2014-01-01

To analyze the photothermal ablation of polymers, we designed a temperature measurement setup based on spectral pyrometry. The setup allows to acquire 2D temperature distributions with 1 μm size and 1 μs time resolution and therefore the determination of the center temperature of a laser heating process. Finite element simulations were used to verify and understand the heat conversion and heat flow in the process. With this setup, the photothermal ablation of polystyrene, poly(α-methylstyrene), a polyimide and a triazene polymer was investigated. The thermal stability, the glass transition temperature Tg and the viscosity above Tg were governing the ablation process. Thermal decomposition for the applied laser pulse of about 10 μs started at temperatures similar to the start of decomposition in thermogravimetry. Furthermore, for polystyrene and poly(α-methylstyrene), both with a Tg in the range between room and decomposition temperature, ablation already occurred at temperatures well below the decomposition temperature, only at 30-40 K above Tg. The mechanism was photomechanical, i.e. a stress due to the thermal expansion of the polymer was responsible for ablation. Low molecular weight polymers showed differences in photomechanical ablation, corresponding to their lower Tg and lower viscosity above the glass transition. However, the difference in ablated volume was only significant at higher temperatures in the temperature regime for thermal decomposition at quasi-equilibrium time scales.

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

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.

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.

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

PubMed

Wu, Qiong; Zhu, Weihua; Xiao, Heming

2014-10-21

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

Study on microstructural changes in thermally-aged stainless steel weld-overlay cladding of nuclear reactor pressure vessels by atom probe tomography

NASA Astrophysics Data System (ADS)

Takeuchi, T.; Kameda, J.; Nagai, Y.; Toyama, T.; Nishiyama, Y.; Onizawa, K.

2011-08-01

The effect of thermal aging on microstructural changes was investigated in stainless steel weld-overlay cladding composed of 90% austenite and 10% δ-ferrite phases using atom probe tomography (APT). In as-received materials subjected to cooling process after post-welding heat treatments (PWHT), a slight fluctuation of the Cr concentration was already observed due to spinodal decomposition in the ferrite phase but not in the austenitic phase. Thermal aging at 400 °C for 10,000 h caused not only an increase in the amplitude of spinodal decomposition but also the precipitation of G phases with composition ratios of Ni:Si:Mn = 16:7:6 in the ferrite phase. The chemical compositions of M 23C 6 type carbides seemed to be formed at the austenite/ferrite interface were analyzed. The analyses of the magnitude of the spinodal decomposition and the hardness implied that the spinodal decomposition was the main cause of the hardening.

Thermochemical generation of hydrogen and carbon dioxide

NASA Technical Reports Server (NTRS)

Lawson, Daniel D. (Inventor); England, Christopher (Inventor)

1984-01-01

Mixing of carbon in the form of high sulfur coal with sulfuric acid reduces the temperature of sulfuric acid decomposition from 830.degree. C. to between 300.degree. C. and 400.degree. C. The low temperature sulfuric acid decomposition is particularly useful in thermal chemical cycles for splitting water to produce hydrogen. Carbon dioxide is produced as a commercially desirable byproduct. Lowering of the temperature for the sulfuric acid decomposition or oxygen release step simplifies equipment requirements, lowers thermal energy input and reduces corrosion problems presented by sulfuric acid at conventional cracking temperatures. Use of high sulfur coal as the source of carbon for the sulfuric acid decomposition provides an environmentally safe and energy efficient utilization of this normally polluting fuel.

Degradation of Perfluorooctanoic Acid and Perfluoroctane Sulfonate by Enzyme Catalyzed Oxidative Humification Reactions

NASA Astrophysics Data System (ADS)

Huang, Q.

2016-12-01

Poly- and perfluoroalkyl substances (PFASs) are alkyl based chemicals having multiple or all hydrogens replaced by fluorine atoms, and thus exhibit high thermal and chemical stability and other unusual characteristics. PFASs have been widely used in a wide variety of industrial and consumer products, and tend to be environmentally persistent. Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) are two representative PFASs that have drawn particular attention because of their ubiquitous presence in the environment, resistance to degradation and toxicity to animals. This study examined the decomposition of PFOA and PFOS in enzyme catalyzed oxidative humification reactions (ECOHR), a class of reactions that are ubiquitous in the environment involved in natural organic humification. Reaction rates and influential factors were examined, and high-resolution mass spectrometry was used to identify possible products. Fluorides and partially fluorinated compounds were identified as likely products from PFOA and PFOS degradation, which were possibly formed via a combination of free radical decomposition, rearrangements and coupling processes. The findings suggest that PFOA and PFOS may be transformed during humification, and ECOHR can potentially be used for the remediation of these chemicals.

New chemical hydrogen storage materials exploiting the self-sustaining thermal decomposition of guanidinium borohydride.

PubMed

Groshens, Thomas J; Hollins, Richard A

2009-06-07

Guanidinium borohydride (GBH) was structurally characterized by single-crystal X-ray diffraction and found to release more than 10 wt% H(2) as a fairly pure stream during a self-sustaining thermal decomposition reaction both with and without additives that were identified to reduce the concentration of the main ammonia impurity and control the reaction sustainability.

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].

Study on Thermal Decomposition Characteristics of Ammonium Nitrate Emulsion Explosive in Different Scales

NASA Astrophysics Data System (ADS)

Wu, Qiujie; Tan, Liu; Xu, Sen; Liu, Dabin; Min, Li

2018-04-01

Numerous accidents of emulsion explosive (EE) are attributed to uncontrolled thermal decomposition of ammonium nitrate emulsion (ANE, the intermediate of EE) and EE in large scale. In order to study the thermal decomposition characteristics of ANE and EE in different scales, a large-scale test of modified vented pipe test (MVPT), and two laboratory-scale tests of differential scanning calorimeter (DSC) and accelerating rate calorimeter (ARC) were applied in the present study. The scale effect and water effect both play an important role in the thermal stability of ANE and EE. The measured decomposition temperatures of ANE and EE in MVPT are 146°C and 144°C, respectively, much lower than those in DSC and ARC. As the size of the same sample in DSC, ARC, and MVPT successively increases, the onset temperatures decrease. In the same test, the measured onset temperature value of ANE is higher than that of EE. The water composition of the sample stabilizes the sample. The large-scale test of MVPT can provide information for the real-life operations. The large-scale operations have more risks, and continuous overheating should be avoided.

Determination of the Volume of Water for Suppressing the Thermal Decomposition of Forest Combustibles

NASA Astrophysics Data System (ADS)

Volkov, R. S.; Zhdanova, A. O.; Kuznetsov, G. V.; Strizhak, P. A.

2017-07-01

From the results of experimental studies of the processes of suppressing the thermal decomposition of the typical forest combustibles (birch leaves, fir needles, asp twigs, and a mixture of these three materials) by water aerosol, the minimum volumes of the fire-extinguishing liquid have been determined (by varying the volume of samples of the forest combustibles from 0.00002 m3 to 0.0003 m3 and the area of their open surface from 0.0001 m2 to 0.018 m2). The dependences of the minimum volume of water on the area of the open surface of the forest combustible have been established. Approximation expressions for these dependences have been obtained. Forecast has been made of the minimum volume of water for suppressing the process of thermal decomposition of forest combustibles in areas from 1 cm2 to 1 km2, as well as of the characteristic quenching times by varying the water concentration per unit time. It has been shown that the amount of water needed for effective suppression of the process of thermal decomposition of forest combustibles is several times less than is customarily assumed.

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

PubMed

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

2017-04-01

This paper deals with the problem of chromium recovery from chrome-tanned waste and thus with reducing the environmental impact of the leather industry. Chrome-tanned waste was transformed by alkaline enzymatic hydrolysis promoted by magnesium oxide into practically chromium-free, commercially applicable collagen hydrolysate and filtration cake containing a high portion of chromium. The crude and magnesium-deprived chromium cakes were subjected to a process of thermal decomposition at 650°C under oxygen-free conditions to reduce the amount of this waste and to study the effect of magnesium removal on the resulting products. Oxygen-free conditions were applied in order to prevent the oxidation of trivalent chromium into the hazardous hexavalent form. Thermal decomposition products from both crude and magnesium-deprived chrome cakes were characterized by high chromium content over 50%, which occurred as eskolaite (Cr 2 O 3 ) and magnesiochromite (MgCr 2 O 4 ) crystal phases, respectively. Thermal decomposition decreased the amount of chrome cake dry feed by 90%. Based on the performed experiments, a scheme for the total control of chromium in the leather industry was designed.

Thermal aging of electrolytes used in lithium-ion batteries - An investigation of the impact of protic impurities and different housing materials

NASA Astrophysics Data System (ADS)

Handel, Patricia; Fauler, Gisela; Kapper, Katja; Schmuck, Martin; Stangl, Christoph; Fischer, Roland; Uhlig, Frank; Koller, Stefan

2014-12-01

Thermal degradation products in lithium-ion batteries result mainly from hydrolysis sensitivity of lithium hexafluorophosphate (LiPF6). As organic carbonate solvents contain traces of protic impurities, the thermal decomposition of electrolytes is enhanced. Therefore, resulting degradation products are studied with nuclear magnetic resonance spectroscopy (NMR) and gas chromatography mass spectrometry (GC-MS). The electrolyte contains 1 M LiPF6 in a binary mixture of ethylene carbonate (EC) and diethylene carbonate (DEC) in a ratio of 1:2 (v/v) and is aged at ambient and elevated temperature. The impact of protic impurities, either added as deionized water or incorporated in positive electrode material, upon aging is investigated. Further, the influence of different housing materials on the electrolyte degradation is shown. Difluorophosphoric acid is identified as main decomposition product by NMR-spectroscopy. Traces of other decomposition products are determined by headspace GC-MS. Acid-base and coulometric titration are used to determine the total amount of acid and water content upon aging, respectively. The aim of this investigation is to achieve profound understanding about the thermal decomposition of one most common used electrolyte in a battery-like housing material.

Fabrication of porous MgCo2O4 with rod-like morphology and its superb catalytic activity towards ammonium perchlorate thermal decomposition

NASA Astrophysics Data System (ADS)

Li, Gang; Liu, Xiaoli; Bai, Weiyang

2018-03-01

In this paper, porous MgCo2O4 with rod-like morphology was successfully synthesized through the thermal treatment of metal oxalates precursor originated by the reaction of metal sulfates and oxalic acid, without the addition of other additives. The porous rod-like MgCo2O4, with a diameter of several hundred nanometers and a length of several micrometers, was formed through the agglomeration of numerous crystalline grains sized in 10–25 nm. Its catalytic effect on ammonium perchlorate (AP) thermal decomposition was evaluated using differential scanning calorimetry (DSC) techniques. It was found that the pyrolysis temperature of AP reduced by 129 °C and the heat release increased more than 3.19-fold with a 2 wt% addition of MgCo2O4. Meanwhile, the addition of MgCo2O4 resulted in an AP decomposition activation energy reduction from 216 kJ mol‑1 to 155 kJ mol‑1, calculated using the Kissinger correlation. This study provides new insights into the design and development of high performance catalysts for AP thermal decomposition.

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.

A Type-2 Block-Component-Decomposition Based 2D AOA Estimation Algorithm for an Electromagnetic Vector Sensor Array

PubMed Central

Gao, Yu-Fei; Gui, Guan; Xie, Wei; Zou, Yan-Bin; Yang, Yue; Wan, Qun

2017-01-01

This paper investigates a two-dimensional angle of arrival (2D AOA) estimation algorithm for the electromagnetic vector sensor (EMVS) array based on Type-2 block component decomposition (BCD) tensor modeling. Such a tensor decomposition method can take full advantage of the multidimensional structural information of electromagnetic signals to accomplish blind estimation for array parameters with higher resolution. However, existing tensor decomposition methods encounter many restrictions in applications of the EMVS array, such as the strict requirement for uniqueness conditions of decomposition, the inability to handle partially-polarized signals, etc. To solve these problems, this paper investigates tensor modeling for partially-polarized signals of an L-shaped EMVS array. The 2D AOA estimation algorithm based on rank-(L1,L2,·) BCD is developed, and the uniqueness condition of decomposition is analyzed. By means of the estimated steering matrix, the proposed algorithm can automatically achieve angle pair-matching. Numerical experiments demonstrate that the present algorithm has the advantages of both accuracy and robustness of parameter estimation. Even under the conditions of lower SNR, small angular separation and limited snapshots, the proposed algorithm still possesses better performance than subspace methods and the canonical polyadic decomposition (CPD) method. PMID:28448431

A Type-2 Block-Component-Decomposition Based 2D AOA Estimation Algorithm for an Electromagnetic Vector Sensor Array.

PubMed

Gao, Yu-Fei; Gui, Guan; Xie, Wei; Zou, Yan-Bin; Yang, Yue; Wan, Qun

2017-04-27

This paper investigates a two-dimensional angle of arrival (2D AOA) estimation algorithm for the electromagnetic vector sensor (EMVS) array based on Type-2 block component decomposition (BCD) tensor modeling. Such a tensor decomposition method can take full advantage of the multidimensional structural information of electromagnetic signals to accomplish blind estimation for array parameters with higher resolution. However, existing tensor decomposition methods encounter many restrictions in applications of the EMVS array, such as the strict requirement for uniqueness conditions of decomposition, the inability to handle partially-polarized signals, etc. To solve these problems, this paper investigates tensor modeling for partially-polarized signals of an L-shaped EMVS array. The 2D AOA estimation algorithm based on rank- ( L 1 , L 2 , · ) BCD is developed, and the uniqueness condition of decomposition is analyzed. By means of the estimated steering matrix, the proposed algorithm can automatically achieve angle pair-matching. Numerical experiments demonstrate that the present algorithm has the advantages of both accuracy and robustness of parameter estimation. Even under the conditions of lower SNR, small angular separation and limited snapshots, the proposed algorithm still possesses better performance than subspace methods and the canonical polyadic decomposition (CPD) method.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Wenwen; Luo, Qingping; Duan, Xiaohui

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 effectmore » 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.« less

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.

Synthesis, characterization, vibrational spectroscopy, and factor group analysis of partially metal-doped phosphate materials

NASA Astrophysics Data System (ADS)

Sronsri, Chuchai; Boonchom, Banjong

2018-04-01

A simple precipitating method was used to synthesize effectively a partially metal-doped phosphate hydrate (Mn0.9Mg0.1HPO4·3H2O), whereas the thermal decomposition process of the above hydrate precursor was used to obtain Mn1.8Mg0.2P2O7 and LiMn0.9Mg0.1PO4 compounds under different conditions. To separate the overlapping thermal decomposition peak, a deconvolution technique was used, and the separated peak was applied to calculate the water content. The factor group splitting analysis was used to exemplify their vibrational spectra obtained from normal vibrations of HPO42-, H2O, P2O74- and PO43- functional groups. Further, the deconvoluted bending mode of water was clearly observed. Mn0.9Mg0.1HPO4·3H2O was observed in the orthorhombic crystal system with the space group of Pbca (D2h15). The formula units per unit cell were found to be eight (Z = 8), and the site symmetric type of HPO42- was observed as Cs. For the HPO42- unit, the correlation filed splitting analysis of type C3v - Cs - D2h15 was calculated and had 96 internal modes, whereas H2O in the above hydrate was symbolized as C2v - Cs - D2h15 and had 24 modes. The symbol C2v - Cs - C2h3 was used for the correlation filed splitting analysis of P2O74- in Mn1.8Mg0.2P2O7 (monoclinic, C2/m (C2h3), Z = 2, and 42 modes). Finally, the symbol Td - Cs - D2h16 was used for the correlation filed splitting analysis of PO43- in LiMn0.9Mg0.1PO4 (orthorhombic, Pnma (D2h16), Z = 4, and 36 modes).

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.

Designing Stability into Thermally Reactive Plumbylenes.

PubMed

Bačić, Goran; Zanders, David; Mallick, Bert; Devi, Anjana; Barry, Seán T

2018-06-26

Lead analogues of N-heterocyclic carbenes (NHPbs) are the least understood members of this increasingly important class of compounds. Here we report the design, preparation, isolation, structure, volatility, and decomposition pathways of a novel aliphatic NHPb: rac- N  2 , N  3 -di- tert-butylbutane-2,3-diamido lead(II) (1Pb). The large steric bulk of the tert-butylamido moieties and rac-butane backbone successfully hinder redox decomposition pathways observed for diamidoethylene and -ethane backbone analogues, pushing the onset of thermal decomposition from below 0 °C to above 150 °C. With an exceptionally high vapor pressure of 1 Torr at 94 ± 2 °C and excellent thermal stability among Pb(II) complexes, 1Pb is a promising precursor for the chemical vapor deposition (CVD) and atomic layer deposition (ALD) of functional lead-containing materials.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leroy, F., E-mail: leroy@cinam.univ-mrs.fr; Passanante, T.; Cheynis, F.

2016-03-14

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 SiO{sub 2}/Si interface that enhances the silicon oxide decomposition at the void periphery.

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.

Influence of density and environmental factors on decomposition kinetics of amorphous polylactide - Reactive molecular dynamics studies.

PubMed

Mlyniec, A; Ekiert, M; Morawska-Chochol, A; Uhl, T

2016-06-01

In this work, we investigate the influence of the surrounding environment and the initial density on the decomposition kinetics of polylactide (PLA). The decomposition of the amorphous PLA was investigated by means of reactive molecular dynamics simulations. A computational model simulates the decomposition of PLA polymer inside the bulk, due to the assumed lack of removal of reaction products from the polymer matrix. We tracked the temperature dependency of the water and carbon monoxide production to extract the activation energy of thermal decomposition of PLA. We found that an increased density results in decreased activation energy of decomposition by about 50%. Moreover, initiation of decomposition of the amorphous PLA is followed by a rapid decline in activation energy caused by reaction products which accelerates the hydrolysis of esters. The addition of water molecules decreases initial energy of activation as well as accelerates the decomposition process. Additionally, we have investigated the dependency of density on external loading. Comparison of pressures needed to obtain assumed densities shows that this relationship is bilinear and the slope changes around a density equal to 1.3g/cm(3). The conducted analyses provide an insight into the thermal decomposition process of the amorphous phase of PLA, which is particularly susceptible to decomposition in amorphous and semi-crystalline PLA polymers. Copyright © 2016 Elsevier Inc. All rights reserved.

Damage characteristics and thermo-physical properties changes of limestone and sandstone during thermal treatment from -30 °C to 1000 °C

NASA Astrophysics Data System (ADS)

Shen, Yanjun; Yang, Yang; Yang, Gengshe; Hou, Xin; Ye, Wanjun; You, Zhemin; Xi, Jiami

2018-05-01

A series of experiments were carried out to measure the damage characteristics of two common sedimentary rocks of limestone and sandstone at temperatures ranging from -30 °C to 1000 °C The apparent thermal conductivity, thermal diffusivity and specific heat capacity were investigated respectively. Then, several discrepancy reasons for the damage characteristics and thermo-physical properties of limestone and sandstone were probed. The results show that water migration and phase transition are two core factors for the frost damage and thermal behaviors improvement during the cooling process(20 °C → -30 °C).The heating process (20 °C → 1000 °C) was divided into three stages of 20 °C → 200 °C, 200 °C → 600 °Cand 600 °C → 1000 °C. The first stage was closely related to pore-water evaporation, and the next two stages were attributed to the thermal reactions of mineral partials. The mineral decomposition tended to be intensified and resulted in the interior damage or even the accelerated degradation of thermal properties until at a threshold temperature of 600 °C. In essential, the structural features and the sensitivity of mineral composition to temperature were two mainly influential factors on the damage effects and heat conduct of the sedimentary rocks during variations in environmental temperature.

Desensitization of Explosive Materials

DTIC Science & Technology

1979-12-01

Decomposition of FEFO and DFF ...... o................. 20 Proposed Reaction Sequence of Initiation ......... o............ 29 Thermal Decomposition of...molecules are admitted to the reactor and, on an average, first decomposition products are analyzed without further reaction . The advantages of the VLPP... Reaction System Decomposition (Pmoles) Nitric acid 24 115 N02/N 204 < I tr Nitric acidc -- 100 aThe reactions were conducted at 100%C for 1 hour in

Organic Combustion in the Presence of Ca-Carbonate and Mg-Perchlorate: A Possible Source for the Low Temperature CO2 Release Seen in Mars Phoenix Thermal and Evolved Gas Analyzer Data

NASA Technical Reports Server (NTRS)

Archer, Douglas; Ming, D.; Niles, P.; Sutter, B.; Lauer, H.

2012-01-01

Two of the most important discoveries of the Phoenix Lander were the detection of approx.0.6% perchlorate [1] and 3-5% carbonate [2] in landing site soils. The Thermal and Evolved Gas Analyzer (TEGA) instrument on the Phoenix lander could heat samples up to approx.1000 C and monitor evolved gases with a mass spectrometer. TEGA detected a low (approx.350 C) and high (approx.750 C) temperature CO2 release. The high temp release was attributed to the thermal decomposition of Ca-carbonate (calcite). The low temperature CO2 release could be due to desorption of CO2, decomposition of a different carbonate mineral, or the combustion of organic material. A new hypothesis has also been proposed that the low temperature CO2 release could be due to the early breakdown of calcite in the presence of the decomposition products of certain perchlorate salts [3]. We have investigated whether or not this new hypothesis is also compatible with organic combustion. Magnesium perchlorate is stable as Mg(ClO4)2-6H2O on the martian surface [4]. During thermal decomposition, this perchlorate salt releases H2O, Cl2, and O2 gases. The Cl2 can react with water to form HCl which then reacts with calcite, releasing CO2 below the standard thermal decomposition temperature of calcite. However, when using concentrations of perchlorate and calcite similar to what was detected by Phoenix, the ratio of high:low temperature CO2 evolved is much larger in the lab, indicating that although this process might contribute to the low temp CO2 release, it cannot account for all of it. While H2O and Cl2 cause calcite decomposition, the O2 evolved during perchlorate decomposition can lead to the combustion of any reduced carbon present in the sample [5]. We investigate the possible contribution of organic molecules to the low temperature CO2 release seen on Mars.

Nanofiller Presence Enhances Polycyclic Aromatic Hydrocarbon (PAH) Profile on Nanoparticles Released during Thermal Decomposition of Nano-enabled Thermoplastics: Potential Environmental Health Implications.

PubMed

Singh, Dilpreet; Schifman, Laura Arabella; Watson-Wright, Christa; Sotiriou, Georgios A; Oyanedel-Craver, Vinka; Wohlleben, Wendel; Demokritou, Philip

2017-05-02

Nano-enabled products are ultimately destined to reach end-of-life with an important fraction undergoing thermal degradation through waste incineration or accidental fires. Although previous studies have investigated the physicochemical properties of released lifecycle particulate matter (called LCPM) from thermal decomposition of nano-enabled thermoplastics, critical questions about the effect of nanofiller on the chemical composition of LCPM still persist. Here, we investigate the potential nanofiller effects on the profiles of 16 Environmental Protection Agency (EPA)-priority polycyclic aromatic hydrocarbons (PAHs) adsorbed on LCPM from thermal decomposition of nano-enabled thermoplastics. We found that nanofiller presence in thermoplastics significantly enhances not only the total PAH concentration in LCPM but most importantly also the high molecular weight (HMW, 4-6 ring) PAHs that are considerably more toxic than the low molecular weight (LMW, 2-3 ring) PAHs. This nano-specific effect was also confirmed during in vitro cellular toxicological evaluation of LCPM for the case of polyurethane thermoplastic enabled with carbon nanotubes (PU-CNT). LCPM from PU-CNT shows significantly higher cytotoxicity compared to PU which could be attributed to its higher HMW PAH concentration. These findings are crucial and make the case that nanofiller presence in thermoplastics can significantly affect the physicochemical and toxicological properties of LCPM released during thermal decomposition.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burnham, A K; Weese, R K; Andrzejewski, W J

Decomposition kinetics are determined for HMX (nitramine octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) and CP (2-(5-cyanotetrazalato) pentaammine cobalt (III) perchlorate) separately and together. For high levels of thermal stress, the two materials decompose faster as a mixture than individually. This effect is observed both in high-temperature thermal analysis experiments and in long-term thermal aging experiments. An Arrhenius plot of the 10% level of HMX decomposition by itself from a diverse set of experiments is linear from 120 to 260 C, with an apparent activation energy of 165 kJ/mol. Similar but less extensive thermal analysis data for the mixture suggests a slightly lower activation energy formore » the mixture, and an analogous extrapolation is consistent with the amount of gas observed in the long-term detonator aging experiments, which is about 30 times greater than expected from HMX by itself for 50 months at 100 C. Even with this acceleration, however, it would take {approx}10,000 years to achieve 10% decomposition at {approx}30 C. Correspondingly, negligible decomposition is predicted by this kinetic model for a few decades aging at temperatures slightly above ambient. This prediction is consistent with additional sealed-tube aging experiments at 100-120 C, which are estimated to have an effective thermal dose greater than that from decades of exposure to temperatures slightly above ambient.« less

Investigation of the sensitivity of MIS-sensor to thermal decomposition products of cables insulation

NASA Astrophysics Data System (ADS)

Filipchuk, D. V.; Litvinov, A. V.; Etrekova, M. O.; Nozdrya, D. A.

2017-12-01

Sensitivity of the MIS-sensor to products of thermal decomposition of insulation and jacket of the most common types of cables is investigated. It is shown that hydrogen is evolved under heating the insulation to temperatures not exceeding 250 °C. Registration of the evolved hydrogen by the MIS-sensor can be used for detection of fires at an early stage.

Thermal Stability of FeS2 Cathode Material in "Thermal" Batteries: Effect of Dissolved Oxides in Molten Salt Electrolytes

NASA Astrophysics Data System (ADS)

Masset, Patrick J.

2008-09-01

The thermal stability of FeS2 cathode material for thermal batteries is investigated in the LiCl-KCl eutectic containing up to 10 wt% Li2O (used as anti-peak). The results show that the decomposition of pyrite shifts to higher temperatures in the presence of molten salts as the S2 gas is repressed by the liquid phase. For high lithium oxide contents the decomposition temperature of pyrite decreases by 100 °C. In addition Li2FeS2 as reaction product is evidenced whereas Li3Fe2S4 is expected from literature data.

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

PubMed Central

Tan, Linghua; Xu, Jianhua; Li, Shiying; Li, Dongnan; Dai, Yuming; Kou, Bo; Chen, Yu

2017-01-01

Novel graphitic carbon nitride/CuO (g-C3N4/CuO) nanocomposite was synthesized through a facile precipitation method. Due to the strong ion-dipole interaction between copper ions and nitrogen atoms of g-C3N4, CuO nanorods (length 200–300 nm, diameter 5–10 nm) were directly grown on g-C3N4, forming a g-C3N4/CuO nanocomposite, which was confirmed via X-ray diffraction (XRD), transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), and X-ray photoelectron spectroscopy (XPS). Finally, thermal decomposition of ammonium perchlorate (AP) in the absence and presence of the prepared g-C3N4/CuO nanocomposite was examined by differential thermal analysis (DTA), and thermal gravimetric analysis (TGA). The g-C3N4/CuO nanocomposite showed promising catalytic effects for the thermal decomposition of AP. Upon addition of 2 wt % nanocomposite with the best catalytic performance (g-C3N4/20 wt % CuO), the decomposition temperature of AP was decreased by up to 105.5 °C and only one decomposition step was found instead of the two steps commonly reported in other examples, demonstrating the synergistic catalytic activity of the as-synthesized nanocomposite. This study demonstrated a successful example regarding the direct growth of metal oxide on g-C3N4 by ion-dipole interaction between metallic ions, and the lone pair electrons on nitrogen atoms, which could provide a novel strategy for the preparation of g-C3N4-based nanocomposite. PMID:28772844

Fabrication of carbon nanotube films from alkyne-transition metal complexes

DOEpatents

Iyer, Vivekanantan S [Delft, NL; Vollhardt, K Peter C. [Oakland, CA

2007-08-28

A simple method for the production or synthesis of carbon nanotubes as free-standing films or nanotube mats by the thermal decomposition of transition metal complexed alkynes with aryl, alkyl, alkenyl, or alkynyl substituents. In particular, transition metal (e.g. Co, Ni, Fe, Mo) complexes of diarylacetylenes, e.g. diphenylacetylene, and solid mixtures of these complexes with suitable, additional carbon sources are heated in a vessel. More specifically, the heating of the transition metal complex is completed at a temperature between 400-800.degree. C. and more particularly 550-700.degree. C. for between 0.1 to 24 hours and more particularly 0.5-3 hours in a sealed vessel under a partial pressure of argon or helium.

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.

Solid solutions of platinum(II) and palladium(II) oxalato-complex salt as precursors of nanoalloys

NASA Astrophysics Data System (ADS)

Zadesenets, A. V.; Asanova, T. I.; Vikulova, E. S.; Filatov, E. Yu.; Plyusnin, P. E.; Baidina, I. A.; Asanov, I. P.; Korenev, S. V.

2013-03-01

A solid solution of platinum (II) and palladium (II) oxalato-complex salt, (NH4)2[Pt0.5Pd0.5(C2O4)2]·2H2O, has been synthesized and studied as a precursor for preparing bimetallic PtPd nanoparticles through its thermal decomposition. The smallest homogenous bimetallic PtPd nanoparticles were found to form in hydrogen and helium atmospheres. The annealing temperature and time have low effect on the bimetallic particles size. Comparative analysis of structural and thermal properties of the solid solution and individual Pt, Pd oxalato-complex salts was performed to investigate a mechanism of thermal decomposition of (NH4)2[Pt0.5Pd0.5(C2O4)2]·2H2O. Based on in situ X-ray photoemission spectroscopy investigation it was proposed a mechanism of formation of bimetallic PtPd nanoparticles from the solid-solution oxalato-complex salt during thermal decomposition.

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

PubMed

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

2017-02-28

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

Thermal degradation of Shredded Oil Palm Empty Fruit Bunches (SOPEFB) embedded with Cobalt catalyst by Thermogravimetric Analysis (TGA)

NASA Astrophysics Data System (ADS)

Alias, R.; Hamid, N. H.; Jaapar, J.; Musa, M.; Alwi, H.; Halim, K. H. Ku

2018-03-01

Thermal behavior and decomposition kinetics of shredded oil palm empty fruit bunches (SOPEFB) were investigated in this study by using thermogravimetric analysis (TGA). The SOPEFB were analyzed under conditions of temperature 30 °C to 900 °C with nitrogen gas flow at 50 ml/min. The SOPEFB were embedded with cobalt (II) nitrate solution with concentration 5%, 10%, 15% and 20%. The TG/DTG curves shows the degradation behavior of SOPEFB following with char production for each heating rate and each concentration of cobalt catalyst. Thermal degradation occurred in three phases, water drying phase, decomposition of hemicellulose and cellulose phase, and lignin decomposition phase. The kinetic equation with relevant parameters described the activation energy required for thermal degradation at the temperature regions of 200 °C to 350 °C. Activation energy (E) for different heating rate with SOPEFB embedded with different concentration of cobalt catalyst showing that the lowest E required was at SOPEFB with 20% concentration of cobalt catalyst..

A study of the relationship between process conditions and mechanical strength of mineralized red algae in the preparation of a marine-derived bone void filler.

PubMed

Walsh, P J; Walker, G M; Maggs, C A; Buchanan, F J

2011-06-01

Bone void fillers that can enhance biological function to augment skeletal repair have significant therapeutic potential in bone replacement surgery. This work focuses on the development of a unique microporous (0.5-10 microm) marine-derived calcium phosphate bioceramic granule. It was prepared from Corallina officinalis, a mineralized red alga, using a novel manufacturing process. This involved thermal processing, followed by a low pressure-temperature chemical synthesis reaction. The study found that the ability to maintain the unique algal morphology was dependent on the thermal processing conditions. This study investigates the effect of thermal heat treatment on the physiochemical properties of the alga. Thermogravimetric analysis was used to monitor its thermal decomposition. The resultant thermograms indicated the presence of a residual organic phase at temperatures below 500 degrees C and an irreversible solid-state phase transition from mg-rich-calcite to calcium oxide at temperatures over 850 degrees C. Algae and synthetic calcite were evaluated following heat treatment in an air-circulating furnace at temperatures ranging from 400 to 800 degrees C. The highest levels of mass loss occurred between 400-500 degrees C and 700-800 degrees C, which were attributed to the organic and carbonate decomposition respectively. The changes in mechanical strength were quantified using a simple mechanical test, which measured the bulk compressive strength of the algae. The mechanical test used may provide a useful evaluation of the compressive properties of similar bone void fillers that are in granular form. The study concluded that soak temperatures in the range of 600 to 700 degrees C provided the optimum physiochemical properties as a precursor to conversion to hydroxyapatite (HA). At these temperatures, a partial phase transition to calcium oxide occurred and the original skeletal morphology of the alga remained intact.

Transformation of zinc hydroxide chloride monohydrate to crystalline zinc oxide.

PubMed

Moezzi, Amir; Cortie, Michael; McDonagh, Andrew

2016-04-25

Thermal decomposition of layered zinc hydroxide double salts provides an interesting alternative synthesis for particles of zinc oxide. Here, we examine the sequence of changes occurring as zinc hydroxide chloride monohydrate (Zn5(OH)8Cl2·H2O) is converted to crystalline ZnO by thermal decomposition. The specific surface area of the resultant ZnO measured by BET was 1.3 m(2) g(-1). A complicating and important factor in this process is that the thermal decomposition of zinc hydroxide chloride is also accompanied by the formation of volatile zinc-containing species under certain conditions. We show that this volatile compound is anhydrous ZnCl2 and its formation is moisture dependent. Therefore, control of atmospheric moisture is an important consideration that affects the overall efficiency of ZnO production by this process.

Thermal Decomposition of Nd3(+), Sr2(+) and Pb2(+) Exchanged Beta’’ Aluminas,

DTIC Science & Technology

1987-07-01

reconstructive recrystallization process is responsible for the formation of the MP phase; this perhaps is a surprising result. The decomposition processes of Nd3... eutectics may be present. A general trend for all decompositions of metastable substituted " aluminas would therefore seem to be that when occurring

Decomposition of multilayer benzene and n-hexane films on vanadium.

PubMed

Souda, Ryutaro

2015-09-21

Reactions of multilayer hydrocarbon films with a polycrystalline V substrate have been investigated using temperature-programmed desorption and time-of-flight secondary ion mass spectrometry. Most of the benzene molecules were dissociated on V, as evidenced by the strong depression in the thermal desorption yields of physisorbed species at 150 K. The reaction products dehydrogenated gradually after the multilayer film disappeared from the surface. Large amount of oxygen was needed to passivate the benzene decomposition on V. These behaviors indicate that the subsurface sites of V play a role in multilayer benzene decomposition. Decomposition of the n-hexane multilayer films is manifested by the desorption of methane at 105 K and gradual hydrogen desorption starting at this temperature, indicating that C-C bond scission precedes C-H bond cleavage. The n-hexane dissociation temperature is considerably lower than the thermal desorption temperature of the physisorbed species (140 K). The n-hexane multilayer morphology changes at the decomposition temperature, suggesting that a liquid-like phase formed after crystallization plays a role in the low-temperature decomposition of n-hexane.

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.

Thermal decomposition of wood: influence of wood components and cellulose crystallite size.

PubMed

Poletto, Matheus; Zattera, Ademir J; Forte, Maria M C; Santana, Ruth M C

2012-04-01

The influence of wood components and cellulose crystallinity on the thermal degradation behavior of different wood species has been investigated using thermogravimetry, chemical analysis and X-ray diffraction. Four wood samples, Pinus elliottii (PIE), Eucalyptus grandis (EUG), Mezilaurus itauba (ITA) and Dipteryx odorata (DIP) were used in this study. The results showed that higher extractives contents associated with lower crystallinity and lower cellulose crystallite size can accelerate the degradation process and reduce the wood thermal stability. On the other hand, the thermal decomposition of wood shifted to higher temperatures with increasing wood cellulose crystallinity and crystallite size. These results indicated that the cellulose crystallite size affects the thermal degradation temperature of wood species. Copyright © 2012. Published by Elsevier Ltd.

Thermal decomposition of the solid phase of nitromethane: ab initio molecular dynamics simulations.

PubMed

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

2010-10-29

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.

Polymethacrylic acid as a new precursor of CuO nanoparticles

NASA Astrophysics Data System (ADS)

Hosny, Nasser Mohammed; Zoromba, Mohamed Shafick

2012-11-01

Polymethacrylic acid and its copper complexes have been synthesized and characterized. These complexes have been used as precursors to produce CuO nanoparticles by thermal decomposition in air. The stages of decompositions and the calcination temperature of the precursors have been determined from thermal analyses (TGA). The obtained CuO nanoparticles have been characterized by X-ray diffraction (XRD), scanning tunneling microscopy (STM) and transmission electron microscopy (TEM). XRD showed a monoclinic structure with particle size 8-20 nm for the synthesized copper oxide nanoparticles. These nanoparticles are catalytically active in decomposing hydrogen peroxide and a mechanism of decomposition has been suggested.

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.

Thermal decomposition of the amino acids glycine, cysteine, aspartic acid, asparagine, glutamic acid, glutamine, arginine and histidine.

PubMed

Weiss, Ingrid M; Muth, Christina; Drumm, Robert; Kirchner, Helmut O K

2018-01-01

The pathways of thermal instability of amino acids have been unknown. New mass spectrometric data allow unequivocal quantitative identification of the decomposition products. Calorimetry, thermogravimetry and mass spectrometry were used to follow the thermal decomposition of the eight amino acids G, C, D, N, E, Q, R and H between 185 °C and 280 °C. Endothermic heats of decomposition between 72 and 151 kJ/mol are needed to form 12 to 70% volatile products. This process is neither melting nor sublimation. With exception of cysteine they emit mainly H 2 O, some NH 3 and no CO 2 . Cysteine produces CO 2 and little else. The reactions are described by polynomials, AA→ a NH 3 + b H 2 O+ c CO 2 + d H 2 S+ e residue, with integer or half integer coefficients. The solid monomolecular residues are rich in peptide bonds. Eight of the 20 standard amino acids decompose at well-defined, characteristic temperatures, in contrast to commonly accepted knowledge. Products of decomposition are simple. The novel quantitative results emphasize the impact of water and cyclic condensates with peptide bonds and put constraints on hypotheses of the origin, state and stability of amino acids in the range between 200 °C and 300 °C.

Thermal decomposition pathways of hydroxylamine: theoretical investigation on the initial steps.

PubMed

Wang, Qingsheng; Wei, Chunyang; Pérez, Lisa M; Rogers, William J; Hall, Michael B; Mannan, M Sam

2010-09-02

Hydroxylamine (NH(2)OH) is an unstable compound at room temperature, and it has been involved in two tragic industrial incidents. Although experimental studies have been carried out to study the thermal stability of hydroxylamine, the detailed decomposition mechanism is still in debate. In this work, several density functional and ab initio methods were used in conjunction with several basis sets to investigate the initial thermal decomposition steps of hydroxylamine, including both unimolecular and bimolecular reaction pathways. The theoretical investigation shows that simple bond dissociations and unimolecular reactions are unlikely to occur. The energetically favorable initial step of decomposition pathways was determined as a bimolecular isomerization of hydroxylamine into ammonia oxide with an activation barrier of approximately 25 kcal/mol at the MPW1K level of theory. Because hydroxylamine is available only in aqueous solutions, solvent effects on the initial decomposition pathways were also studied using water cluster methods and the polarizable continuum model (PCM). In water, the activation barrier of the bimolecular isomerization reaction decreases to approximately 16 kcal/mol. The results indicate that the bimolecular isomerization pathway of hydroxylamine is more favorable in aqueous solutions. However, the bimolecular nature of this reaction means that more dilute aqueous solution will be more stable.

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

Study of a Novel Method for the Thermolysis of Solutes in Aqueous Solution Using a Low Temperature Bubble Column Evaporator.

PubMed

Shahid, Muhammad; Xue, Xinkai; Fan, Chao; Ninham, Barry W; Pashley, Richard M

2015-06-25

An enhanced thermal decomposition of chemical compounds in aqueous solution has been achieved at reduced solution temperatures. The technique exploits hitherto unrecognized properties of a bubble column evaporator (BCE). It offers better heat transfer efficiency than conventional heat transfer equipment. This is obtained via a continuous flow of hot, dry air bubbles of optimal (1-3 mm) size. Optimal bubble size is maintained by using the bubble coalescence inhibition property of some salts. This novel method is illustrated by a study of thermal decomposition of ammonium bicarbonate (NH4HCO3) and potassium persulfate (K2S2O8) in aqueous solutions. The decomposition occurs at significantly lower temperatures than those needed in bulk solution. The process appears to work via the continuous production of hot (e.g., 150 °C) dry air bubbles, which do not heat the solution significantly but produce a transient hot surface layer around each rising bubble. This causes the thermal decomposition of the solute. The decomposition occurs due to the effective collision of the solute with the surface of the hot bubbles. The new process could, for example, be applied to the regeneration of the ammonium bicarbonate draw solution used in forward osmosis.

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.

Characterization and Thermal Decomposition of Nanometer 2,2', 4,4', 6,6'-Hexanitro-Stilbene and 1,3,5-Triamino-2,4,6-Trinitrobenzene Fabricated by a Mechanical Milling Method

NASA Astrophysics Data System (ADS)

Song, Xiaolan; Wang, Yi; Zhao, Shanshan; An, Chongwei; Wang, Jingyu; Zhang, Jinglin

2018-04-01

Nanometer 2,2', 4,4', 6,6'-hexanitro-stilbene (HNS) and 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) were fabricated on a high-energy ball mill. The particle sizes of nano-HNS and nano-TATB were 98.4 and 57.8 nm, respectively. An SEM analysis was employed to image the micron morphology of nano-explosives. The particle size distribution was calculated by measuring the size of 300 particles in SEM images. XRD, IR, and XPS analyses were used to confirm whether the crystal phase, molecule structure, and surface elements were changed by the milling process. Thermal decomposition of nano-HNS and nano-TATB was investigated by differential scanning calorimetry (DSC) and thermal-infrared spectrometry online (DSC-IR) analyses. Using DSC traces collected from different heating rates, the kinetic and thermodynamic parameters of thermolysis of raw and nano-explosives were calculated (activation energy (EK), pre-exponential factor (lnAK), rate constant (k), activation heat (ΔH≠), activation free energy (ΔG≠), activation entropy (ΔS≠), critical temperature of thermal explosion (Tb), and critical heating rate of thermal explosion (dT/dt)Tb). The results indicated that nano-explosives were of different kinetic and thermodynamic properties from starting explosives. In addition, the gas products for thermal decomposition of nano-HNS and nano-TATB were detected. Although HNS and TATB are both nitro explosives, the decomposition products of the two were different. A mechanism to explain the difference is proposed.

New insights into thermal decomposition of polycyclic aromatic hydrocarbon oxyradicals.

PubMed

Liu, Peng; Lin, He; Yang, Yang; Shao, Can; Gu, Chen; Huang, Zhen

2014-12-04

Thermal decompositions of polycyclic aromatic hydrocarbon (PAH) oxyradicals on various surface sites including five-membered ring, free-edge, zigzag, and armchair have been systematically investigated by using ab initio density functional theory B3LYP/6-311+G(d,p) basis set. The calculation based on Hückel theory indicates that PAHs (3H-cydopenta[a]anthracene oxyradical) with oxyradicals on a five-membered ring site have high chemical reactivity. The rate coefficients of PAH oxyradical decomposition were evaluated by using Rice-Ramsperger-Kassel-Marcus theory and solving the master equations in the temperature range of 1500-2500 K and the pressure range of 0.1-10 atm. The kinetic calculations revealed that the rate coefficients of PAH oxyradical decomposition are temperature-, pressure-, and surface site-dependent, and the oxyradical on a five-membered ring is easier to decompose than that on a six-membered ring. Four-membered rings were found in decomposition of the five-membered ring, and a new reaction channel of PAH evolution involving four-membered rings is recommended.

DART-MS analysis of inorganic explosives using high temperature thermal desorption†‡

PubMed Central

Sisco, Edward; Staymates, Matthew; Gillen, Greg

2018-01-01

An ambient mass spectrometry (MS) platform coupling resistive Joule heating thermal desorption (JHTD) and direct analysis in real time (DART) was implemented for the analysis of inorganic nitrite, nitrate, chlorate, and perchlorate salts. The resistive heating component generated discrete and rapid heating ramps and elevated temperatures, up to approximately 400 °C s−1 and 750 °C, by passing a few amperes of DC current through a nichrome wire. JHTD enhanced the utility and capabilities of traditional DART-MS for the trace detection of previously difficult to detect inorganic compounds. A partial factorial design of experiments (DOE) was implemented for the systematic evaluation of five system parameters. A base set of conditions for JHTD-DART-MS was derived from this evaluation, demonstrating sensitive detection of a range of inorganic oxidizer salts, down to single nanogram levels. DOE also identified JHTD filament current and in-source collision induced dissociation (CID) energy as inducing the greatest effect on system response. Tuning of JHTD current provided a method for controlling the relative degrees of thermal desorption and thermal decomposition. Furthermore, in-source CID provided manipulation of adduct and cluster fragmentation, optimizing the detection of molecular anion species. Finally, the differential thermal desorption nature of the JHTD-DART platform demonstrated efficient desorption and detection of organic and inorganic explosive mixtures, with each desorbing at its respective optimal temperature. PMID:29651308

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aviles-Ramos, Cuauhtemoc

A thermal decomposition model for PBX 9501 (95% HMX, 2.5% Estane® binder, 2.5% BDNPA/F nitro-plasticizer) was implemented by Dickson, et. al. The objective in this study is to estimate parameters associated with this kinetics model so it can be applied to carry out thermal ignition predictions for LX-07 (90% HMX, 10% Viton binder). LX-07 thermal ignition experiments have been carried out using the “Sandia Instrumented Thermal Ignition Apparatus”, SITI. The SITI design consists of solid cylinders (1” diameter × 1” height) of high explosive (HE) confined by a cylindrical aluminum case. An electric heater is wrapped around the outer surfacemore » of the case. This heater produces a temperature heating ramp on the outer surface of the case. Internal thermocouples measure the HE temperature rise from the center to locations close to the HE-aluminum interface. The energetic material is heated until thermal ignition occurs. A two–dimensional axisymmetric heat conduction finite element model is used to simulate these experiments. The HE thermal decomposition kinetics is coupled to a heat conduction model trough the definition of an energy source term. The parameters used to define the HE thermal decomposition model are optimized to obtain a good agreement with the experimental time to thermal ignition and temperatures. Also, heat capacity and thermal conductivity of the LX-07 mixture were estimated using temperatures measured at the center of the HE before the solid to solid HMX phase transition occurred.« less

Electrochemical Energy Summit An International Summit in Support of Societal Energy Needs

DTIC Science & Technology

2015-03-31

40A/dm2, 80 deg.C. Raney Ni alloy coating had advantage for oxygen over- voltage. (100mV – 200mV saving against Ni metal) Thermal decomposition...100mV – 200mV saving against Ni base metal. Cathode: Thermal decomposition coating of mixed noble metal on Ni base metal showed low hydrogen over... thermal stability up to 210 ◦C, and exhibited a high proton conductivity (2.4×10−2 S cm−1 at 80 ◦C) and a low methanol permeability (3.3×10−7 cm2 s−1

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hobbs, Michael L.

We previously developed a PETN thermal decomposition model that accurately predicts thermal ignition and detonator failure [1]. This model was originally developed for CALORE [2] and required several complex user subroutines. Recently, a simplified version of the PETN decomposition model was implemented into ARIA [3] using a general chemistry framework without need for user subroutines. Detonator failure was also predicted with this new model using ENCORE. The model was simplified by 1) basing the model on moles rather than mass, 2) simplifying the thermal conductivity model, and 3) implementing ARIA’s new phase change model. This memo briefly describes the model,more » implementation, and validation.« less

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.

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.

ReaxFF molecular dynamics simulation of thermal stability of a Cu3(BTC)2 metal-organic framework.

PubMed

Huang, Liangliang; Joshi, Kaushik L; van Duin, Adri C T; Bandosz, Teresa J; Gubbins, Keith E

2012-08-28

The thermal stability of a dehydrated Cu(3)(BTC)(2) (copper(II) benzene 1,3,5-tricarboxylate) metal-organic framework was studied by molecular dynamics simulation with a ReaxFF reactive force field. The results show that Cu(3)(BTC)(2) is thermally stable up to 565 K. When the temperature increases between 600 K and 700 K, the framework starts to partially collapse. The RDF analysis shows that the long range correlations between Cu dimers disappear, indicating the loss of the main channels of Cu(3)(BTC)(2). When the temperature is above 800 K, we find the decomposition of the Cu(3)(BTC)(2) framework. CO is the major product, and we also observe the release of CO(2), O(2), 1,3,5-benzenetricarboxylate (C(6)H(3)(CO(2))(3), BTC) and glassy carbon. The Cu dimer is stable up to 1100 K, but we find the formation of new copper oxide clusters at 1100 K. These results are consistent with experimental findings, and provide valuable information for future theoretical investigations of Cu(3)(BTC)(2) and its application in adsorption, separation and catalytic processes.

Influence of SiO2 Addition on Properties of PTFE/TiO2 Microwave Composites

NASA Astrophysics Data System (ADS)

Yuan, Ying; Wang, Jie; Yao, Minghao; Tang, Bin; Li, Enzhu; Zhang, Shuren

2018-01-01

Composite substrates for microwave circuit applications have been fabricated by filling polytetrafluoroethylene (PTFE) polymer matrix with ceramic powder consisting of rutile TiO2 ( D 50 ≈ 5 μm) partially substituted with fused amorphous SiO2 ( D 50 ≈ 8 μm) with composition x vol.% SiO2 + (50 - x) vol.% TiO2 ( x = 0, 3, 6, 9, 12), and the effects of SiO2 addition on characteristics such as the density, moisture absorption, microwave dielectric properties, and thermal properties systematically investigated. The results show that the filler was well distributed throughout the matrix. High dielectric constant ( ɛ r > 7.19) and extremely low moisture absorption (<0.02%) were obtained, resulting from the relatively high density of the composites. The ceramic particles served as barriers and improved the thermal stability of the PTFE polymer, retarding its decomposition. The temperature coefficient of dielectric constant ( τ ɛ ) of the composites shifted toward the positive direction (from - 309 ppm/°C to - 179 ppm/°C) as the SiO2 content was increased, while the coefficient of thermal expansion remained almost unchanged (˜ 35 ppm/°C).

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.

System for thermal energy storage, space heating and cooling and power conversion

DOEpatents

Gruen, Dieter M.; Fields, Paul R.

1981-04-21

An integrated system for storing thermal energy, for space heating and cong and for power conversion is described which utilizes the reversible thermal decomposition characteristics of two hydrides having different decomposition pressures at the same temperature for energy storage and space conditioning and the expansion of high-pressure hydrogen for power conversion. The system consists of a plurality of reaction vessels, at least one containing each of the different hydrides, three loops of circulating heat transfer fluid which can be selectively coupled to the vessels for supplying the heat of decomposition from any appropriate source of thermal energy from the outside ambient environment or from the spaces to be cooled and for removing the heat of reaction to the outside ambient environment or to the spaces to be heated, and a hydrogen loop for directing the flow of hydrogen gas between the vessels. When used for power conversion, at least two vessels contain the same hydride and the hydrogen loop contains an expansion engine. The system is particularly suitable for the utilization of thermal energy supplied by solar collectors and concentrators, but may be used with any source of heat, including a source of low-grade heat.

Calculation of the Full Scattering Amplitude without Partial Wave Decomposition. 2; Inclusion of Exchange

NASA Technical Reports Server (NTRS)

Shertzer, Janine; Temkin, Aaron

2004-01-01

The development of a practical method of accurately calculating the full scattering amplitude, without making a partial wave decomposition is continued. The method is developed in the context of electron-hydrogen scattering, and here exchange is dealt with by considering e-H scattering in the static exchange approximation. The Schroedinger equation in this approximation can be simplified to a set of coupled integro-differential equations. The equations are solved numerically for the full scattering wave function. The scattering amplitude can most accurately be calculated from an integral expression for the amplitude; that integral can be formally simplified, and then evaluated using the numerically determined wave function. The results are essentially identical to converged partial wave results.

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

PubMed

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

2018-03-01

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

Kinetics of non-isothermal decomposition of cinnamic acid

NASA Astrophysics Data System (ADS)

Zhao, Ming-rui; Qi, Zhen-li; Chen, Fei-xiong; Yue, Xia-xin

2014-07-01

The thermal stability and kinetics of decomposition of cinnamic acid were investigated by thermogravimetry and differential scanning calorimetry at four heating rates. The activation energies of this process were calculated from analysis of TG curves by methods of Flynn-Wall-Ozawa, Doyle, Distributed Activation Energy Model, Šatava-Šesták and Kissinger, respectively. There are only one stage of thermal decomposition process in TG and two endothermic peaks in DSC. For this decomposition process of cinnamic acid, E and log A[s-1] were determined to be 81.74 kJ mol-1 and 8.67, respectively. The mechanism was Mampel Power law (the reaction order, n = 1), with integral form G(α) = α (α = 0.1-0.9). Moreover, thermodynamic properties of Δ H ≠, Δ S ≠, Δ G ≠ were 77.96 kJ mol-1, -90.71 J mol-1 K-1, 119.41 kJ mol-1.

Exothermic or Endothermic Decomposition of Disubstituted Tetrazoles Tuned by Substitution Fashion and Substituents.

PubMed

Jia, Yu-Hui; Yang, Kai-Xiang; Chen, Shi-Lu; Huang, Mu-Hua

2018-01-11

Nitrogen-rich compounds such as tetrazoles are widely used as candidates in gas-generating agents. However, the details of the differentiation of the two isomers of disubstituted tetrazoles are rarely studied, which is very important information for designing advanced materials based on tetrazoles. In this article, pairs of 2,5- and 1,5-disubstituted tetrazoles were carefully designed and prepared for study on their thermal decomposition behavior. Also, the substitution fashion of 2,5- and 1,5- and the substituents at C-5 position were found to affect the endothermic or exothermic properties. This is for the first time to the best of our knowledge that the thermal decomposition properties of different tetrazoles could be tuned by substitution ways and substitute groups, which could be used as a useful platform to design advanced materials for temperature-dependent rockets. The aza-Claisen rearrangement was proposed to understand the endothermic decomposition behavior.

Laboratory Tests to Determine the Chemical and Physical Characteristics of Propellant-Solvent-Fuel Oil Mixtures

DTIC Science & Technology

1990-02-01

Decomposition ................ 165 Part IV. Thermal Decomposition - Analytical Methodologies .............. 167 Part V. Miscellaneous...500C ................... 45 12 Differential Scanning Calorimetry Curve for the Decomposition of a Smokeless-Grade Nitrocellulose .......... 62 13 Process...cellulose backbone with nitrating acids of high water content resulted in hydrolysis of the pentosans without the desired 3 result of nitration. Furthermore

Thermal and Chemical Characterization of Non-Metallic Materials Using Coupled Thermogravimetric Analysis and Infrared Spectroscopy

NASA Technical Reports Server (NTRS)

Huff, Timothy L.

2002-01-01

Thermogravimetric analysis (TGA) is widely employed in the thermal characterization of non-metallic materials, yielding valuable information on decomposition characteristics of a sample over a wide temperature range. However, a potential wealth of chemical information is lost during the process, with the evolving gases generated during thermal decomposition escaping through the exhaust line. Fourier Transform-Infrared spectroscopy (FT-IR) is a powerful analytical technique for determining many chemical constituents while in any material state, in this application, the gas phase. By linking these two techniques, evolving gases generated during the TGA process are directed into an appropriately equipped infrared spectrometer for chemical speciation. Consequently, both thermal decomposition and chemical characterization of a material may be obtained in a single sample run. In practice, a heated transfer line is employed to connect the two instruments while a purge gas stream directs the evolving gases into the FT-IR. The purge gas can be either high purity air or an inert gas such as nitrogen to allow oxidative and pyrolytic processes to be examined, respectively. The FT-IR data is collected realtime, allowing continuous monitoring of chemical compositional changes over the course of thermal decomposition. Using this coupled technique, an array of diverse materials has been examined, including composites, plastics, rubber, fiberglass epoxy resins, polycarbonates, silicones, lubricants and fluorocarbon materials. The benefit of combining these two methodologies is of particular importance in the aerospace community, where newly developing materials have little available data with which to refer. By providing both thermal and chemical data simultaneously, a more definitive and comprehensive characterization of the material is possible. Additionally, this procedure has been found to be a viable screening technique for certain materials, with the generated data useful in the selection of other appropriate analytical procedures for further material characterization.

Methane Decomposition and Carbon Growth on Y2O3, Yttria-Stabilized Zirconia, and ZrO2

PubMed Central

2014-01-01

Carbon deposition following thermal methane decomposition under dry and steam reforming conditions has been studied on yttria-stabilized zirconia (YSZ), Y2O3, and ZrO2 by a range of different chemical, structural, and spectroscopic characterization techniques, including aberration-corrected electron microscopy, Raman spectroscopy, electric impedance spectroscopy, and volumetric adsorption techniques. Concordantly, all experimental techniques reveal the formation of a conducting layer of disordered nanocrystalline graphite covering the individual grains of the respective pure oxides after treatment in dry methane at temperatures T ≥ 1000 K. In addition, treatment under moist methane conditions causes additional formation of carbon-nanotube-like architectures by partial detachment of the graphite layers. All experiments show that during carbon growth, no substantial reduction of any of the oxides takes place. Our results, therefore, indicate that these pure oxides can act as efficient nonmetallic substrates for methane-induced growth of different carbon species with potentially important implications regarding their use in solid oxide fuel cells. Moreover, by comparing the three oxides, we could elucidate differences in the methane reactivities of the respective SOFC-relevant purely oxidic surfaces under typical SOFC operation conditions without the presence of metallic constituents. PMID:24587591

Prolonged respiratory symptoms caused by thermal degradation products of freons.

PubMed

Piirilä, Päivi; Espo, Timo; Pfäffli, Pirkko; Riihimäki, Vesa; Wolff, Henrik; Nordman, Henrik

2003-02-01

The chlorofluorocarbons (CFC) used in refrigeration systems decompose on heating and produce substances that are highly irritating to the airways (eg, chlorine, carbonyl fluoride, and hydrogen fluoride). This study examined persistent respiratory symptoms among several workers exposed to thermal decomposition products of CFC. Seven patients with respiratory symptoms caused by inadvertent exposure to thermal decomposition products of CFC in a restaurant kitchen or during refrigerator repair were studied with the use of spirometry, peak flow follow-up, and histamine challenge tests. Three patients also underwent bronchoscopy and bronchoalveolar lavage. In five of the cases, cough or dyspnea lasted longer than 1 month; for three of the five, the symptoms lasted more than 4 years. Three cases showed increased bronchial hyperreactivity, and two of the three had increased diurnal peak flow variation. Three patients fulfilled the criteria for acute irritant-induced asthma or reactive airway dysfunction syndrome. One case exhibited bronchiolitis while, for the other six, the clinical picture was consistent with bronchitis. The studied cases indicate that the thermal decomposition products of CFC used in refrigerators may cause irritant-induced airway diseases of long duration.

Application of vacuum stability test to determine thermal decomposition kinetics of nitramines bonded by polyurethane matrix

NASA Astrophysics Data System (ADS)

Elbeih, Ahmed; Abd-Elghany, Mohamed; Elshenawy, Tamer

2017-03-01

Vacuum stability test (VST) is mainly used to study compatibility and stability of energetic materials. In this work, VST has been investigated to study thermal decomposition kinetics of four cyclic nitramines, 1,3,5-trinitro-1,3,5-triazinane (RDX) and 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX), cis-1,3,4,6-tetranitrooctahydroimidazo-[4,5-d]imidazole (BCHMX), 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (ε-HNIW, CL-20), bonded by polyurethane matrix based on hydroxyl terminated polybutadiene (HTPB). Model fitting and model free (isoconversional) methods have been applied to determine the decomposition kinetics from VST results. For comparison, the decomposition kinetics were determined isothermally by ignition delay technique and non-isothermally by Advanced Kinetics and Technology Solution (AKTS) software. The activation energies for thermolysis obtained by isoconversional method based on VST technique of RDX/HTPB, HMX/HTPB, BCHMX/HTPB and CL20/HTPB were 157.1, 203.1, 190.0 and 176.8 kJ mol-1 respectively. Model fitting method proved that the mechanism of thermal decomposition of BCHMX/HTPB is controlled by the nucleation model while all the other studied PBXs are controlled by the diffusion models. A linear relationship between the ignition temperatures and the activation energies was observed. BCHMX/HTPB is interesting new PBX in the research stage.

Structural changes and thermal stability of charged LiNixMnyCozO₂ cathode materials studied by combined in situ time-resolved XRD and mass spectroscopy.

PubMed

Bak, Seong-Min; Hu, Enyuan; Zhou, Yongning; Yu, Xiqian; Senanayake, Sanjaya D; Cho, Sung-Jin; Kim, Kwang-Bum; Chung, Kyung Yoon; Yang, Xiao-Qing; Nam, Kyung-Wan

2014-12-24

Thermal stability of charged LiNixMnyCozO2 (NMC, with x + y + z = 1, x:y:z = 4:3:3 (NMC433), 5:3:2 (NMC532), 6:2:2 (NMC622), and 8:1:1 (NMC811)) cathode materials is systematically studied using combined in situ time-resolved X-ray diffraction and mass spectroscopy (TR-XRD/MS) techniques upon heating up to 600 °C. The TR-XRD/MS results indicate that the content of Ni, Co, and Mn significantly affects both the structural changes and the oxygen release features during heating: the more Ni and less Co and Mn, the lower the onset temperature of the phase transition (i.e., thermal decomposition) and the larger amount of oxygen release. Interestingly, the NMC532 seems to be the optimized composition to maintain a reasonably good thermal stability, comparable to the low-nickel-content materials (e.g., NMC333 and NMC433), while having a high capacity close to the high-nickel-content materials (e.g., NMC811 and NMC622). The origin of the thermal decomposition of NMC cathode materials was elucidated by the changes in the oxidation states of each transition metal (TM) cations (i.e., Ni, Co, and Mn) and their site preferences during thermal decomposition. It is revealed that Mn ions mainly occupy the 3a octahedral sites of a layered structure (R3̅m) but Co ions prefer to migrate to the 8a tetrahedral sites of a spinel structure (Fd3̅m) during the thermal decomposition. Such element-dependent cation migration plays a very important role in the thermal stability of NMC cathode materials. The reasonably good thermal stability and high capacity characteristics of the NMC532 composition is originated from the well-balanced ratio of nickel content to manganese and cobalt contents. This systematic study provides insight into the rational design of NMC-based cathode materials with a desired balance between thermal stability and high energy density.

Structural changes and thermal stability of charged LiNi xMn yCo zO 2 cathode materials studied by combined in situ time-resolved XRD and mass spectroscopy

DOE PAGES

Bak, Seong -Min; Hu, Enyuan; Zhou, Yongning; ...

2014-11-24

Thermal stability of charged LiNi xMn yCo zO 2 (NMC, with x + y + z = 1, x:y:z = 4:3:3 (NMC433), 5:3:2 (NMC532), 6:2:2 (NMC622), and 8:1:1 (NMC811)) cathode materials is systematically studied using combined in situ time- resolved X-ray diffraction and mass spectroscopy (TR-XRD/MS) techniques upon heating up to 600 °C. The TR-XRD/MS results indicate that the content of Ni, Co, and Mn significantly affects both the structural changes and the oxygen release features during heating: the more Ni and less Co and Mn, the lower the onset temperature of the phase transition (i.e., thermal decomposition) and themore » larger amount of oxygen release. Interestingly, the NMC532 seems to be the optimized composition to maintain a reasonably good thermal stability, comparable to the low-nickel-content materials (e.g., NMC333 and NMC433), while having a high capacity close to the high-nickel-content materials (e.g., NMC811 and NMC622). The origin of the thermal decomposition of NMC cathode materials was elucidated by the changes in the oxidation states of each transition metal (TM) cations (i.e., Ni, Co, and Mn) and their site preferences during thermal decomposition. It is revealed that Mn ions mainly occupy the 3a octahedral sites of a layered structure (R3¯m) but Co ions prefer to migrate to the 8a tetrahedral sites of a spinel structure (Fd3¯m) during the thermal decomposition. Such element-dependent cation migration plays a very important role in the thermal stability of NMC cathode materials. The reasonably good thermal stability and high capacity characteristics of the NMC532 composition is originated from the well-balanced ratio of nickel content to manganese and cobalt contents. As a result, this systematic study provides insight into the rational design of NMC-based cathode materials with a desired balance between thermal stability and high energy density.« less

Hydrogenation catalysts were derived from Mo(Co)/sub 6//alumina

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bowman, R.G.

1979-01-01

Alumina hydrogenation catalysts were derived from mo(CO)/sub 6//alumina with characteristics dependent upon the activation temperature, degree of alumina hydroxylation, and carrier gas used. Decomposition of Mo(CO)/sub 6/ at 100/sup 0/C on partially hydroxylated alumina in helium or hydrogen yielded Mo(CO)/sub 3//alumina, which catalyzed olefin metathesis in helium carrier and both metathesis and hydrogenation in hydrogen carrier. Decomposition of Mo(CO)/sub 6/ on dehydroxylated alumina at 100/sup 0/C in helium and in hydrogen resulted in complete decarbonylation and partial oxidation of molybdenum; this catalyst was 10 times as active as Mo(CO)/sub 3//alumina for hydrogenation. Decomposition of Mo(CO)/sub 6/ on dehydroxylated alumina atmore » 500/sup 0/C in helium gave essentially Mo(0)/alumina, which catalyzed hydrogenation, methanation, and hydrogenolysis in hydrogen. Catalysts activated on dehydroxylated alumina were ten times more active for methanation at 300/sup 0/C than catalyst activated on partially hydroxylated alumina and showed differences in selectivity for cyclopropane hydrogenolysis at 100/sup 0/C.« less

Recent Advances in Understanding the Reactivity of Energetic Ionic Liquids in Propulsion Applications

DTIC Science & Technology

2014-08-12

vacuum ultraviolet photoionization of catalytically decomposed aerosols of EILs will be discussed. 15. SUBJECT TERMS 16. SECURITY CLASSIFICATION...45 photoionization , fragmentation: thermal decomposition, photoionization : M06/6-31+G(d,p) AE = 10.37 eV Distribution A:  Approved for public... photoionization , fragmentation: thermal decomposition, photoionization : M06/6-31+G(d,p) Distribution A:  Approved for public release; distribution

High-Temperature Adhesives for Thermally Stable Aero-Assist Technologies

NASA Technical Reports Server (NTRS)

Eberts, Kenneth; Ou, Runqing

2013-01-01

Aero-assist technologies are used to control the velocity of exploration vehicles (EVs) when entering Earth or other planetary atmospheres. Since entry of EVs in planetary atmospheres results in significant heating, thermally stable aero-assist technologies are required to avoid the high heating rates while maintaining low mass. Polymer adhesives are used in aero-assist structures because of the need for high flexibility and good bonding between layers of polymer films or fabrics. However, current polymer adhesives cannot withstand temperatures above 400 C. This innovation utilizes nanotechnology capabilities to address this need, leading to the development of high-temperature adhesives that exhibit high thermal conductivity in addition to increased thermal decomposition temperature. Enhanced thermal conductivity will help to dissipate heat quickly and effectively to avoid temperature rising to harmful levels. This, together with increased thermal decomposition temperature, will enable the adhesives to sustain transient high-temperature conditions.

Reduced carbonic fluid at magmatic PT conditions: new experimental data.

NASA Astrophysics Data System (ADS)

Simakin, Alexander; Salova, Tamara; Rinat, Gabitov; Sergey, Isaenko

2017-04-01

We study properties of the dry fluid of C-O-S composition at P=2000 bar and T=900-1000oC. Dry carbonic fluid was generated at the thermal decomposition of FeCO3 and (Fe,Mg)CO3. At the decomposition of pure FeCO3 assemblages of Wus-Mt and pure Mt was recognized. Wus-Mt corresponds to the fO2 on the level around QFM-2. Native carbon was formed from the fluid when CO concentration was above constrained by CCO buffer. Generated fluid was trapped as the bubbles within welded albite glass matrix. Micro-Raman study yields around 15 vol.% of CO in the mixture with CO2. The glass trap composition was interpreted to estimate the minimum solubilities of different elements in the studied fluid: Pt - 15 ppm, Mn - 262 ppm, P - 4100 ppm, Ce -22 ppm, S- 3400 ppm, Sr - 3300 ppm (Simakin et al., 2016). We add sulfur to the system in the form of FeS2, thermally decomposing after carbonates. Fluid interaction with platinum capsule walls to form PtS leads to the fast removal of sulfur. Analysis of the interaction products provides preliminary estimate of the Pt solubility. We observe transformation of magnetite to FeS at the reaction with COS. Pyrrhotite formed from oxide contains in average 1.5 wt.% of Pt. Assuming that at the reaction 1/3Fe3O4+COS+1/3CO = FeS +CO2 all dissolved in the fluid platinum was incorporated into the sulfide we get minimum Pt solubility of about 5000 ppm. To capture fluid composition we perform experiments in the Au capsules with sodium-silicate glass trap. Micro-Raman shows that presence of water in sodium-silicate leads to the partial COS decomposition to thiols and H2S, however, COS still was prevailing form of sulfur in the fluid as predicted theoretically (Simakin, 2014). Transport of siderophile (Ni, Cr, PGE, Au), LILE (Ba, Cs, Rb, Sr), LREE and chalcophile (Ag, Zn, Cu) elements by the dry fluid of C-O-S composition can be decisive during the formation of different volcanic aerosol phases. Study was partially supported by RFBR-DFG grant # 16-55-12040. References. Simakin AG, Salova TP, Gabitov RI and Isaenko SI. Dry CO2-CO fluid as an important potential deep Earth solvent. Geofluids (2016, online). Simakin AG (2014) Peculiarities of the fluid composition in the dry C-O-S system at PT parameters of the low crust by the data of the thermodynamic modeling. Petrology, 22, 50-59.

Sponge-like silver obtained by decomposition of silver nitrate hexamethylenetetramine complex

DOE Office of Scientific and Technical Information (OSTI.GOV)

Afanasiev, Pavel, E-mail: pavel.afanasiev@ircelyon.univ-lyon.fr

2016-07-15

Silver nitrate hexamethylenetetramine [Ag(NO{sub 3})·N{sub 4}(CH{sub 2}){sub 6}] coordination compound has been prepared via aqueous route and characterized by chemical analysis, XRD and electron microscopy. Decomposition of [Ag(NO{sub 3})·N{sub 4}(CH{sub 2}){sub 6}] under hydrogen and under inert has been studied by thermal analysis and mass spectrometry. Thermal decomposition of [Ag(NO{sub 3})·N{sub 4}(CH{sub 2}){sub 6}] proceeds in the range 200–250 °C as a self-propagating rapid redox process accompanied with the release of multiple gases. The decomposition leads to formation of sponge-like silver having hierarchical open pore system with pore size spanning from 10 µm to 10 nm. The as-obtained silver spongesmore » exhibited favorable activity toward H{sub 2}O{sub 2} electrochemical reduction, making them potentially interesting as non-enzyme hydrogen peroxide sensors. - Graphical abstract: Thermal decomposition of silver nitrate hexamethylenetetramine coordination compound [Ag(NO{sub 3})·N{sub 4}(CH{sub 2}){sub 6}] leads to sponge like silver that possesses open porous structure and demonstrates interesting properties as an electrochemical hydrogen peroxide sensor. Display Omitted - Highlights: • [Ag(NO{sub 3})·N{sub 4}(CH{sub 2}){sub 6}] orthorhombic phase prepared and characterized. • Decomposition of [Ag(NO{sub 3})·N{sub 4}(CH{sub 2}){sub 6}] leads to metallic silver sponge with opened porosity. • Ag sponge showed promising properties as a material for hydrogen peroxide sensors.« less

Characterization of Thermo-Physical Properties of EVA/ATH: Application to Gasification Experiments and Pyrolysis Modeling.

PubMed

Girardin, Bertrand; Fontaine, Gaëlle; Duquesne, Sophie; Försth, Michael; Bourbigot, Serge

2015-11-20

The pyrolysis of solid polymeric materials is a complex process that involves both chemical and physical phenomena such as phase transitions, chemical reactions, heat transfer, and mass transport of gaseous components. For modeling purposes, it is important to characterize and to quantify the properties driving those phenomena, especially in the case of flame-retarded materials. In this study, protocols have been developed to characterize the thermal conductivity and the heat capacity of an ethylene-vinyl acetate copolymer (EVA) flame retarded with aluminum tri-hydroxide (ATH). These properties were measured for the various species identified across the decomposition of the material. Namely, the thermal conductivity was found to decrease as a function of temperature before decomposition whereas the ceramic residue obtained after the decomposition at the steady state exhibits a thermal conductivity as low as 0.2 W/m/K. The heat capacity of the material was also investigated using both isothermal modulated Differential Scanning Calorimetry (DSC) and the standard method (ASTM E1269). It was shown that the final residue exhibits a similar behavior to alumina, which is consistent with the decomposition pathway of EVA/ATH. Besides, the two experimental approaches give similar results over the whole range of temperatures. Moreover, the optical properties before decomposition and the heat capacity of the decomposition gases were also analyzed. Those properties were then used as input data for a pyrolysis model in order to predict gasification experiments. Mass losses of gasification experiments were well predicted, thus validating the characterization of the thermo-physical properties of the material.

Characterization of Thermo-Physical Properties of EVA/ATH: Application to Gasification Experiments and Pyrolysis Modeling

PubMed Central

Girardin, Bertrand; Fontaine, Gaëlle; Duquesne, Sophie; Försth, Michael; Bourbigot, Serge

2015-01-01

The pyrolysis of solid polymeric materials is a complex process that involves both chemical and physical phenomena such as phase transitions, chemical reactions, heat transfer, and mass transport of gaseous components. For modeling purposes, it is important to characterize and to quantify the properties driving those phenomena, especially in the case of flame-retarded materials. In this study, protocols have been developed to characterize the thermal conductivity and the heat capacity of an ethylene-vinyl acetate copolymer (EVA) flame retarded with aluminum tri-hydroxide (ATH). These properties were measured for the various species identified across the decomposition of the material. Namely, the thermal conductivity was found to decrease as a function of temperature before decomposition whereas the ceramic residue obtained after the decomposition at the steady state exhibits a thermal conductivity as low as 0.2 W/m/K. The heat capacity of the material was also investigated using both isothermal modulated Differential Scanning Calorimetry (DSC) and the standard method (ASTM E1269). It was shown that the final residue exhibits a similar behavior to alumina, which is consistent with the decomposition pathway of EVA/ATH. Besides, the two experimental approaches give similar results over the whole range of temperatures. Moreover, the optical properties before decomposition and the heat capacity of the decomposition gases were also analyzed. Those properties were then used as input data for a pyrolysis model in order to predict gasification experiments. Mass losses of gasification experiments were well predicted, thus validating the characterization of the thermo-physical properties of the material. PMID:28793682

Tautomerism and thermal decomposition of tetrazole: high-level ab initio study.

PubMed

Kiselev, Vitaly G; Cheblakov, Pavel B; Gritsan, Nina P

2011-03-10

The mutual interconversion and decomposition reactions of four tetrazole isomers (1H-TZ, 2H-TZ, 5H-TZ, and an N-heterocyclic carbene 14H) have been studied theoretically using the W1 high-level procedure. Computations allowed resolution of the existing discrepancies in the mechanism and key intermediates of TZ thermolysis. The tautomeric equilibria between 1H-TZ, 2H-TZ, and 14H turned out to play a very important role in the mechanism of thermal decomposition. Although the barriers of monomolecular tautomeric transformations were found to be high (∼50-70 kcal/mol), the concerted double H atom transfer reactions in the H-bonded complexes of TZ tautomers have profoundly lower barriers (∼18-28 kcal/mol). These reactions lead to fast interconversion between 1H-TZ, 2H-TZ, and 14H. The carbene 14H has never been considered before; however, it was predicted to be a key intermediate in the mechanism of thermal decomposition of TZ. For all species considered, the unimolecular reactions of N(2) elimination were predicted to dominate over the elimination of hydrazoic acid. In agreement with existing experimental data, the effective activation energy of thermolysis was calculated to be 36.2 kcal/mol.

Synthesis, spectroscopic, biological activity and thermal characterization of ceftazidime with transition metals

NASA Astrophysics Data System (ADS)

Masoud, Mamdouh S.; Ali, Alaa E.; Elasala, Gehan S.; Kolkaila, Sherif A.

2018-03-01

Synthesis, physicochemical characterization and thermal analysis of ceftazidime complexes with transition metals (Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II)) were discussed. It's obtained that ceftazidime act as bidentate ligand. From magnetic measurement and spectral data, octahedral structures were proposed for all complexes except for cobalt, nickel and mercury had tetrahedral structural. Hyper chemistry program confirmed binding sites of ceftazidime. Ceftazidime complexes show higher activity than ceftazidime for some strains. From TG and DTA curves the thermal decomposition mechanisms of ceftazidime and their metal complexes were suggested. The thermal decomposition of the complexes ended with the formation of metal oxides as a final product except in case of Hg complex.

Long-term straw decomposition in agro-ecosystems described by a unified three-exponentiation equation with thermal time.

PubMed

Cai, Andong; Liang, Guopeng; Zhang, Xubo; Zhang, Wenju; Li, Ling; Rui, Yichao; Xu, Minggang; Luo, Yiqi

2018-05-01

Understanding drivers of straw decomposition is essential for adopting appropriate management practice to improve soil fertility and promote carbon (C) sequestration in agricultural systems. However, predicting straw decomposition and characteristics is difficult because of the interactions between many factors related to straw properties, soil properties, and climate, especially under future climate change conditions. This study investigated the driving factors of straw decomposition of six types of crop straw including wheat, maize, rice, soybean, rape, and other straw by synthesizing 1642 paired data from 98 published papers at spatial and temporal scales across China. All the data derived from the field experiments using little bags over twelve years. Overall, despite large differences in climatic and soil properties, the remaining straw carbon (C, %) could be accurately represented by a three-exponent equation with thermal time (accumulative temperature). The lignin/nitrogen and lignin/phosphorus ratios of straw can be used to define the size of labile, intermediate, and recalcitrant C pool. The remaining C for an individual type of straw in the mild-temperature zone was higher than that in the warm-temperature and subtropical zone within one calendar year. The remaining straw C after one thermal year was 40.28%, 37.97%, 37.77%, 34.71%, 30.87%, and 27.99% for rice, soybean, rape, wheat, maize, and other straw, respectively. Soil available nitrogen and phosphorus influenced the remaining straw C at different decomposition stages. For one calendar year, the total amount of remaining straw C was estimated to be 29.41 Tg and future temperature increase of 2 °C could reduce the remaining straw C by 1.78 Tg. These findings confirmed the long-term straw decomposition could be mainly driven by temperature and straw quality, and quantitatively predicted by thermal time with the three-exponent equation for a wide array of straw types at spatial and temporal scales in agro-ecosystems of China. Copyright © 2018 Elsevier B.V. All rights reserved.

Engineering applications and analysis of vibratory motion fourth order fluid film over the time dependent heated flat plate

NASA Astrophysics Data System (ADS)

Mohmand, Muhammad Ismail; Mamat, Mustafa Bin; Shah, Qayyum

2017-07-01

This article deals with the time dependent analysis of thermally conducting and Magneto-hydrodynamic (MHD) liquid film flow of a fourth order fluid past a vertical and vibratory plate. In this article have been developed for higher order complex nature fluids. The governing-equations have been modeled in the terms of nonlinear partial differential equations with the help of physical boundary circumstances. Two different analytical approaches i.e. Adomian decomposition method (ADM) and the optimal homotopy asymptotic method (OHAM), have been used for discoveryof the series clarification of the problems. Solutions obtained via two diversemethods have been compared using the graphs, tables and found an excellent contract. Variants of the embedded flow parameters in the solution have been analysed through the graphical diagrams.

Prediction of in situ root decomposition rates in an interspecific context from chemical and morphological traits

PubMed Central

Aulen, Maurice; Shipley, Bill; Bradley, Robert

2012-01-01

Background and Aims We quantitatively relate in situ root decomposition rates of a wide range of trees and herbs used in agroforestry to root chemical and morphological traits in order to better describe carbon fluxes from roots to the soil carbon pool across a diverse group of plant species. Methods In situ root decomposition rates were measured over an entire year by an intact core method on ten tree and seven herb species typical of agroforestry systems and were quantified using decay constants (k values) from Olson's single exponential model. Decay constants were related to root chemical (total carbon, nitrogen, soluble carbon, cellulose, hemicellulose, lignin) and morphological (specific root length, specific root length) traits. Traits were measured for both absorbing and non-absorbing roots. Key Results From 61 to 77 % of the variation in the different root traits and 63 % of that in root decomposition rates was interspecific. N was positively correlated, but total carbon and lignin were negatively correlated with k values. Initial root traits accounted for 75 % of the variation in interspecific decomposition rates using partial least squares regressions; partial slopes attributed to each trait were consistent with functional ecology expectations. Conclusions Easily measured initial root traits can be used to predict rates of root decomposition in soils in an interspecific context. PMID:22003237

In-situ and self-distributed: A new understanding on catalyzed thermal decomposition process of ammonium perchlorate over Nd{sub 2}O{sub 3}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zou, Min, E-mail: zoumin3362765@163.com; Wang, Xin, E-mail: wangx@mail.njust.edu.cn; Jiang, Xiaohong, E-mail: jxh0668@sina.com

2014-05-01

Catalyzed thermal decomposition process of ammonium perchlorate (AP) over neodymium oxide (Nd{sub 2}O{sub 3}) was investigated. Catalytic performances of nanometer-sized Nd{sub 2}O{sub 3} and micrometer-sized Nd{sub 2}O{sub 3} were evaluated by differential scanning calorimetry (DSC). In contrast to universal concepts, catalysts in different sizes have nearly similar catalytic activities. Based on structural and morphological variation of the catalysts during the reaction, combined with mass spectrum analyses and studies of unmixed style, a new understanding of this catalytic process was proposed. We believed that the newly formed chloride neodymium oxide (NdOCl) was the real catalytic species in the overall thermal decompositionmore » 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.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu Shanshan; Jing Xiaoyan; Liu Jingyuan

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 ammoniummore » 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.« less

Complexity of parallel implementation of domain decomposition techniques for elliptic partial differential equations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gropp, W.D.; Keyes, D.E.

1988-03-01

The authors discuss the parallel implementation of preconditioned conjugate gradient (PCG)-based domain decomposition techniques for self-adjoint elliptic partial differential equations in two dimensions on several architectures. The complexity of these methods is described on a variety of message-passing parallel computers as a function of the size of the problem, number of processors and relative communication speeds of the processors. They show that communication startups are very important, and that even the small amount of global communication in these methods can significantly reduce the performance of many message-passing architectures.

Partial information decomposition as a spatiotemporal filter.

PubMed

Flecker, Benjamin; Alford, Wesley; Beggs, John M; Williams, Paul L; Beer, Randall D

2011-09-01

Understanding the mechanisms of distributed computation in cellular automata requires techniques for characterizing the emergent structures that underlie information processing in such systems. Recently, techniques from information theory have been brought to bear on this problem. Building on this work, we utilize the new technique of partial information decomposition to show that previous information-theoretic measures can confound distinct sources of information. We then propose a new set of filters and demonstrate that they more cleanly separate out the background domains, particles, and collisions that are typically associated with information storage, transfer, and modification in cellular automata.

Domain decomposition for aerodynamic and aeroacoustic analyses, and optimization

NASA Technical Reports Server (NTRS)

Baysal, Oktay

1995-01-01

The overarching theme was the domain decomposition, which intended to improve the numerical solution technique for the partial differential equations at hand; in the present study, those that governed either the fluid flow, or the aeroacoustic wave propagation, or the sensitivity analysis for a gradient-based optimization. The role of the domain decomposition extended beyond the original impetus of discretizing geometrical complex regions or writing modular software for distributed-hardware computers. It induced function-space decompositions and operator decompositions that offered the valuable property of near independence of operator evaluation tasks. The objectives have gravitated about the extensions and implementations of either the previously developed or concurrently being developed methodologies: (1) aerodynamic sensitivity analysis with domain decomposition (SADD); (2) computational aeroacoustics of cavities; and (3) dynamic, multibody computational fluid dynamics using unstructured meshes.

Infrared thermography non-destructive evaluation of lithium-ion battery

NASA Astrophysics Data System (ADS)

Wang, Zi-jun; Li, Zhi-qiang; Liu, Qiang

2011-08-01

The power lithium-ion battery with its high specific energy, high theoretical capacity and good cycle-life is a prime candidate as a power source for electric vehicles (EVs) and hybrid electric vehicles (HEVs). Safety is especially important for large-scale lithium-ion batteries, especially the thermal analysis is essential for their development and design. Thermal modeling is an effective way to understand the thermal behavior of the lithium-ion battery during charging and discharging. With the charging and discharging, the internal heat generation of the lithium-ion battery becomes large, and the temperature rises leading to an uneven temperature distribution induces partial degradation. Infrared (IR) Non-destructive Evaluation (NDE) has been well developed for decades years in materials, structures, and aircraft. Most thermographic methods need thermal excitation to the measurement structures. In NDE of battery, the thermal excitation is the heat generated from carbon and cobalt electrodes in electrolyte. A technique named "power function" has been developed to determine the heat by chemical reactions. In this paper, the simulations of the transient response of the temperature distribution in the lithium-ion battery are developed. The key to resolving the security problem lies in the thermal controlling, including the heat generation and the internal and external heat transfer. Therefore, three-dimensional modelling for capturing geometrical thermal effects on battery thermal abuse behaviour is required. The simulation model contains the heat generation during electrolyte decomposition and electrical resistance component. Oven tests are simulated by three-dimensional model and the discharge test preformed by test system. Infrared thermography of discharge is recorded in order to analyze the security of the lithium-ion power battery. Nondestructive detection is performed for thermal abuse analysis and discharge analysis.

Challenges and opportunities of torrefaction technology

NASA Astrophysics Data System (ADS)

Kosov, V. F.; Kuzmina, J. S.; Sytchev, G. A.; Zaichenko, V. M.

2016-11-01

Since the active exploitation and usage of classical non-renewable energy resources the most promising direction is the development of technologies of heat and electricity production from renewable sources—biomass. This is important in terms of reducing the harmful man-made influence of fuel-and-energy sector on the ecological balance. One of the most important aims when using biomass is its pre-treatment. The paper describes the fuel preliminary preparation for combustion with such technological process as torrefaction. Torrefaction allows bringing the biomass fuel as close as it possible to fossil coals for the main thermotechnical parameters. During torrefaction moisture is removed from initial material and the partial thermal decomposition of its components appears. The final torrefied product can be recommended for utilization in existing coal-fired boilers without their major reconstruction. Thus torrefaction technology enables the partial or complete replacement of fossil coal. At JIHT RAS, a torrefaction pilot plant is developed. As heat transfer medium the gas-piston engine exhaust gases were used. Results of researching and proposals for further development are showed in this paper.

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

2014-11-07

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).

Application of thermogravimetric studies for optimization of lithium hexafluorophosphate production

NASA Astrophysics Data System (ADS)

Smagin, A. A.; Matyukha, V. A.; Korobtsev, V. P.

Lithium hexafluorophosphate, isolated from hydrogen fluoride solution (anhydrous) by decanting and filtering, is an adduct of composition LiPF 6*HF. By thermogravimetric investigations the dynamics of HF removal from LiPF 6 by LiPF 6*HF thermal decomposition was studied. Based on the experimental data the constants entering into the equations as C = C0*exp( t*K0* exp(- E/RT)) were calculated, explaining the thermal decomposition processes of LiPF 6*HF and LiPF 6.

Development of methodologies to assess the relative hazards from thermal decomposition products of polymeric materials.

PubMed

Barrow, C S; Lucia, H; Stock, M F; Alarie, Y

1979-05-01

The physiological stress imposed upon mice due to the irritating properties of thermal decomposition products of polymeric materials was evaluated. Acute lethality and histopathological evaluation were included in the study. The rankings of the polymeric materials studied from most to least hazardous was concluded to be polytetrafluoroethylene greater than polyvinyl chloride greater than Douglas Fir and flexible polyurethane foam greater than fiber glass reinforced polyester greater than copper coated wire with mineral insulation.

Superconductivity above 100 K in Bi(Pb)-Ca-Sr-Cu-O films made by thermal decomposition of metal carboxylates

NASA Astrophysics Data System (ADS)

Klee, M.; de Vries, J. W. C.; Brand, W.

1988-11-01

Superconducting layers in the Bi(Pb)-Ca-Sr-Cu-O system are prepared by thermal decomposition of metal carboxylates. The films are deposited on MgO single crystal and ceramic substrates using a spin-coating and dip-coating process. The Bi-Ca-Sr-Cu-O films consist mainly of the low- Tc phase ( c-axis=3.073 nm), whereas partial substitution of Bi by Pb favours the formation of the high- Tc phase ( c-axis=3.707 nm). Films deposited on MgO (100) are strong c-axis preferentially oriented grown. While the Bi-Ca-Sr-Cu-O films show a step in the resistance versus temperature curve ( Tcf⋍80 K) due to the presence of the low- Tc and the high- Tc phase, the Bi(Pb)-Ca-Sr-Cu-O films have an onset at 110 K and are superconducting at 104 K. The temperature dependence of the critical current indicates that in the Bi-Ca-Sr-Cu-O system weak links of superconductor-isolator-superconductor type are present, while in the Bi(Pb)-Ca-Sr-Cu-O samples the contact is formed by normal-metal barriers. Using magnetic fields up to 5 T, the anisotropy of the resistive transition of the high- Tc phase was studied. In Bi(Pb)-Ca-Sr-Cu-O films the anisotropy ratio is about 18, and the corresponding coherence lengths are ξ ab(0)⋍3.6 nm and ξ c(0)⋍0.2 nm. These values are nearly the same as in the low- Tc phase.

Thermal decomposition in thermal desorption instruments: importance of thermogram measurements for analysis of secondary organic aerosol

NASA Astrophysics Data System (ADS)

Stark, H.; Yatavelli, R. L. N.; Thompson, S.; Kang, H.; Krechmer, J. E.; Kimmel, J.; Palm, B. B.; Hu, W.; Hayes, P.; Day, D. A.; Campuzano Jost, P.; Ye, P.; Canagaratna, M. R.; Jayne, J. T.; Worsnop, D. R.; Jimenez, J. L.

2017-12-01

Understanding the chemical composition of secondary organic aerosol (SOA) is crucial for explaining sources and fate of this important aerosol class in tropospheric chemistry. Further, determining SOA volatility is key in predicting its atmospheric lifetime and fate, due to partitioning from and to the gas phase. We present three analysis approaches to determine SOA volatility distributions from two field campaigns in areas with strong biogenic emissions, a Ponderosa pine forest in Colorado, USA, from the BEACHON-RoMBAS campaign, and a mixed forest in Alabama, USA, from the SOAS campaign. We used a high-resolution-time-of-flight chemical ionization mass spectrometer (CIMS) for both campaigns, equipped with a micro-orifice volatilization impactor (MOVI) inlet for BEACHON and a filter inlet for gases and aerosols (FIGAERO) for SOAS. These inlets allow near simultaneous analysis of particle and gas-phase species by the CIMS. While gas-phase species are directly measured without heating, particles undergo thermal desorption prior to analysis. Volatility distributions can be estimated in three ways: (1) analysis of the thermograms (signal vs. temperature); (2) via partitioning theory using the gas- and particle-phase measurements; (3) from measured chemical formulas via a group contribution model. Comparison of the SOA volatility distributions from the three methods shows large discrepancies for both campaigns. Results from the thermogram method are the most consistent of the methods when compared with independent AMS-thermal denuder measurements. The volatility distributions estimated from partitioning measurements are very narrow, likely due to signal-to-noise limits in the measurements. The discrepancy between the formula and the thermogram methods indicates large-scale thermal decomposition of the SOA species. We will also show results of citric acid thermal decomposition, where, in addition to the mass spectra, measurements of CO, CO2 and H2O were made, showing thermal decomposition of up to 65% of the citric acid molecules.

An Extension of the Partial Credit Model with an Application to the Measurement of Change.

ERIC Educational Resources Information Center

Fischer, Gerhard H.; Ponocny, Ivo

1994-01-01

An extension to the partial credit model, the linear partial credit model, is considered under the assumption of a certain linear decomposition of the item x category parameters into basic parameters. A conditional maximum likelihood algorithm for estimating basic parameters is presented and illustrated with simulation and an empirical study. (SLD)

Thermal decomposition and kinetic evaluation of decanted 2,4,6-trinitrotoluene (TNT) for reutilization as composite material

NASA Astrophysics Data System (ADS)

Ahmed, M. F.; Hussain, A.; Malik, A. Q.

2016-08-01

Use of energetic materials has long been considered for only military purposes. However, it is very recent that their practical applications in wide range of commercial fields such as mining, road building, under water blasting and rocket propulsion system have been considered. About 5mg of 2,4,6-trinitrotoluene (TNT) in serviceable (Svc) as well as unserviceable (Unsvc) form were used for their thermal decomposition and kinetic parameters investigation. Thermogravimetric/ differential thermal analysis (TG/DTA), X-ray diffraction (XRD) and Scanning electron microscope (SEM) were used to characterize two types of TNT. Arrhenius kinetic parameters like activation energy (E) and enthalpy (AH) of both TNT samples were determined using TG curves with the help of Horowitz and Metzger method. Simultaneously, thermal decomposition range was evaluated from DTA curves. Distinct diffraction peaks showing crystalline nature were obtained from XRD analysis. SEM results indicated that Unsvc TNT contained a variety of defects like cracks and porosity. Similarly, it is observed that thermal as well as kinetic behavior of both TNT samples vary to a great extent. Likewise, a prominent change in the activation energies (E) of both samples is observed. This in-depth study provides a way forward in finding solutions for the safe reutilization of decanted TNT.

Preparation, characterization and catalytic property of CuO nano/microspheres via thermal decomposition of cathode-plasma generating Cu2(OH)3NO3 nano/microspheres.

PubMed

Zhang, Zhi-Kun; Guo, Deng-Zhu; Zhang, Geng-Min

2011-05-01

CuO nano/microspheres with a wide diametric distribution were prepared by thermal decomposition of Cu(2)(OH)(3)NO(3) nano/microspheres formed in a simple asymmetric-electrode based cathodic-plasma electrolysis. The morphological, componential, and structural information about the two kinds of spheres were characterized in detail by SEM, TEM, EDX, XPS and XRD, and the results revealed that the morphology of the spheres were well kept after the componential and structural transformation from Cu(2)(OH)(3)NO(3) into CuO. The TGA/DSC study showed that the CuO nano/microspheres could be explored to be a promising additive for accelerating the thermal decomposition of ammonium perchlorate (AP). Combining with the current curve and emission spectrum measured in the plasma electrolysis, formation mechanism of the Cu(2)(OH)(3)NO(3) spheres was also discussed. Copyright © 2011 Elsevier Inc. All rights reserved.

Synthesis and characterization of an energetic compound Cu(Mtta)2(NO3)2 and effect on thermal decomposition of ammonium perchlorate.

PubMed

Yang, Qi; Chen, Sanping; Xie, Gang; Gao, Shengli

2011-12-15

An energetic coordination compound Cu(Mtta)(2)(NO(3))(2) has been synthesized by using 1-methyltetrazole (Mtta) as ligand and its structure has been characterized by X-ray single crystal diffraction. The central copper (II) cation was coordinated by four O atoms from two Mtta ligands and two N atoms from two NO(3)(-) anions to form a six-coordinated and distorted octahedral structure. 2D superamolecular layer structure was formed by the extensive intermolecular hydrogen bonds between Mtta ligands and NO(3)(-) anions. Thermal decomposition process of the compound was predicted based on DSC and TG-DTG analyses results. The kinetic parameters of the first exothermic process of the compound were studied by the Kissinger's and Ozawa-Doyle's methods. Sensitivity tests revealed that the compound was insensitive to mechanical stimuli. In addition, compound was explored as additive to promote the thermal decomposition of ammonium perchlorate (AP) by differential scanning calorimetry. Copyright © 2011 Elsevier B.V. All rights reserved.

On formation mechanism of Pd-Ir bimetallic nanoparticles through thermal decomposition of [Pd(NH3)4][IrCl6

NASA Astrophysics Data System (ADS)

Asanova, Tatyana I.; Asanov, Igor P.; Kim, Min-Gyu; Gerasimov, Evgeny Yu.; Zadesenets, Andrey V.; Plyusnin, Pavel E.; Korenev, Sergey V.

2013-10-01

The formation mechanism of Pd-Ir nanoparticles during thermal decomposition of double complex salt [Pd(NH3)4][IrCl6] has been studied by in situ X-ray absorption (XAFS) and photoelectron (XPS) spectroscopies. The changes in the structure of the Pd and Ir closest to the surroundings and chemical states of Pd, Ir, Cl, and N atoms were traced in the range from room temperature to 420 °C in inert atmosphere. It was established that the thermal decomposition process is carried out in 5 steps. The Pd-Ir nanoparticles are formed in pyramidal/rounded Pd-rich (10-200 nm) and dendrite Ir-rich (10-50 nm) solid solutions. A d charge depletion at Ir site and a gain at Pd, as well as the intra-atomic charge redistribution between the outer d and s and p electrons of both Ir and Pd in Pd-Ir nanoparticles, were found to occur.

Determination of Kinetic Parameters for the Thermal Decomposition of Parthenium hysterophorus

NASA Astrophysics Data System (ADS)

Dhaundiyal, Alok; Singh, Suraj B.; Hanon, Muammel M.; Rawat, Rekha

2018-02-01

A kinetic study of pyrolysis process of Parthenium hysterophorous is carried out by using thermogravimetric analysis (TGA) equipment. The present study investigates the thermal degradation and determination of the kinetic parameters such as activation E and the frequency factor A using model-free methods given by Flynn Wall and Ozawa (FWO), Kissinger-Akahira-Sonuse (KAS) and Kissinger, and model-fitting (Coats Redfern). The results derived from thermal decomposition process demarcate decomposition of Parthenium hysterophorous among the three main stages, such as dehydration, active and passive pyrolysis. It is shown through DTG thermograms that the increase in the heating rate caused temperature peaks at maximum weight loss rate to shift towards higher temperature regime. The results are compared with Coats Redfern (Integral method) and experimental results have shown that values of kinetic parameters obtained from model-free methods are in good agreement. Whereas the results obtained through Coats Redfern model at different heating rates are not promising, however, the diffusion models provided the good fitting with the experimental data.

Evidence for alkali metal formation at a cathode interface of organic electroluminescent devices by thermal decomposition of alkali metal carboxylates during their vapor deposition

NASA Astrophysics Data System (ADS)

Ganzorig, Chimed; Fujihira, Masamichi

2004-11-01

This study examines the possibility of thermal decomposition of Na salts of acetate, benzoate, and fluoride during vacuum vapor deposition using a quartz crystal microbalance to measure negative frequency shift (Δf) caused by increasing mass deposited from the same amount of source materials. Cs acetate is also examined. We compare the negative frequency shift-source current (Δf -I) curves of the Na salts with those of organic materials such as tris(8-hydroxyquinoline)aluminum and N ,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine. CH3COONa and C6H5COONa exhibit much lower Δf than the organic materials. CH3COOCs gives much larger Δf than CH3COONa due to the higher atomic weight of Cs. These exhibit clear evidence for alkali metal formation by thermal decomposition during vapor deposition of alkali metal carboxylates.

Microstructural changes of a thermally aged stainless steel submerged arc weld overlay cladding of nuclear reactor pressure vessels

NASA Astrophysics Data System (ADS)

Takeuchi, T.; Kameda, J.; Nagai, Y.; Toyama, T.; Matsukawa, Y.; Nishiyama, Y.; Onizawa, K.

2012-06-01

The effect of thermal aging on microstructural changes in stainless steel submerged arc weld-overlay cladding of reactor pressure vessels was investigated using atom probe tomography (APT). In as-received materials subjected to post-welding heat treatments (PWHTs), with a subsequent furnace cooling, a slight fluctuation of the Cr concentration was observed due to spinodal decomposition in the δ-ferrite phase but not in the austenitic phase. Thermal aging at 400 °C for 10,000 h caused not only an increase in the amplitude of spinodal decomposition but also the precipitation of G phases with composition ratios of Ni:Si:Mn = 16:7:6 in the δ-ferrite phase. The degree of the spinodal decomposition in the submerged arc weld sample was similar to that in the electroslag weld one reported previously. We also observed a carbide on the γ-austenite and δ-ferrite interface. There were no Cr depleted zones around the carbide.

Preparation and catalytic activities of LaFeO3 and Fe2O3 for HMX thermal decomposition.

PubMed

Wei, Zhi-Xian; Xu, Yan-Qing; Liu, Hai-Yan; Hu, Chang-Wen

2009-06-15

Perovskite-type LaFeO(3) and alpha-Fe(2)O(3) with high specific surface areas were directly prepared with appropriate stearic acid-nitrates ratios by a novel stearic acid solution combustion method. The obtained powders were characterized by XRD, FT-IR and XPS techniques. The catalytic activities of perovskite-type LaFeO(3) and alpha-Fe(2)O(3) for the thermal decomposition of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) were investigated by TG and TG-EGA techniques. The experimental results show that the catalytic activity of perovskite-type LaFeO(3) was much higher than that of alpha-Fe(2)O(3) because of higher concentration of surface-adsorbed oxygen (O(ad)) and hydroxyl of LaFeO(3). The study points out a potential way to develop new and more active perovskite-type catalysts for the HMX thermal decomposition.

Formability and thermal stability of phase in (Fe1-y Coy)-(B, C, N) films

NASA Astrophysics Data System (ADS)

Sunaga, K.; Kadowaki, S.; Tsunoda, M.; Takahashi, M.

2004-06-01

In order to find a way to obtain stable -Fe16X2 phase, the formability and thermal stability of (bct) phase were discussed. According to a rigid sphere model, we concluded that the less formability of B for the phase is due to its large atomic radius. We elucidated the difference of thermal stability of -Fe-X, taking into account their decomposition process. While, the decomposition of -Fe-N progresses only by the migration of N, without changing the bone structure of Fe lattice, the additional energy is needed to break the original α-Fe lattice in the cases of α-Fe-B and α-Fe-C. Therefore thermal stability of α-Fe-B and α-Fe-C is higher than that of α-Fe-N.

Primary decomposition of zero-dimensional ideals over finite fields

NASA Astrophysics Data System (ADS)

Gao, Shuhong; Wan, Daqing; Wang, Mingsheng

2009-03-01

A new algorithm is presented for computing primary decomposition of zero-dimensional ideals over finite fields. Like Berlekamp's algorithm for univariate polynomials, the new method is based on the invariant subspace of the Frobenius map acting on the quotient algebra. The dimension of the invariant subspace equals the number of primary components, and a basis of the invariant subspace yields a complete decomposition. Unlike previous approaches for decomposing multivariate polynomial systems, the new method does not need primality testing nor any generic projection, instead it reduces the general decomposition problem directly to root finding of univariate polynomials over the ground field. Also, it is shown how Groebner basis structure can be used to get partial primary decomposition without any root finding.

Diclofenac salts. III. Alkaline and earth alkaline salts.

PubMed

Fini, Adamo; Fazio, Giuseppe; Rosetti, Francesca; Angeles Holgado, M; Iruín, Ana; Alvarez-Fuentes, Josefa

2005-11-01

Diclofenac salts containing the alkaline and two earth alkaline cations have been prepared and characterized by scanning electron microscopy (SEM) and EDAX spectroscopy; and by thermal and thermogravimetric analysis (TGA): all of them crystallize as hydrate when precipitated from water. The salts dehydrate at room temperature and more easily on heating, but recovery the hydration, when placed in a humid environment. X-ray diffraction spectra suggest that on dehydration new peaks appear on diffractograms and the lattice of the salts partially looses crystallinity. This phenomenon is readily visible in the case of the calcium and magnesium salts, whose thermograms display a crystallization exotherm, before melting or decomposing at temperatures near or above 200 degrees C; these last salts appear to form solvates, when prepared from methanol. The thermogram of each salt shows a complex endotherm of dehydration about 100 degrees C; the calcium salt displays two endotherms, well separated at about 120 and 160 degrees C, which disappear after prolonged heating. Decomposition exotherms, before or soon after the melting, appear below 300 degrees C. The ammonium salt is thermally unstable and, when heated to start dehydration, dissociates and leaves acidic diclofenac.

Equivalence of the EMD- and NEMD-based decomposition of thermal conductivity into microscopic building blocks.

PubMed

Matsubara, Hiroki; Kikugawa, Gota; Ishikiriyama, Mamoru; Yamashita, Seiji; Ohara, Taku

2017-09-21

Thermal conductivity of a material can be comprehended as being composed of microscopic building blocks relevant to the energy transfer due to a specific microscopic process or structure. The building block is called the partial thermal conductivity (PTC). The concept of PTC is essential to evaluate the contributions of various molecular mechanisms to heat conduction and has been providing detailed knowledge of the contribution. The PTC can be evaluated by equilibrium molecular dynamics (EMD) and non-equilibrium molecular dynamics (NEMD) in different manners: the EMD evaluation utilizes the autocorrelation of spontaneous heat fluxes in an equilibrium state whereas the NEMD one is based on stationary heat fluxes in a non-equilibrium state. However, it has not been fully discussed whether the two methods give the same PTC or not. In the present study, we formulate a Green-Kubo relation, which is necessary for EMD to calculate the PTCs equivalent to those by NEMD. Unlike the existing theories, our formulation is based on the local equilibrium hypothesis to describe a clear connection between EMD and NEMD simulations. The equivalence of the two derivations of PTCs is confirmed by the numerical results for liquid methane and butane. The present establishment of the EMD-NEMD correspondence makes the MD analysis of PTCs a robust way to clarify the microscopic origins of thermal conductivity.

Thermal rejuvenation in metallic glasses

NASA Astrophysics Data System (ADS)

Saida, Junji; Yamada, Rui; Wakeda, Masato; Ogata, Shigenobu

2017-12-01

Structural rejuvenation in metallic glasses by a thermal process (i.e. through recovery annealing) was investigated experimentally and theoretically for various alloy compositions. An increase in the potential energy, a decrease in the density, and a change in the local structure as well as mechanical softening were observed after thermal rejuvenation. Two parameters, one related to the annealing temperature, Ta/Tg, and the other related to the cooling rate during the recovery annealing process, Vc/Vi, were proposed to evaluate the rejuvenation phenomena. A rejuvenation map was constructed using these two parameters. Since the thermal history of metallic glasses is reset above 1.2Tg, accompanied by a change in the local structure, it is essential that the condition of Ta/Tg ≥ 1.2 is satisfied during annealing. The glassy structure transforms into a more disordered state with the decomposition of icosahedral short-range order within this temperature range. Therefore, a new glassy structure (rejuvenation) depending on the subsequent quenching rate is generated. Partial rejuvenation also occurs in a Zr55Al10Ni5Cu30 bulk metallic glass when annealing is performed at a low temperature (Ta/Tg 1.07) followed by rapid cooling. This behavior probably originates from disordering in the weakly bonded (loosely packed) region. This study provides a novel approach to improving the mechanical properties of metallic glasses by controlling their glassy structure.

Constructing Sheet-On-Sheet Structured Graphitic Carbon Nitride/Reduced Graphene Oxide/Layered MnO₂ Ternary Nanocomposite with Outstanding Catalytic Properties on Thermal Decomposition of Ammonium Perchlorate.

PubMed

Xu, Jianhua; Li, Dongnan; Chen, Yu; Tan, Linghua; Kou, Bo; Wan, Fushun; Jiang, Wei; Li, Fengsheng

2017-12-15

We unprecedentedly report that layered MnO₂ nanosheets were in situ formed onto the surface of covalently bonded graphitic carbon nitride/reduced graphene oxide nanocomposite (g-C₃N₄/rGO), forming sheet-on-sheet structured two dimension (2D) graphitic carbon nitride/reduced graphene oxide/layered MnO₂ ternary nanocomposite (g-C₃N₄/rGO/MnO₂) with outstanding catalytic properties on thermal decomposition of ammonium perchlorate (AP). The covalently bonded g-C₃N₄/rGO was firstly prepared by the calcination of graphene oxide-guanidine hydrochloride precursor (GO-GndCl), following by its dispersion into the KMnO₄ aqueous solution to construct the g-C₃N₄/rGO/MnO₂ ternary nanocomposite. FT-IR, XRD, Raman as well as the XPS results clearly demonstrated the chemical interaction between g-C₃N₄, rGO and MnO₂. TEM and element mapping indicated that layered g-C₃N₄/rGO was covered with thin MnO₂ nanosheets. Furthermore, the obtained g-C₃N₄/rGO/MnO₂ nanocomposite exhibited promising catalytic capacity on thermal decomposition of AP. Upon addition of 2 wt % g-C₃N₄/rGO/MnO₂ ternary nanocomposite as catalyst, the thermal decomposition temperature of AP was largely decreased up by 142.5 °C, which was higher than that of pure g-C₃N₄, g-C₃N₄/rGO and MnO₂, respectively, demonstrating the synergistic catalysis of the as-prepared nanocomposite.

Decompositions of the polyhedral product functor with applications to moment-angle complexes and related spaces

PubMed Central

Bahri, A.; Bendersky, M.; Cohen, F. R.; Gitler, S.

2009-01-01

This article gives a natural decomposition of the suspension of a generalized moment-angle complex or partial product space which arises as the polyhedral product functor described below. The introduction and application of the smash product moment-angle complex provides a precise identification of the stable homotopy type of the values of the polyhedral product functor. One direct consequence is an analysis of the associated cohomology. For the special case of the complements of certain subspace arrangements, the geometrical decomposition implies the homological decomposition in earlier work of others as described below. Because the splitting is geometric, an analogous homological decomposition for a generalized moment-angle complex applies for any homology theory. Implied, therefore, is a decomposition for the Stanley–Reisner ring of a finite simplicial complex, and natural generalizations. PMID:19620727

Decompositions of the polyhedral product functor with applications to moment-angle complexes and related spaces.

PubMed

Bahri, A; Bendersky, M; Cohen, F R; Gitler, S

2009-07-28

This article gives a natural decomposition of the suspension of a generalized moment-angle complex or partial product space which arises as the polyhedral product functor described below. The introduction and application of the smash product moment-angle complex provides a precise identification of the stable homotopy type of the values of the polyhedral product functor. One direct consequence is an analysis of the associated cohomology. For the special case of the complements of certain subspace arrangements, the geometrical decomposition implies the homological decomposition in earlier work of others as described below. Because the splitting is geometric, an analogous homological decomposition for a generalized moment-angle complex applies for any homology theory. Implied, therefore, is a decomposition for the Stanley-Reisner ring of a finite simplicial complex, and natural generalizations.

Thermal dissociation cavity attenuated phase shift spectroscopy for continuous measurement of total peroxy and organic nitrates in the clean atmosphere

NASA Astrophysics Data System (ADS)

Sadanaga, Yasuhiro; Takaji, Ryo; Ishiyama, Ayana; Nakajima, Kazuo; Matsuki, Atsushi; Bandow, Hiroshi

2016-07-01

A thermal dissociation cavity attenuated phase shift spectroscopy (TD-CAPS) instrument was developed for measuring total peroxy nitrates (PNs) and organic nitrates (ONs) concentrations in the clean atmosphere. This instrument is easy to operate and can be applied to continuous measurement of PNs and ONs. A continuously measurable system is convenient to perform observations, especially in remote areas. Three lines (NO2, PNs, and ONs lines) were used for thermal dissociation. The NO2 line contains a quartz tube that is not heated, while the PN and ON lines contain quartz tubes that are heated at 433 K and 633 K, respectively. The concentrations of NO2, NO2 + PNs, and NO2 + PNs + ONs can be obtained from the NO2, PN, and ON lines, respectively. The lower limit values of the detection limit (3σ) for PNs and ONs were estimated to be 21 parts per trillion by volume with an integration time of 2 min. PNs were selectively thermally decomposed in the PNs line and formed NO2 quantitatively. In the ONs line, both PNs and ONs were thermally decomposed to produce NO2 quantitatively, but partial decomposition of HNO3 at 633 K interfered with the ONs measurement. Therefore, a HNO3 scrubber is required before the ONs line. Continuous observations were conducted with the TD-CAPS instrument in a remote area, and the instrument performed well for obtaining PNs and ONs concentrations.

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.

Using FT-IR Spectroscopy to Elucidate the Structures of Ablative Polymers

NASA Technical Reports Server (NTRS)

Fan, Wendy

2011-01-01

The composition and structure of an ablative polymer has a multifaceted influence on its thermal, mechanical and ablative properties. Understanding the molecular level information is critical to the optimization of material performance because it helps to establish correlations with the macroscopic properties of the material, the so-called structure-property relationship. Moreover, accurate information of molecular structures is also essential to predict the thermal decomposition pathways as well as to identify decomposition species that are fundamentally important to modeling work. In this presentation, I will describe the use of infrared transmission spectroscopy (FT-IR) as a convenient tool to aid the discovery and development of thermal protection system materials.

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

PubMed

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

2015-02-05

A series of new VO(IV) complexes of tetradentate N2O2 Schiff base ligands (L(1)-L(4)), were synthesized and characterized by FT-IR, UV-vis and elemental analysis. The structure of the complex VOL(1)⋅DMF was also investigated by X-ray crystallography which revealed a vanadyl center with distorted octahedral coordination where the 2-aza and 2-oxo coordinating sites of the ligand were perpendicular to the "-yl" oxygen. The electrochemical properties of the vanadyl complexes were investigated by cyclic voltammetry. A good correlation was observed between the oxidation potentials and the electron withdrawing character of the substituents on the Schiff base ligands, showing the following trend: MeO5-H>5-Br>5-Cl. Furthermore, the kinetic parameters of thermal decomposition were calculated by using the Coats-Redfern equation. According to the Coats-Redfern plots the kinetics of thermal decomposition of studied complexes is of the first-order in all stages, the free energy of activation for each following stage is larger than the previous one and the complexes have good thermal stability. The preparation of VOL(1)⋅DMF yielded also another compound, one kind of vanadium oxide [VO]X, with different habitus of crystals, (platelet instead of prisma) and without L(1) ligand, consisting of a V10O28 cage, diaminium moiety and dimethylamonium as a counter ions. Because its crystal structure was also new, we reported it along with the targeted complex. Copyright © 2014 Elsevier B.V. All rights reserved.

Influence of gamma-irradiation on the non-isothermal decomposition of calcium-gadolinium oxalate

NASA Astrophysics Data System (ADS)

Moharana, S. C.; Praharaj, J.; Bhatta, D.

Thermal decomposition of co-precipitated unirradiated and irradiated Ca-Gd oxalate has been studied by adopting differential thermal analysis (DTA) and thermogravimetric (TG) techniques. The reaction occurs through two stages corresponding to the decomposition of gadolinium oxalate (Gd-Ox) followed by that of calcium oxalate (Ca-Ox). The kinetic parameters for both the stages are calculated by using solid state reaction models and Coats-Redfern's equation. The co-precipitation as well as irradiation alter the DTA peak temperatures and the kinetic parameters of Ca-Ox. The decomposition of Gd-Ox follows the two dimensional Contracting area (R-2) mechanism, while that of Ca-Ox follows the Avrami-Erofeev (A(2)) mechanism (n =2), which are also exhibited by the co-precipitated and irradiated samples. Co-precipitation decreases the energy of activation and the pre-exponential factor of the individual components but the reverse phenomenon takes place upon irradiation of the co-precipitate. The mechanisms underlying the phenomena are explored.

A Survey of Singular Value Decomposition Methods and Performance Comparison of Some Available Serial Codes

NASA Technical Reports Server (NTRS)

Plassman, Gerald E.

2005-01-01

This contractor report describes a performance comparison of available alternative complete Singular Value Decomposition (SVD) methods and implementations which are suitable for incorporation into point spread function deconvolution algorithms. The report also presents a survey of alternative algorithms, including partial SVD's special case SVD's, and others developed for concurrent processing systems.

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

NASA Astrophysics Data System (ADS)

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

2017-06-01

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

Coherency strain engineered decomposition of unstable multilayer alloys for improved thermal stability

NASA Astrophysics Data System (ADS)

Forsén, R.; Ghafoor, N.; Odén, M.

2013-12-01

A concept to improve hardness and thermal stability of unstable multilayer alloys is presented based on control of the coherency strain such that the driving force for decomposition is favorably altered. Cathodic arc evaporated cubic TiCrAlN/Ti1-xCrxN multilayer coatings are used as demonstrators. Upon annealing, the coatings undergo spinodal decomposition into nanometer-sized coherent Ti- and Al-rich cubic domains which is affected by the coherency strain. In addition, the growth of the domains is restricted by the surrounding TiCrN layer compared to a non-layered TiCrAlN coating which together results in an improved thermal stability of the cubic structure. A significant hardness increase is seen during decomposition for the case with high coherency strain while a low coherency strain results in a hardness decrease for high annealing temperatures. The metal diffusion paths during the domain coarsening are affected by strain which in turn is controlled by the Cr-content (x) in the Ti1-xCrxN layers. For x = 0 the diffusion occurs both parallel and perpendicular to the growth direction but for x > =0.9 the diffusion occurs predominantly parallel to the growth direction. Altogether this study shows a structural tool to alter and fine-tune high temperature properties of multicomponent materials.

Effect of gamma-irradiation on thermal decomposition kinetics, X-ray diffraction pattern and spectral properties of tris(1,2-diaminoethane)nickel(II)sulphate

NASA Astrophysics Data System (ADS)

Jayashri, T. A.; Krishnan, G.; Rema Rani, N.

2014-12-01

Tris(1,2-diaminoethane)nickel(II)sulphate was prepared, and characterised by various chemical and spectral techniques. The sample was irradiated with 60Co gamma rays for varying doses. Sulphite ion and ammonia were detected and estimated in the irradiated samples. Non-isothermal decomposition kinetics, X-ray diffraction pattern, Fourier transform infrared spectroscopy, electronic, fast atom bombardment mass spectra, and surface morphology of the complex were studied before and after irradiation. Kinetic parameters were evaluated by integral, differential, and approximation methods. Irradiation enhanced thermal decomposition, lowering thermal and kinetic parameters. The mechanism of decomposition is controlled by R3 function. From X-ray diffraction studies, change in lattice parameters and subsequent changes in unit cell volume and average crystallite size were observed. Both unirradiated and irradiated samples of the complex belong to trigonal crystal system. Decrease in the intensity of the peaks was observed in the infrared spectra of irradiated samples. Electronic spectral studies revealed that the M-L interaction is unaffected by irradiation. Mass spectral studies showed that the fragmentation patterns of the unirradiated and irradiated samples are similar. The additional fragment with m/z 256 found in the irradiated sample is attributed to S8+. Surface morphology of the complex changed upon irradiation.

Synthesis, characterization and non-isothermal decomposition kinetic of a new galactochloralose based polymer.

PubMed

Kök, Gökhan; Ay, Kadir; Ay, Emriye; Doğan, Fatih; Kaya, Ismet

2014-01-30

A glycopolymer, poly(3-O-methacroyl-5,6-O-isopropylidene-1,2-O-(S)-trichloroethylidene-α-d-galactofuranose) (PMIPTEG) was synthesized from the sugar-carrying methacrylate monomer, 3-O-methacroyl-5,6-O-isopropylidene-1,2-O-(S)-trichloroethylidene-α-d-galactofuranose (MIPTEG) via conventional free radical polymerization with AIBN in 1,4-dioxane. The structures of glycomonomer and their polymers were confirmed by UV-vis, FT-IR, (1)H NMR, (13)C NMR, GPC, TG/DTG-DTA, DSC, and SEM techniques. SEM images showed that PMIPTEG had a straight-chain length structure. On the other hand, the thermal decomposition kinetics of polymer were investigated by means of thermogravimetric analysis in dynamic nitrogen atmosphere at different heating rates. The apparent activation energies for thermal decomposition of the PMIPTEG were calculated using the Kissinger, Kim-Park, Tang, Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS) and Friedman methods and were found to be 100.15, 104.40, 102.0, 102.2, 103.2 and 99.6 kJ/mol, respectively. The most likely process mechanism related to the thermal decomposition stage of PMIPTEG was determined to be a Dn deceleration type in terms of master plots results. Copyright © 2013 Elsevier Ltd. All rights reserved.

Thermochemical characterization of polymers for improved fire safety

NASA Technical Reports Server (NTRS)

Lerner, N. R.

1977-01-01

Apparatus has been constructed for studying the thermal decomposition of polymers as a function of temperature. Such data is needed to evaluate the toxic threat presented by polymeric materials under fire conditions such as the smoldering fire of the type that occurs in closed areas such as coat closets in which anaerobic decomposition of polymers occurs. The apparatus allows the products of thermal decomposition to be collected and analyzed by infrared spectrometry and mass spectrometry. Data obtained from dog hair, an aromatic polyamide, polyphenylene sulfide, and polybenzimidazole are presented. It was found that significant amounts of toxic gas were evolved from dog hair at temperatures as low as 250 C, while temperatures in excess of 500 C were necessary in order for the evolution of toxic gas from the aromatic polymers to become significant.

Isoconversional approach for non-isothermal decomposition of un-irradiated and photon-irradiated 5-fluorouracil.

PubMed

Mohamed, Hala Sh; Dahy, AbdelRahman A; Mahfouz, Refaat M

2017-10-25

Kinetic analysis for the non-isothermal decomposition of un-irradiated and photon-beam-irradiated 5-fluorouracil (5-FU) as anti-cancer drug, was carried out in static air. Thermal decomposition of 5-FU proceeds in two steps. One minor step in the temperature range of (270-283°C) followed by the major step in the temperature range of (285-360°C). The non-isothermal data for un-irradiated and photon-irradiated 5-FU were analyzed using linear (Tang) and non-linear (Vyazovkin) isoconversional methods. The results of the application of these free models on the present kinetic data showed quite a dependence of the activation energy on the extent of conversion. For un-irradiated 5-FU, the non-isothermal data analysis indicates that the decomposition is generally described by A3 and A4 modeles for the minor and major decomposition steps, respectively. For a photon-irradiated sample of 5-FU with total absorbed dose of 10Gy, the decomposition is controlled by A2 model throughout the coversion range. The activation energies calculated in case of photon-irradiated 5-FU were found to be lower compared to the values obtained from the thermal decomposition of the un-irradiated sample probably due to the formation of additional nucleation sites created by a photon-irradiation. The decomposition path was investigated by intrinsic reaction coordinate (IRC) at the B3LYP/6-311++G(d,p) level of DFT. Two transition states were involved in the process by homolytic rupture of NH bond and ring secession, respectively. Published by Elsevier B.V.

Effect of thermal annealing on the structural and optical properties of tris-(8-hydroxyquinoline)aluminum(III) (Alq3 ) films.

PubMed

Cuba, M; Muralidharan, G

2015-05-01

Tris-(8-hydroxyquionoline)aluminum (Alq3 ) was synthesized and coated on to a glass substrate using the dip coating method. The structural and optical properties of the Alq3 film after thermal annealing from 50°C to 300°C in 50° steps was studied. The films have been prepared with 2 to 16 layers (42-324 nm). The thickness and thermal annealing of Alq3 films were optimized for maximum luminescence yield. The Fourier transform infrared spectrum confirms the formation of quinoline with absorption in the region 700 - 500/cm. Partial sublimation and decomposition of quinoline ion was observed with the Alq3 films annealed at 300°C. The X-ray diffraction pattern of the Alq3 film annealed at 50°C to 150°C reveals the amorphous nature of the films. The Alq3 film annealed above 150°C were crystalline nature. Film annealed at 150°C exhibits a photoluminescence intensity maximum at 512 nm when excited at 390 nm. The Alq3 thin film deposited with 10 layers (220 nm) at 150°C exhibited maximum luminescence yield. Copyright © 2014 John Wiley & Sons, Ltd.

Catalytic and inhibiting effects of lithium peroxide and hydroxide on sodium chlorate decomposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cannon, J.C.; Zhang, Y.

1995-09-01

Chemical oxygen generators based on sodium chlorate and lithium perchlorate are used in airplanes, submarines, diving, and mine rescue. Catalytic decomposition of sodium chlorate in the presence of cobalt oxide, lithium peroxide, and lithium hydroxide is studied using thermal gravimetric analysis. Lithium peroxide and hydroxide are both moderately active catalysts for the decomposition of sodium chlorate when used alone, and inhibitors when used with the more active catalyst cobalt oxide.

Thermal decomposition of hydroxylamine: isoperibolic calorimetric measurements at different conditions.

PubMed

Adamopoulou, Theodora; Papadaki, Maria I; Kounalakis, Manolis; Vazquez-Carreto, Victor; Pineda-Solano, Alba; Wang, Qingsheng; Mannan, M Sam

2013-06-15

Thermal decomposition of hydroxylamine, NH2OH, was responsible for two serious accidents. However, its reactive behavior and the synergy of factors affecting its decomposition are not being understood. In this work, the global enthalpy of hydroxylamine decomposition has been measured in the temperature range of 130-150 °C employing isoperibolic calorimetry. Measurements were performed in a metal reactor, employing 30-80 ml solutions containing 1.4-20 g of pure hydroxylamine (2.8-40 g of the supplied reagent). The measurements showed that increased concentration or temperature, results in higher global enthalpies of reaction per unit mass of reactant. At 150 °C, specific enthalpies as high as 8 kJ per gram of hydroxylamine were measured, although in general they were in the range of 3-5 kJ g(-1). The accurate measurement of the generated heat was proven to be a cumbersome task as (a) it is difficult to identify the end of decomposition, which after a fast initial stage, proceeds very slowly, especially at lower temperatures and (b) the environment of gases affects the reaction rate. Copyright © 2013 Elsevier B.V. All rights reserved.

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 of RDX. Therefore, the decomposition of GUzT affects reactions that are dominant in the liquid phase of RDX. Although GUzT is not an effective burning-rate modifier, features of its decomposition where the reaction between amines formed in the decomposition of GUzT react with the aldehydes, formed in the decomposition of RDX, may have implications from an insensitive-munitions perspective.

Thermal and Chemical Characterization of Non-metallic Materials Using Coupled Thermogravimetric Analysis and Infrared Spectroscopy

NASA Technical Reports Server (NTRS)

Huff, Timothy L.; Griffin, Dennis E. (Technical Monitor)

2001-01-01

Thermogravimetric analysis (TGA) is widely employed in the thermal characterization of non-metallic materials, yielding valuable information on decomposition characteristics of a sample over a wide temperature range. However, a potential wealth of chemical information is lost during the process, with the evolving gases generated during thermal decomposition escaping through the exhaust line. Fourier Transform-Infrared spectroscopy (FT-IR) is a powerful analytical technique for determining many chemical constituents while in any material state, in this application, the gas phase. By linking these two techniques, evolving gases generated during the TGA process are directed into an appropriately equipped infrared spectrometer for chemical speciation. Consequently, both thermal decomposition and chemical characterization of a material may be obtained in a single sample run. In practice, a heated transfer line is employed to connect the two instruments while a purge gas stream directs the evolving gases into the FT-IR, The purge gas can be either high purity air or an inert gas such as nitrogen to allow oxidative and pyrolytic processes to be examined, respectively. The FT-IR data is collected real-time, allowing continuous monitoring of chemical compositional changes over the course of thermal decomposition. Using this coupled technique, an array of diverse materials has been examined, including composites, plastics, rubber, fiberglass epoxy resins, polycarbonates, silicones, lubricants and fluorocarbon materials. The benefit of combining these two methodologies is of particular importance in the aerospace community, where newly developing materials have little available data with which to refer. By providing both thermal and chemical data simultaneously, a more definitive and comprehensive characterization of the material is possible. Additionally, this procedure has been found to be a viable screening technique for certain materials, with the generated data useful in the selection of other appropriate analytical procedures for further material characterization.

A comparison of reduced-order modelling techniques for application in hyperthermia control and estimation.

PubMed

Bailey, E A; Dutton, A W; Mattingly, M; Devasia, S; Roemer, R B

1998-01-01

Reduced-order modelling techniques can make important contributions in the control and state estimation of large systems. In hyperthermia, reduced-order modelling can provide a useful tool by which a large thermal model can be reduced to the most significant subset of its full-order modes, making real-time control and estimation possible. Two such reduction methods, one based on modal decomposition and the other on balanced realization, are compared in the context of simulated hyperthermia heat transfer problems. The results show that the modal decomposition reduction method has three significant advantages over that of balanced realization. First, modal decomposition reduced models result in less error, when compared to the full-order model, than balanced realization reduced models of similar order in problems with low or moderate advective heat transfer. Second, because the balanced realization based methods require a priori knowledge of the sensor and actuator placements, the reduced-order model is not robust to changes in sensor or actuator locations, a limitation not present in modal decomposition. Third, the modal decomposition transformation is less demanding computationally. On the other hand, in thermal problems dominated by advective heat transfer, numerical instabilities make modal decomposition based reduction problematic. Modal decomposition methods are therefore recommended for reduction of models in which advection is not dominant and research continues into methods to render balanced realization based reduction more suitable for real-time clinical hyperthermia control and estimation.

Molecular structure, thermal behavior and adiabatic time-to-explosion of 3,3-dinitroazetidinium picrate

NASA Astrophysics Data System (ADS)

Ma, Haixia; Yan, Biao; Li, Junfeng; Ren, Yinghui; Chen, Yongshi; Zhao, Fengqi; Song, Jirong; Hu, Rongzu

2010-09-01

3,3-Dinitroazetidinium picrate (DNAZṡPA) was synthesized by adding 3,3-dinitroazetidine (DNAZ) to picric acid (PA) in methanol, the single crystals suitable for X-ray measurement were obtained by recrystallization at room temperature. The compound crystallises orthorhombic with space group P2 12 12 1 and crystal parameters of a = 0.7655(1) nm, b = 0.8962(2) nm, c = 2.0507(4) nm, V = 1.4069(5) nm 3, D c = 1.776 g cm -3, Z = 4, F(0 0 0) = 768 and μ = 0.166 mm -1. The thermal behavior of DNAZṡPA was studied under a non-isothermal condition by DSC and TG-DTG methods. The kinetic parameters of the first exothermic thermal decomposition process were obtained from analysis of the DSC and TG curves by Kissinger method, Ozawa method and the integral method. The specific heat capacity of DNAZṡPA was determined with a continuous C p mode of micro-calorimeter and the standard mole specific heat capacity was 436.56 J mol -1 K -1 at 298.15 K. Using the relationship of C p with T and the thermal decomposition parameters, the time of the thermal decomposition from initialization to thermal explosion (adiabatic time-to-explosion) was evaluated to be 40.7 s. The free radical signals of DNAZṡPA and 1,3,3-trinitroazetidine (TNAZ) were detected by electron spin resonance (ESR) technique to estimate its sensitivity.

Enhancement of discharge performance of Li/CF x cell by thermal treatment of CF x cathode material

NASA Astrophysics Data System (ADS)

Zhang, Sheng S.; Foster, Donald; Read, Jeffrey

In this work we demonstrate that the thermal treatment of CF x cathode material just below the decomposition temperature can enhance discharge performance of Li/CF x cells. The performance enhancement becomes more effective when heating a mixture of CF x and citric acid (CA) since CA serves as an extra carbon source. Discharge experiments show that the thermal treatment not only reduces initial voltage delay, but also raises discharge voltage. Whereas the measurement of powder impedance indicates the thermal treatment does not increase electronic conductivity of CF x material. Based on these facts, we propose that the thermal treatment results in a limited decomposition of CF x, which yields a subfluorinated carbon (CF x- δ), instead of a highly conductive carbon. In the case of CF x/AC mixture, the AC provides extra carbon that reacts with F 2 and fluorocarbon radicals generated by the thermal decomposition of CF x to form subfluorinated carbon. The process of thermal treatment is studied by thermogravimetric analysis and X-ray diffraction, and the effect of treatment conditions such as heating temperature, heating time and CF x/CA ratio on the discharge performance of CF x cathode is discussed. As an example, a Li/CF x cell using CF x treated with CA at 500 °C under nitrogen for 2 h achieved theretical specific capacity when being discharged at C/5. Impedance analysis indicates that the enhanced performance is attributed to a significant reduction in the cell reaction resistance.

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

NASA Astrophysics Data System (ADS)

Sharma, Vikram

2017-11-01

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

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.

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.

Thermal Decomposition of Energetic Materials. 2. Deuterium Isotope Effects and Isotopic Scrambling in Condensed-Phase Decomposition of Octahydro-1, 3,5,7-Tetranitro-1,3,5,7-Tetrazocine

DTIC Science & Technology

1993-02-01

HMX , 1) and hexahydro- 1,3,5-trinitro-s-triazine decomposition of H MX show that the identity and rates of release ( RDX , 11) are energetic ingredients...quadruple scission pathway Reviews$ of the literature on RDX and HMX have discussed HMX -- 4H2C=N-NO2 (R2) the roles of unimolecular decomposition and...N-NO2 -- CH 2O + NO (R3) lavior otCyclotrimethylene-trinitraminr ( RDX ) and Cycloteiramethylene- tctranitramine ( HMX ). In Fundamentals of Solid

Jellyfish (Cyanea nozakii) decomposition and its potential influence on marine environments studied via simulation experiments.

PubMed

Qu, Chang-Feng; Song, Jin-Ming; Li, Ning; Li, Xue-Gang; Yuan, Hua-Mao; Duan, Li-Qin; Ma, Qing-Xia

2015-08-15

A growing body of evidence suggests that the jellyfish population in Chinese seas is increasing, and decomposition of jellyfish strongly influences the marine ecosystem. This study investigated the change in water quality during Cyanea nozakii decomposition using simulation experiments. The results demonstrated that the amount of dissolved nutrients released by jellyfish was greater than the amount of particulate nutrients. NH4(+) was predominant in the dissolved matter, whereas the particulate matter was dominated by organic nitrogen and inorganic phosphorus. The high N/P ratios demonstrated that jellyfish decomposition may result in high nitrogen loads. The inorganic nutrients released by C. nozakii decomposition were important for primary production. Jellyfish decomposition caused decreases in the pH and oxygen consumption associated with acidification and hypoxia or anoxia; however, sediments partially mitigated the changes in the pH and oxygen. These results imply that jellyfish decomposition can result in potentially detrimental effects on marine environments. Copyright © 2015 Elsevier Ltd. All rights reserved.

Silvicultural management within streamside management zones of intermittent streams: effects on decomposition, productivity, nutrient cycling, and channel vegetation

Treesearch

R. Governo; B. G. Lockaby; Robert B. Rummer; C. Colson

2004-01-01

The purpose of this watershed study on three intermittent streams was to evaluate responses of riparian processes to three streamside management zone (SMZ) treatments; no harvest, clearcut, and partial hawest (50% basal area removal). Riparian response variables measured included litter$all, leaf litter decomposition, understory vegetation, soil temperature and water...

Thermochemical and kinetic analysis of the thermal decomposition of monomethylhydrazine: an elementary reaction mechanism.

PubMed

Sun, Hongyan; Law, Chung K

2007-05-17

The reaction kinetics for the thermal decomposition of monomethylhydrazine (MMH) was studied with quantum Rice-Ramsperger-Kassel (QRRK) theory and a master equation analysis for pressure falloff. Thermochemical properties were determined by ab initio and density functional calculations. The entropies, S degrees (298.15 K), and heat capacities, Cp degrees (T) (0 < or = T/K < or = 1500), from vibrational, translational, and external rotational contributions were calculated using statistical mechanics based on the vibrational frequencies and structures obtained from the density functional study. Potential barriers for internal rotations were calculated at the B3LYP/6-311G(d,p) level, and hindered rotational contributions to S degrees (298.15 K) and Cp degrees (T) were calculated by solving the Schrödinger equation with free rotor wave functions, and the partition coefficients were treated by direct integration over energy levels of the internal rotation potentials. Enthalpies of formation, DeltafH degrees (298.15 K), for the parent MMH (CH3NHNH2) and its corresponding radicals CH3N*NH2, CH3NHN*H, and C*H2NHNH2 were determined to be 21.6, 48.5, 51.1, and 62.8 kcal mol(-1) by use of isodesmic reaction analysis and various ab initio methods. The kinetic analysis of the thermal decomposition, abstraction, and substitution reactions of MMH was performed at the CBS-QB3 level, with those of N-N and C-N bond scissions determined by high level CCSD(T)/6-311++G(3df,2p)//MPWB1K/6-31+G(d,p) calculations. Rate constants of thermally activated MMH to dissociation products were calculated as functions of pressure and temperature. An elementary reaction mechanism based on the calculated rate constants, thermochemical properties, and literature data was developed to model the experimental data on the overall MMH thermal decomposition rate. The reactions of N-N and C-N bond scission were found to be the major reaction paths for the modeling of MMH homogeneous decomposition at atmospheric conditions.

The Elusive Universal Post-Mortem Interval Formula

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vass, Arpad Alexander

The following manuscript details our initial attempt at developing universal post-mortem interval formulas describing human decomposition. These formulas are empirically derived from data collected over the last 20 years from the University of Tennessee's Anthropology Research Facility, in Knoxville, Tennessee, USA. Two formulas were developed (surface decomposition and burial decomposition) based on temperature, moisture, and the partial pressure of oxygen, as being three of the four primary drivers for human decomposition. It is hoped that worldwide application of these formulas to environments and situations not readily studied in Tennessee will result in interdisciplinary cooperation between scientists and law enforcement personnelmore » that will allow for future refinements of these models leading to increased accuracy.« less

Improve the catalytic activity of {alpha}-Fe{sub 2}O{sub 3} particles in decomposition of ammonium perchlorate by coating amorphous carbon on their surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang Yifu; Liu Xinghai, E-mail: liuxh@whu.edu.c; Nie Jiaorong

2011-02-15

Sphere- and pod-like {alpha}-Fe{sub 2}O{sub 3} particles have been selectively synthesized using NH{sub 3}.H{sub 2}O and NaOH solution to adjust the pH value of the designed synthetic system, respectively. The sphere-like {alpha}-Fe{sub 2}O{sub 3} particles with diameter about 25 nm on average were encapsulated into carbon shells to fabricate a novel core-shell composite ({alpha}-Fe{sub 2}O{sub 3}-C) through the coating experiments. The catalytic performance of the products on the thermal decomposition of ammonium perchlorate (AP) was investigated by thermal gravimetric analyzer (TG) and differential thermal analysis (DTA). The thermal decomposition temperatures of AP in the presence of pod-like {alpha}-Fe{sub 2}O{sub 3},more » sphere-like {alpha}-Fe{sub 2}O{sub 3} and {alpha}-Fe{sub 2}O{sub 3}-C are reduced by 72, 81 and 109 {sup o}C, respectively, which show that {alpha}-Fe{sub 2}O{sub 3}-C core-shell composites have higher catalytic activity than that of {alpha}-Fe{sub 2}O{sub 3}. -- Graphical abstract: The catalytic performance of pod-like {alpha}-Fe{sub 2}O{sub 3}, sphere-like {alpha}-Fe{sub 2}O{sub 3} and {alpha}-Fe{sub 2}O{sub 3}-C on the thermal decomposition of ammonium perchlorate (AP). Display Omitted Research highlights: {yields} Sphere- and pod-like {alpha}-Fe{sub 2}O{sub 3} particles have been selectively synthesized using NH{sub 3}.H{sub 2}O and NaOH solution to adjust the pH value. {yields} A novel core-shell composite ({alpha}-Fe{sub 2}O{sub 3}-C core-shell structured composite) has been successfully synthesized using sphere-like {alpha}-Fe{sub 2}O{sub 3} particles as the cores and glucose as the source of carbon. {yields} The thermal decomposition temperatures of AP in the presence of pod-like {alpha}-Fe{sub 2}O{sub 3}, sphere-like {alpha}-Fe{sub 2}O{sub 3} and {alpha}-Fe{sub 2}O{sub 3}-C are reduced by 72, 81 and 109 {sup o}C, respectively, which shows that these materials have high catalytic activity.« less

Study of thermal, flammability and mechanical properties of intumescent flame retardant PP/kenaf nanocomposites

NASA Astrophysics Data System (ADS)

Subasinghe; Das; Bhattacharyya

2016-07-01

Detrimental physical and mechanical properties are common problems for composites when their flame retardancy is improved through filler additions. An increased interest of the synergistic nanoparticle addition to improve the flame retardancy of natural fiber composites is the aim of this work. The paper investigates the synergistic effect of two different nanoparticles (halloysite nanotubes (HNTs) and montmorillonite (MMT) nanoclay) on the flame and mechanical properties in an intumescent ammonium polyphosphate (APP)-based polypropylene (PP)/kenaf composite system. First, the nature of nanoparticle dispersion in PP through X-ray diffraction (XRD) and transmission electron microscopy (TEM) reveals that under twin screw compounding process, the partial exfoliation and intercalation have taken place within the nanocomposites. An increase in the decomposition temperature was observed under thermogravimetric analysis (TGA), with the presence of HNT. However, MMT tends to lower the maximum decomposition temperature under inert atmosphere. The flammability analysis in an intumescent flame retardant (IFR) system shows that the suitable amount of high aspect ratio nanoparticles with their exfoliation characteristics effectively helps to reduce the sustained combustion. Even though, improved stiffness properties can be observed with the presence of increased filler content, particle agglomeration tends to reduce the mechanical strengths of these composites due to low compatibilization and crack propagation.

Size-controlled magnetic nanoparticles with lecithin for biomedical applications

NASA Astrophysics Data System (ADS)

Park, S. I.; Kim, J. H.; Kim, C. G.; Kim, C. O.

2007-05-01

Lecithin-adsorbed magnetic nanoparticles were prepared by three-step process that the thermal decomposition was combined with ultrasonication. Experimental parameters were three items—molar ratio between Fe(CO) 5 and oleic acid, keeping time at decomposition temperature and lecithin concentration. As the molar ratio between Fe(CO) 5 and oleic acid, and keeping time at decomposition temperature increased, the particle size increased. However, the change of lecithin concentration did not show the remarkable particle size variation.

Proceedings of International Pyrotechnics Seminar (4th), Held at Steamboat Village, Colorado, 22-26 July 1974

DTIC Science & Technology

1974-06-17

10-1 I1. Burning Rate Modifiers, D.R. Dillehay ............................. 11-1 12. Spectroscopic Analysis of Azide Decomposition Products for use...solid, and Pit that they ignite a short distance from the surface. Further- more, decomposition of sodium nitrate, which produces the gas to blow the...decreasing U the thermal conductivity of the basic binary. Class 2 compounds, con- sisting of nanganese oxides, catalyze the normal decomposition of

The Application of Thermal Plasma to Extraction Metallurgy and Related Fields

NASA Technical Reports Server (NTRS)

Akashi, K.

1980-01-01

Various applications of thermal plasma to extraction metallurgy and related fields are surveyed, chiefly on the basis of documents published during the past two or three years. Applications to melting and smelting, to thermal decomposition, to reduction, to manufacturing of inorganic compounds, and to other fields are considered.

Solventless synthesis, morphology, structure and magnetic properties of iron oxide nanoparticles

NASA Astrophysics Data System (ADS)

Das, Bratati; Kusz, Joachim; Reddy, V. Raghavendra; Zubko, Maciej; Bhattacharjee, Ashis

2017-12-01

In this study we report the solventless synthesis of iron oxide through thermal decomposition of acetyl ferrocene as well as its mixtures with maliec anhydride and characterization of the synthesized product by various comprehensive physical techniques. Morphology, size and structure of the reaction products were investigated by scanning electron microscopy, transmission electron microscopy and X-ray powder diffraction technique, respectively. Physical characterization techniques like FT-IR spectroscopy, dc magnetization study as well as 57Fe Mössbauer spectroscopy were employed to characterize the magnetic property of the product. The results observed from these studies unequivocally established that the synthesized materials are hematite. Thermal decomposition has been studied with the help of thermogravimetry. Reaction pathway for synthesis of hematite has been proposed. It is noted that maliec anhydride in the solid reaction environment as well as the gaseous reaction atmosphere strongly affect the reaction yield as well as the particle size. In general, a method of preparing hematite nanoparticles through solventless thermal decomposition technique using organometallic compounds and the possible use of reaction promoter have been discussed in detail.

Probing the thermal stability and the decomposition mechanism of a magnesium-fullerene polymer via X-ray Raman spectroscopy, X-ray diffraction and molecular dynamics simulations.

PubMed

Aramini, Matteo; Niskanen, Johannes; Cavallari, Chiara; Pontiroli, Daniele; Musazay, Abdurrahman; Krisch, Michael; Hakala, Mikko; Huotari, Simo

2016-02-21

We report the microscopic view of the thermal structural stability of the magnesium intercalated fullerene polymer Mg2C60. With the application of X-ray Raman spectroscopy and X-ray diffraction, we study in detail the decomposition pathways of the polymer system upon annealing at temperatures between 300 and 700 °C. We show that there are at least two energy scales involved in the decomposition reaction. Intermolecular carbon bonds, which are responsible for the formation of a 2D fullerene polymer, are broken with a relatively modest thermal energy, while the long-range order of the original polymer remains intact. With an increased thermal energy, the crystal structure in turn is found to undergo a transition to a novel intercalated cubic phase that is stable up to the highest temperature studied here. The local structure surrounding magnesium ions gets severely modified close to, possibly at, the phase transition. We used density functional theory based calculations to study the thermodynamic and kinetic aspects of the collapse of the fullerene network, and to explain the intermediate steps as well as the reaction pathways in the break-up of this peculiar C60 intermolecular bonding architecture.

Rapid characterization of lithium ion battery electrolytes and thermal aging products by low-temperature plasma ambient ionization high-resolution mass spectrometry.

PubMed

Vortmann, Britta; Nowak, Sascha; Engelhard, Carsten

2013-03-19

Lithium ion batteries (LIBs) are key components for portable electronic devices that are used around the world. However, thermal decomposition products in the battery reduce its lifetime, and decomposition processes are still not understood. In this study, a rapid method for in situ analysis and reaction monitoring in LIB electrolytes is presented based on high-resolution mass spectrometry (HR-MS) with low-temperature plasma probe (LTP) ambient desorption/ionization for the first time. This proof-of-principle study demonstrates the capabilities of ambient mass spectrometry in battery research. LTP-HR-MS is ideally suited for qualitative analysis in the ambient environment because it allows direct sample analysis independent of the sample size, geometry, and structure. Further, it is environmental friendly because it eliminates the need of organic solvents that are typically used in separation techniques coupled to mass spectrometry. Accurate mass measurements were used to identify the time-/condition-dependent formation of electrolyte decomposition compounds. A LIB model electrolyte containing ethylene carbonate and dimethyl carbonate was analyzed before and after controlled thermal stress and over the course of several weeks. Major decomposition products identified include difluorophosphoric acid, monofluorophosphoric acid methyl ester, monofluorophosphoric acid dimethyl ester, and hexafluorophosphate. Solvents (i.e., dimethyl carbonate) were partly consumed via an esterification pathway. LTP-HR-MS is considered to be an attractive method for fundamental LIB studies.

Sandia Laboratories in-house activities in support of solar thermal large power applications

NASA Astrophysics Data System (ADS)

Mar, R. W.

1980-03-01

The development of thermal energy storage subsystems for solar thermal large power applications is described. The emphasis is on characterizing the behavior of molten nitrate salts with regard to thermal decomposition, environmental interactions, and corrosion. Electrochemical techniques to determine the ionic species in the melt and for use in real time studies of corrosion are also briefly discussed.

Sandia Laboratories in-house activities in support of solar thermal large power applications

NASA Technical Reports Server (NTRS)

Mar, R. W.

1980-01-01

The development of thermal energy storage subsystems for solar thermal large power applications is described. The emphasis is on characterizing the behavior of molten nitrate salts with regard to thermal decomposition, environmental interactions, and corrosion. Electrochemical techniques to determine the ionic species in the melt and for use in real time studies of corrosion are also briefly discussed.

Thermal response of a 4D carbon/carbon composite with volume ablation: a numerical simulation study

NASA Astrophysics Data System (ADS)

Zhang, Bai; Li, Xudong

2018-02-01

As carbon/carbon composites usually work at high temperature environments, material ablation inevitably occurs, which further affects the system stability and safety. In this paper, the thermal response of a thermoprotective four-directional carbon/carbon (4D C/C) composite is studied herein using a numerical model focusing on volume ablation. The model is based on energy- and mass-conservation principles as well as on the thermal decomposition equation of solid materials. The thermophysical properties of the C/C composite during the ablation process are calculated, and the thermal response during ablation, including temperature distribution, density, decomposition rate, char layer thickness, and mass loss, are quantitatively predicted. The present numerical study provides a fundamental understanding of the ablative mechanisms of a 4D C/C composite, serving as a reference and basis for further designs and optimizations of thermoprotective materials.

Thermal decomposition pathways of ethane

NASA Astrophysics Data System (ADS)

Gordon, Mark S.; Truong, Thanh N.; Pople, John A.

1986-10-01

The alternate thermal decomposition pathways for ethane in its ground state have been investigated, using ab initio electronic structure calculations. Single-point energies were obtained at the full MP4/6-311 G ∗∗ level, using 6-31 G ∗ geometries for reactant, products, and transition states. The thermodynamically favored products are ethylene and molecular hydrogen, but a very large barrier (130 kcal/mol) is found for the direct 1,2-elimination of hydrogen. When calculated barriers are taken into account, the lowest-energy process is the homolytic cleavage of the C-C bond to form two methyl radicals.

Numerical Investigation of Physicochemical Processes Occurring During Water Evaporation in the Surface Layer Pores of a Forest Combustible Material

NASA Astrophysics Data System (ADS)

Zhdanova, A. O.; Kuznetsov, G. V.; Strizhak, P. A.

2014-07-01

A numerical investigation of the physicochemical processes occurring during water evaporation from the pores of the surface layer of a forest combustible material has been carried out. The characteristic features of the suppression of the thermal decomposition reaction of a combustible material with water filling fullyits pores and formation of a water fi lm over its surface have been determined. The characteristic times of suppression of thermal decomposition reactions under various environmental conditions and the thickness and kinds of forest combustible material (birch leaves, pine and spruce needles, etc.) have been established.

Studies on thermal decomposition behaviors of polypropylene using molecular dynamics simulation

NASA Astrophysics Data System (ADS)

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

2017-11-01

Polypropylene (PP) is one of the main components of waste plastics. In order to understand the mechanism of PP thermal decomposition, the pyrolysis behaviour of PP has been simulated from 300 to 1000 K in periodic boundary conditions by molecular dynamic method, based on AMBER force field. The simulation results show that the pyrolysis process of PP can mostly be divided into three stages: low temperature pyrolysis stage, intermediate temperature stage and high temperature pyrolysis stage. PP pyrolysis is typical of random main-chain scission, and the possible formation mechanism of major pyrolysis products was analyzed.

PROCESS OF COATING WITH NICKEL BY THE DECOMPOSITION OF NICKEL CARBONYL

DOEpatents

Hoover, T.B.

1959-04-01

An improved process is presented for the deposition of nickel coatings by the thermal decomposition of nickel carbonyl vapor. The improvement consists in incorporating a small amount of hydrogen sulfide gas in the nickel carbonyl plating gas. It is postulated that the hydrogen sulfide functions as a catalyst. i

High-purity Cu nanocrystal synthesis by a dynamic decomposition method.

PubMed

Jian, Xian; Cao, Yu; Chen, Guozhang; Wang, Chao; Tang, Hui; Yin, Liangjun; Luan, Chunhong; Liang, Yinglin; Jiang, Jing; Wu, Sixin; Zeng, Qing; Wang, Fei; Zhang, Chengui

2014-12-01

Cu nanocrystals are applied extensively in several fields, particularly in the microelectron, sensor, and catalysis. The catalytic behavior of Cu nanocrystals depends mainly on the structure and particle size. In this work, formation of high-purity Cu nanocrystals is studied using a common chemical vapor deposition precursor of cupric tartrate. This process is investigated through a combined experimental and computational approach. The decomposition kinetics is researched via differential scanning calorimetry and thermogravimetric analysis using Flynn-Wall-Ozawa, Kissinger, and Starink methods. The growth was found to be influenced by the factors of reaction temperature, protective gas, and time. And microstructural and thermal characterizations were performed by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and differential scanning calorimetry. Decomposition of cupric tartrate at different temperatures was simulated by density functional theory calculations under the generalized gradient approximation. High crystalline Cu nanocrystals without floccules were obtained from thermal decomposition of cupric tartrate at 271°C for 8 h under Ar. This general approach paves a way to controllable synthesis of Cu nanocrystals with high purity.

High-purity Cu nanocrystal synthesis by a dynamic decomposition method

NASA Astrophysics Data System (ADS)

Jian, Xian; Cao, Yu; Chen, Guozhang; Wang, Chao; Tang, Hui; Yin, Liangjun; Luan, Chunhong; Liang, Yinglin; Jiang, Jing; Wu, Sixin; Zeng, Qing; Wang, Fei; Zhang, Chengui

2014-12-01

Cu nanocrystals are applied extensively in several fields, particularly in the microelectron, sensor, and catalysis. The catalytic behavior of Cu nanocrystals depends mainly on the structure and particle size. In this work, formation of high-purity Cu nanocrystals is studied using a common chemical vapor deposition precursor of cupric tartrate. This process is investigated through a combined experimental and computational approach. The decomposition kinetics is researched via differential scanning calorimetry and thermogravimetric analysis using Flynn-Wall-Ozawa, Kissinger, and Starink methods. The growth was found to be influenced by the factors of reaction temperature, protective gas, and time. And microstructural and thermal characterizations were performed by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and differential scanning calorimetry. Decomposition of cupric tartrate at different temperatures was simulated by density functional theory calculations under the generalized gradient approximation. High crystalline Cu nanocrystals without floccules were obtained from thermal decomposition of cupric tartrate at 271°C for 8 h under Ar. This general approach paves a way to controllable synthesis of Cu nanocrystals with high purity.

Changes in the quality of chromophoric dissolved organic matter leached from senescent leaf litter during the early decomposition.

PubMed

Nishimura, Satoshi; Maie, Nagamitsu; Baba, Mitsuhisa; Sudo, Takahiro; Sugiura, Toshihiro; Shima, Eikichi

2012-01-01

Chromophoric dissolved organic matter (CDOM) leached from leaf litter is a major source of humus in mineral soil of forest ecosystems. While their functions and refractoriness depend on the physicochemical structure, there is little information on the quality of CDOM, especially for that leached in the very early stages of litter decomposition when a large amount of dissolved organic matter (DOM) is leached. This study aimed to better understand the variations/changes in the composition of CDOM leached from senescent leaf litter from two tree species during the early stage of decomposition. Leaf litter from a conifer tree (Japanese cedar, D. Don) and a deciduous broad-leaved tree (Konara oak, Thunb.) were incubated in columns using simulated rainfall events periodically for a total of 300 d at 20°C. The quality of CDOM was investigated based on the fluorescence properties by using a combination of excitation-emission matrix fluorescence (EEM) and parallel factor analysis (PARAFAC). In addition, the phenolic composition of DOM was investigated at a molecular level by thermally assisted hydrolysis and methylation-gas chromatography-mass spectrometry (THM-GC-MS) in the presence of tetramethylammonium hydroxide (TMAH). The EEM was statistically decomposed into eight fluorescence components (two tannin/peptide-like peaks, one protein-like peak, and five humic-like peaks). A significant contribution of tannin/peptide-like peaks was observed at the beginning of incubation, but these peaks decreased quickly and humic-like peaks increased within 1 mo of incubation. The composition of humic-like peaks was different between tree species and changed over the incubation period. Since tannin-derived phenolic compounds were detected in the DOM collected after 254 d of incubation on THM-GC-MS, it was suggested that tannins partially changed its structure, forming various humic-like peaks during the early decomposition. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Development of rate expressions for the thermal decomposition of RDX

DOE Office of Scientific and Technical Information (OSTI.GOV)

Erickson, K.L.; Behrens, R. Jr.; Bulusu, S.

Decomposition and combustion of energetic materials involve processes in both condensed and gas phases. Development of reliable models for design, performance, stability, and hazard analyses requires detailed understanding of the mechanisms for both the initial condensed phase decomposition of the energetic material and the subsequent reaction of the decomposition species to form the ultimate reaction products. Those mechanisms must be described in terms of constitutive rate expressions that can be incorporated into mathematical models. The thermal decomposition of RDX has been studied by Behrens and Bulusu using Simultaneous Thermogravimetric Modulated Beam Mass Spectrometry (STMBMS). Their work provides a basis formore » developing some of the constitutive rate expressions that are needed in models for design, performance, stability and hazard analyses involving RDX. Behrens and Bulusu have identified four primary reaction pathways that control the liquid-phase decomposition of RDX at temperatures between 200 and 215{degrees}C, and one that controls solid-phase decomposition at temperatures below 200{degrees}C. Two of the liquid-phase pathways appear to be first order in RDX. Arrhenius parameters for the first-order rate constants were evaluated from data reported by Behrens and Bulusu. Reaction rates extrapolated to temperatures between 370 and 450{degrees}C are in good agreement with global reaction rates observed by Trott et al. using high-speed photography and laser-heated thin-film samples. Furthermore, the STMBMS results of Behrens and Bulusu appear to be consistent with condensed-phase infrared results reported by Trott et al. and Erickson et al.« less

Development of rate expressions for the thermal decomposition of RDX

DOE Office of Scientific and Technical Information (OSTI.GOV)

Erickson, K.L.; Behrens, R. Jr.; Bulusu, S.

Decomposition and combustion of energetic materials involve processes in both condensed and gas phases. Development of reliable models for design, performance, stability, and hazard analyses requires detailed understanding of the mechanisms for both the initial condensed phase decomposition of the energetic material and the subsequent reaction of the decomposition species to form the ultimate reaction products. Those mechanisms must be described in terms of constitutive rate expressions that can be incorporated into mathematical models. The thermal decomposition of RDX has been studied by Behrens and Bulusu using Simultaneous Thermogravimetric Modulated Beam Mass Spectrometry (STMBMS). Their work provides a basis formore » developing some of the constitutive rate expressions that are needed in models for design, performance, stability and hazard analyses involving RDX. Behrens and Bulusu have identified four primary reaction pathways that control the liquid-phase decomposition of RDX at temperatures between 200 and 215[degrees]C, and one that controls solid-phase decomposition at temperatures below 200[degrees]C. Two of the liquid-phase pathways appear to be first order in RDX. Arrhenius parameters for the first-order rate constants were evaluated from data reported by Behrens and Bulusu. Reaction rates extrapolated to temperatures between 370 and 450[degrees]C are in good agreement with global reaction rates observed by Trott et al. using high-speed photography and laser-heated thin-film samples. Furthermore, the STMBMS results of Behrens and Bulusu appear to be consistent with condensed-phase infrared results reported by Trott et al. and Erickson et al.« less

Theoretical study of hydrated copper(II) interactions with guanine: a computational density functional theory study.

PubMed

Pavelka, Matej; Shukla, Manoj K; Leszczynski, Jerzy; Burda, Jaroslav V

2008-01-17

Optimization of the hydrated Cu(II)(N7-guanine) structures revealed a number of minima on the potential energy surface. For selected structures, energy decompositions together with the determination of electronic properties (partial charges and electron spin densities) were performed. In the complexes of guanine with the bare copper cation and that with the monoaqua ligated cation, an electron transfer from guanine to Cu(II) was observed, resulting in a Cu(I)-guanine(+) type of complex. Conformers with two aqua ligands are borderline systems characterized by a Cu partial charge of +0.7e and a similar value of the spin density (0.6e) localized on guanine. When tetracoordination of copper was achieved, only then the prevailing electron spin density is unambiguously localized on copper. The energetic preference of diaqua-Cu-(N7,O6-guanine) over triaqua-Cu-(N7-guanine) was found for the four-coordinate structures. However, the energy difference between these two conformations decreases with the number of water molecules present in the systems, and in complexes with five water molecules this preference is preserved only at DeltaG level where thermal and entropy terms are included.

Modeling Oil Shale Pyrolysis: High-Temperature Unimolecular Decomposition Pathways for Thiophene.

PubMed

Vasiliou, AnGayle K; Hu, Hui; Cowell, Thomas W; Whitman, Jared C; Porterfield, Jessica; Parish, Carol A

2017-10-12

The thermal decomposition mechanism of thiophene has been investigated both experimentally and theoretically. Thermal decomposition experiments were done using a 1 mm × 3 cm pulsed silicon carbide microtubular reactor, C 4 H 4 S + Δ → Products. Unlike previous studies these experiments were able to identify the initial thiophene decomposition products. Thiophene was entrained in either Ar, Ne, or He carrier gas, passed through a heated (300-1700 K) SiC microtubular reactor (roughly ≤100 μs residence time), and exited into a vacuum chamber. The resultant molecular beam was probed by photoionization mass spectroscopy and IR spectroscopy. The pyrolysis mechanisms of thiophene were also investigated with the CBS-QB3 method using UB3LYP/6-311++G(2d,p) optimized geometries. In particular, these electronic structure methods were used to explore pathways for the formation of elemental sulfur as well as for the formation of H 2 S and 1,3-butadiyne. Thiophene was found to undergo unimolecular decomposition by five pathways: C 4 H 4 S → (1) S═C═CH 2 + HCCH, (2) CS + HCCCH 3 , (3) HCS + HCCCH 2 , (4) H 2 S + HCC-CCH, and (5) S + HCC-CH═CH 2 . The experimental and theoretical findings are in excellent agreement.

Thermal decomposition of condensed-phase nitromethane from molecular dynamics from ReaxFF reactive dynamics.

PubMed

Han, Si-ping; van Duin, Adri C T; Goddard, William A; Strachan, Alejandro

2011-05-26

We studied the thermal decomposition and subsequent reaction of the energetic material nitromethane (CH(3)NO(2)) using molecular dynamics with ReaxFF, a first principles-based reactive force field. We characterize the chemistry of liquid and solid nitromethane at high temperatures (2000-3000 K) and density 1.97 g/cm(3) for times up to 200 ps. At T = 3000 K the first reaction in the decomposition of nitromethane is an intermolecular proton transfer leading to CH(3)NOOH and CH(2)NO(2). For lower temperatures (T = 2500 and 2000 K) the first reaction during decomposition is often an isomerization reaction involving the scission of the C-N bond the formation of a C-O bond to form methyl nitrate (CH(3)ONO). Also at very early times we observe intramolecular proton transfer events. The main product of these reactions is H(2)O which starts forming following those initiation steps. The appearance of H(2)O marks the beginning of the exothermic chemistry. Recent quantum-mechanics-based molecular dynamics simulations on the chemical reactions and time scales for decomposition of a crystalline sample heated to T = 3000 K for a few picoseconds are in excellent agreement with our results, providing an important, direct validation of ReaxFF.

Thermal stabilities of drops of burning thermoplastics under the UL 94 vertical test conditions.

PubMed

Wang, Yong; Zhang, Jun

2013-02-15

The properties of polymer melts will strongly affect the fire hazard of the pool induced by polymer melt flow. In this study the thermal stabilities of eight thermoplastic polymers as well as their melting drops generated under the UL 94 vertical burning test conditions were investigated by thermogravimetric experiments. It was found that the kinetic compensation effect existed for the decomposition reactions of the polymers and their drops. For polymethylmethacrylate (PMMA), high impact polystyrene (HIPS), poly(acrylonitrile-butadiene-styrene) (ABS), polyamide 6 (PA6), polypropylene (PP) and low density polyethylene (LDPE), the onset decomposition temperature and the two decomposition kinetic parameters (the pre-exponential factor and the activation energy) of the drop were less than those of the polymer. However, the onset decomposition temperature and the two kinetic parameters of PC's drop were greater than those of polycarbonate (PC). Interestingly, for polyethylenevinylacetate (EVA18) the drop hardly contained the vinyl acetate chain segments. Similarly, for the PMMA/LDPE blends and the PMMA/PP blends, when the volume fraction of PMMA was less than 50% the drop hardly contained PMMA, implying that the blend would not drip until PMMA burned away and its surface temperature approached the decomposition temperature of the continuous phase composed of LDPE or PP. Copyright © 2012 Elsevier B.V. All rights reserved.

Thermoanalytical Investigation of Some Sulfone-Containing Drugs

PubMed Central

Salama, Nahla N.; El Ries, Mohammed A.; Toubar, Safaa; Abd El Hamid, Maha; Walash, Mohammed I.

2012-01-01

The thermal behavior of some sulfone-containing drugs, namely, dapsone (DDS), dimethylsulfone (MSM), and topiramate (TOP) in drug substances, and products were investigated using different thermal techniques. These include thermogravimetry (TGA), derivative thermogravimetry (DTG), differential thermal analysis (DTA), and differential scanning calorimetry (DSC). The thermogravimetric data allowed the determination of the kinetic parameters: activation energy (E a), frequency factor (A), and reaction order (n). The thermal degradation of dapsone and topiramate was followed a first-order kinetic behavior. The calculated data evidenced a zero-order kinetic for dimethylsulfone. The relative thermal stabilities of the studied drugs have been evaluated and follow the order DDS > TOP > MSM. The purity was determined using DSC for the studied compounds, in drug substances and products. The results were in agreement with the recommended pharmacopoeia and manufacturer methods. DSC curves obtained from the tablets suggest compatibility between the drugs, excipients and/or coformulated drugs. The fragmentation pathway of dapsone with mass spectrometry was taken as example, to correlate the thermal decomposition with the resulted MS-EI. The decomposition modes were investigated, and the possible fragmentation pathways were suggested by mass spectrometry. PMID:22792516

Thermoanalytical investigation of some sulfone-containing drugs.

PubMed

Salama, Nahla N; El Ries, Mohammed A; Toubar, Safaa; Abd El Hamid, Maha; Walash, Mohammed I

2012-01-01

The thermal behavior of some sulfone-containing drugs, namely, dapsone (DDS), dimethylsulfone (MSM), and topiramate (TOP) in drug substances, and products were investigated using different thermal techniques. These include thermogravimetry (TGA), derivative thermogravimetry (DTG), differential thermal analysis (DTA), and differential scanning calorimetry (DSC). The thermogravimetric data allowed the determination of the kinetic parameters: activation energy (E(a)), frequency factor (A), and reaction order (n). The thermal degradation of dapsone and topiramate was followed a first-order kinetic behavior. The calculated data evidenced a zero-order kinetic for dimethylsulfone. The relative thermal stabilities of the studied drugs have been evaluated and follow the order DDS > TOP > MSM. The purity was determined using DSC for the studied compounds, in drug substances and products. The results were in agreement with the recommended pharmacopoeia and manufacturer methods. DSC curves obtained from the tablets suggest compatibility between the drugs, excipients and/or coformulated drugs. The fragmentation pathway of dapsone with mass spectrometry was taken as example, to correlate the thermal decomposition with the resulted MS-EI. The decomposition modes were investigated, and the possible fragmentation pathways were suggested by mass spectrometry.

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

2014-12-25

Land surface temperature (LST) images retrieved from the thermal infrared (TIR) band data of Moderate Resolution Imaging Spectroradiometer (MODIS) have much lower spatial resolution than the MODIS visible and near-infrared (VNIR) band data. The coarse pixel scale of MODIS LST images (1000 m under nadir) have limited their capability in applying to many studies required high spatial resolution in comparison of the MODIS VNIR band data with pixel scale of 250-500 m. In this paper we intend to develop an efficient approach for pixel decomposition to increase the spatial resolution of MODIS LST image using the VNIR band data as assistance. The unique feature of this approach is to maintain the thermal radiance of parent pixels in the MODIS LST image unchanged after they are decomposed into the sub-pixels in the resulted image. There are two important steps in the decomposition: initial temperature estimation and final temperature determination. Therefore the approach can be termed double-step pixel decomposition (DSPD). Both steps involve a series of procedures to achieve the final result of decomposed LST image, including classification of the surface patterns, establishment of LST change with normalized difference of vegetation index (NDVI) and building index (NDBI), reversion of LST into thermal radiance through Planck equation, and computation of weights for the sub-pixels of the resulted image. Since the Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) with much higher spatial resolution than MODIS data was on-board the same platform (Terra) as MODIS for Earth observation, an experiment had been done in the study to validate the accuracy and efficiency of our approach for pixel decomposition. The ASTER LST image was used as the reference to compare with the decomposed LST image. The result showed that the spatial distribution of the decomposed LST image was very similar to that of the ASTER LST image with a root mean square error (RMSE) of 2.7 K for entire image. Comparison with the evaluation DisTrad (E-DisTrad) and re-sampling methods for pixel decomposition also indicate that our DSPD has the lowest RMSE in all cases, including urban region, water bodies, and natural terrain. The obvious increase in spatial resolution remarkably uplifts the capability of the coarse MODIS LST images in highlighting the details of LST variation. Therefore it can be concluded that, in spite of complicated procedures, the proposed DSPD approach provides an alternative to improve the spatial resolution of MODIS LST image hence expand its applicability to the real world.

Thermally induced growth of ZnO nanocrystals on mixed metal oxide surfaces.

PubMed

Inayat, Alexandra; Makky, Ayman; Giraldo, Jose; Kuhnt, Andreas; Busse, Corinna; Schwieger, Wilhelm

2014-06-23

An in situ method for the growth of ZnO nanocrystals on Zn/Al mixed metal oxide (MMO) surfaces is presented. The key to this method is the thermal treatment of Zn/Al layered double hydroxides (Zn/Al LDHs) in the presence of nitrate anions, which results in partial demixing of the LDH/MMO structure and the subsequent crystallization of ZnO crystals on the surface of the forming MMO layers. In a first experimental series, thermal treatment of Zn/Al LDHs with different fractions of nitrate and carbonate in the interlayer space was examined by thermogravimetry coupled with mass spectrometry (TG-MS) and in situ XRD. In a second experimental series, Zn/Al LDHs with only carbonate in the interlayer space were thermally treated in the presence of different amounts of an external nitrate source (NH4NO3). All obtained Zn/Al MMO samples were analysed by electron microscopy, nitrogen physisorption and powder X-ray diffraction. The gas phase formed during nitrate decomposition turned out to be responsible for the formation of crystalline ZnO nanoparticles. Accordingly, both interlayer nitrate and the presence of ammonium nitrate led to the formation of supported ZnO nanocrystals with mean diameters between 100 and 400 nm, and both methods offer the possibility to tailor the amount and size of the ZnO crystals by means of the amount of nitrate. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Block recursive LU preconditioners for the thermally coupled incompressible inductionless MHD problem

NASA Astrophysics Data System (ADS)

Badia, Santiago; Martín, Alberto F.; Planas, Ramon

2014-10-01

The thermally coupled incompressible inductionless magnetohydrodynamics (MHD) problem models the flow of an electrically charged fluid under the influence of an external electromagnetic field with thermal coupling. This system of partial differential equations is strongly coupled and highly nonlinear for real cases of interest. Therefore, fully implicit time integration schemes are very desirable in order to capture the different physical scales of the problem at hand. However, solving the multiphysics linear systems of equations resulting from such algorithms is a very challenging task which requires efficient and scalable preconditioners. In this work, a new family of recursive block LU preconditioners is designed and tested for solving the thermally coupled inductionless MHD equations. These preconditioners are obtained after splitting the fully coupled matrix into one-physics problems for every variable (velocity, pressure, current density, electric potential and temperature) that can be optimally solved, e.g., using preconditioned domain decomposition algorithms. The main idea is to arrange the original matrix into an (arbitrary) 2 × 2 block matrix, and consider an LU preconditioner obtained by approximating the corresponding Schur complement. For every one of the diagonal blocks in the LU preconditioner, if it involves more than one type of unknowns, we proceed the same way in a recursive fashion. This approach is stated in an abstract way, and can be straightforwardly applied to other multiphysics problems. Further, we precisely explain a flexible and general software design for the code implementation of this type of preconditioners.

Synthesis of In2O3nanoparticles by thermal decomposition of a citrate gel precursor

NASA Astrophysics Data System (ADS)

Rey, J. F. Q.; Plivelic, T. S.; Rocha, R. A.; Tadokoro, S. K.; Torriani, I.; Muccillo, E. N. S.

2005-06-01

This paper describes the synthesis of indium oxide by a modified sol-gel method, and the study of thermal decomposition of the metal complex in air. The characterization of the intermediate as well as the final compounds was carried out by thermogravimetry, differential thermal analysis, Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy, and small angle X-ray scattering. The results show that the indium complex decomposes to In2O3 with the formation of an intermediate compound. Nanoparticles of cubic In2O3 with crystallite sizes in the nanosize range were formed after calcination at temperatures up to 900°C. Calcined materials are characterized by a polydisperse distribution of spherical particles with sharp and smooth surfaces.

Physical Properties and Thermal Decomposition of Aqueous Solutions of 2-Amino-2-hydroxymethyl-1, 3-propanediol (AHPD)

NASA Astrophysics Data System (ADS)

Murshid, Ghulam; Shariff, Azmi Mohd; Lau, K. K.; Bustam, Mohammad Azmi; Ahmad, Faizan

2011-10-01

Physical properties such as density, viscosity, refractive index, surface tension, and thermal stability of 2-amino-2-hydroxymethyl-1,3-propanediol (AHPD) were experimentally measured. All the experimental measurements were made over a wide range of temperatures from (298.15 to 333.15) K and AHPD concentrations of (1, 7, 13, 19, and 25) mass%. An overall decrease in all the measured physical properties was observed with increasing temperature. The experimental results are presented as a function of temperature and AHPD mass fraction. All the measured physical properties were correlated as a function of temperature. Thermal decomposition of pure and aqueous solutions of AHPD was investigated using a thermo-gravimetric analyzer (TGA) at a heating rate of 10 K · min-1.

Thermal properties of Bentonite Modified with 3-aminopropyltrimethoxysilane

NASA Astrophysics Data System (ADS)

Pramono, E.; Pratiwi, W.; Wahyuningrum, D.; Radiman, C. L.

2018-03-01

Chemical modifications of Bentonite (BNT) clay have been carried out by using 3-aminoprophyltrimethoxysilane (APS) in various solvent media. The degradation properties of products (BNTAPS) were characterized by thermogravimetric analysis (TGA). Samples were heated at 30 to 700°C with a heating rate 10 deg/min, and the total silane-grafted amount was determined by calculating the weight loss at 200 – 600°C. The thermogram of TGA showed that there were three main decomposition regions which are attributed to the elimination of physically adsorbed water, decomposition of silane and dehydroxylation of Bentonite. High weight loss attributed to the thermal decomposition of silane was observed between 200 to 550°C. Quantitative analysis of grafted silane results high silane loaded using a solvent with high surface energy, which indicates the type of solvent affected interaction and adsorption of APS in BNT platelets.

Thermal shock resistance ceramic insulator

DOEpatents

Morgan, Chester S.; Johnson, William R.

1980-01-01

Thermal shock resistant cermet insulators containing 0.1-20 volume % metal present as a dispersed phase. The insulators are prepared by a process comprising the steps of (a) providing a first solid phase mixture of a ceramic powder and a metal precursor; (b) heating the first solid phase mixture above the minimum decomposition temperature of the metal precursor for no longer than 30 minutes and to a temperature sufficiently above the decomposition temperature to cause the selective decomposition of the metal precursor to the metal to provide a second solid phase mixture comprising particles of ceramic having discrete metal particles adhering to their surfaces, said metal particles having a mean diameter no more than 1/2 the mean diameter of the ceramic particles, and (c) densifying the second solid phase mixture to provide a cermet insulator having 0.1-20 volume % metal present as a dispersed phase.

Acid-catalyzed oxidation of 2,4-dichlorophenoxyacetic acid by ammonium nitrate in aqueous solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leavitt, D.D.; Abraham, M.A.

1990-04-01

2,4-Dichlorophenoxyacetic acid (2,4-D) was oxidized to CO{sub 2} and water by homogeneous, liquid-phase reaction with ammonium nitrate at temperatures between 250 and 450{degree}F and pressures below 100 psi. N{sub 2} and N{sub 2}O were produced from the thermal decomposition of the ammonium nitrate oxidant. An unexpected maximum in conversion was observed at an intermediate reaction temperature, which was consistent with rapid thermal decomposition of the NH{sub 4}NO{sub 3} oxidant. Postulated reaction pathways consisting of simultaneous oxidation of 2,4-D and decomposition of the oxidant allowed estimation of kinetic constants from best-fit analysis of the data. The proposed reaction model provided amore » mathematical description of 2,4-D conversion, which allowed extrapolation of the results to reaction conditions and reactor configurations that were not experimentally investigated.« less

TRUMP. Transient & S-State Temperature Distribution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elrod, D.C.; Turner, W.D.

1992-03-03

TRUMP solves a general nonlinear parabolic partial differential equation describing flow in various kinds of potential fields, such as fields of temperature, pressure, or electricity and magnetism; simultaneously, it will solve two additional equations representing, in thermal problems, heat production by decomposition of two reactants having rate constants with a general Arrhenius temperature dependence. Steady-state and transient flow in one, two, or three dimensions are considered in geometrical configurations having simple or complex shapes and structures. Problem parameters may vary with spatial position, time, or primary dependent variables, temperature, pressure, or field strength. Initial conditions may vary with spatial position,more » and among the criteria that may be specified for ending a problem are upper and lower limits on the size of the primary dependent variable, upper limits on the problem time or on the number of time-steps or on the computer time, and attainment of steady state.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elrod, D.C.; Turner, W.D.

TRUMP solves a general nonlinear parabolic partial differential equation describing flow in various kinds of potential fields, such as fields of temperature, pressure, or electricity and magnetism; simultaneously, it will solve two additional equations representing, in thermal problems, heat production by decomposition of two reactants having rate constants with a general Arrhenius temperature dependence. Steady-state and transient flow in one, two, or three dimensions are considered in geometrical configurations having simple or complex shapes and structures. Problem parameters may vary with spatial position, time, or primary dependent variables, temperature, pressure, or field strength. Initial conditions may vary with spatial position,more » and among the criteria that may be specified for ending a problem are upper and lower limits on the size of the primary dependent variable, upper limits on the problem time or on the number of time-steps or on the computer time, and attainment of steady state.« less

Thermal decomposition of FC(O)OCH3 and FC(O)OCH2CH3.

PubMed

Berasategui, M; Argüello, G A; Burgos Paci, M A

2018-05-09

The thermal decomposition of methyl and ethyl formates has been extensively studied due to their importance in the oxidation of several fuels, pesticidal properties and their presence in interstellar space. We hitherto present the study of the thermal decomposition of methyl and ethyl fluoroformates, which could help in the elucidation of the reaction mechanisms. The reaction mechanisms were studied using FTIR spectroscopy in the temperature range of 453-733 K in the presence of different pressures of N2 as bath gas. For FC(O)OCH3 two different channels were observed; the unimolecular decomposition which is favored at higher temperatures and has a rate constant kFC(O)OCH3 = (5.3 ± 0.5) × 1015 exp[-(246 ± 10 kJ mol-1/RT)] (in units of s-1) and a bimolecular channel with a rate constant kFC(O)OCH3 = (1.6 ± 0.5) × 1011 exp[-(148 ± 10 kJ mol-1/RT)] (in units of s-1 (mol L)-1). However for ethyl formate, only direct elimination of CO2, HF and ethylene operates. The rate constants of the homogeneous first-order process fit the Arrhenius equation kFC(O)OCH2CH3 = (2.06 ± 0.09) × 1013 exp[-(169 ± 6 kJ mol-1/RT)] (in units of s-1). The difference between the mechanisms of the two fluoroformates relies on the stabilization of a six-centered transition state that only exists for ethyl formate. First principles calculations for the different channels were carried out to understand the dynamics of the decomposition.

Constructing Sheet-On-Sheet Structured Graphitic Carbon Nitride/Reduced Graphene Oxide/Layered MnO2 Ternary Nanocomposite with Outstanding Catalytic Properties on Thermal Decomposition of Ammonium Perchlorate

PubMed Central

Xu, Jianhua; Li, Dongnan; Chen, Yu; Tan, Linghua; Kou, Bo; Wan, Fushun; Jiang, Wei; Li, Fengsheng

2017-01-01

We unprecedentedly report that layered MnO2 nanosheets were in situ formed onto the surface of covalently bonded graphitic carbon nitride/reduced graphene oxide nanocomposite (g-C3N4/rGO), forming sheet-on-sheet structured two dimension (2D) graphitic carbon nitride/reduced graphene oxide/layered MnO2 ternary nanocomposite (g-C3N4/rGO/MnO2) with outstanding catalytic properties on thermal decomposition of ammonium perchlorate (AP). The covalently bonded g-C3N4/rGO was firstly prepared by the calcination of graphene oxide-guanidine hydrochloride precursor (GO-GndCl), following by its dispersion into the KMnO4 aqueous solution to construct the g-C3N4/rGO/MnO2 ternary nanocomposite. FT-IR, XRD, Raman as well as the XPS results clearly demonstrated the chemical interaction between g-C3N4, rGO and MnO2. TEM and element mapping indicated that layered g-C3N4/rGO was covered with thin MnO2 nanosheets. Furthermore, the obtained g-C3N4/rGO/MnO2 nanocomposite exhibited promising catalytic capacity on thermal decomposition of AP. Upon addition of 2 wt % g-C3N4/rGO/MnO2 ternary nanocomposite as catalyst, the thermal decomposition temperature of AP was largely decreased up by 142.5 °C, which was higher than that of pure g-C3N4, g-C3N4/rGO and MnO2, respectively, demonstrating the synergistic catalysis of the as-prepared nanocomposite. PMID:29244721

Thermal Dissociation and Roaming Isomerization of Nitromethane: Experiment and Theory.

PubMed

Annesley, Christopher J; Randazzo, John B; Klippenstein, Stephen J; Harding, Lawrence B; Jasper, Ahren W; Georgievskii, Yuri; Ruscic, Branko; Tranter, Robert S

2015-07-16

The thermal decomposition of nitromethane provides a classic example of the competition between roaming mediated isomerization and simple bond fission. A recent theoretical analysis suggests that as the pressure is increased from 2 to 200 Torr the product distribution undergoes a sharp transition from roaming dominated to bond-fission dominated. Laser schlieren densitometry is used to explore the variation in the effect of roaming on the density gradients for CH3NO2 decomposition in a shock tube for pressures of 30, 60, and 120 Torr at temperatures ranging from 1200 to 1860 K. A complementary theoretical analysis provides a novel exploration of the effects of roaming on the thermal decomposition kinetics. The analysis focuses on the roaming dynamics in a reduced dimensional space consisting of the rigid-body motions of the CH3 and NO2 radicals. A high-level reduced-dimensionality potential energy surface is developed from fits to large-scale multireference ab initio calculations. Rigid body trajectory simulations coupled with master equation kinetics calculations provide high-level a priori predictions for the thermal branching between roaming and dissociation. A statistical model provides a qualitative/semiquantitative interpretation of the results. Modeling efforts explore the relation between the predicted roaming branching and the observed gradients. Overall, the experiments are found to be fairly consistent with the theoretically proposed branching ratio, but they are also consistent with a no-roaming scenario and the underlying reasons are discussed. The theoretical predictions are also compared with prior theoretical predictions, with a related statistical model, and with the extant experimental data for the decomposition of CH3NO2, and for the reaction of CH3 with NO2.

Effect of Hydration State of Martian Perchlorate Salts on their Decomposition Temperatures during Thermal Extraction

NASA Astrophysics Data System (ADS)

Royle, S. H.; Montgomery, W.; Kounaves, S. P.; Sephton, M. A.

2017-12-01

A number of missions to Mars have analyzed the composition of surface samples using thermal extraction techniques. The temperatures of decomposition have been used as diagnostic information for the materials present. One material of great current interest is perchlorate, a relatively recently discovered component of Mars surface geochemistry that leads to deleterious effects on organic matter during thermal extraction. Knowledge of the thermal decomposition behavior of perchlorate salts is essential for mineral identification and possible avoidance of confounding interactions with organic matter. We have performed a series of stepped pyrolysis experiments on samples of magnesium perchlorate hydrate which were dehydrated to various extents - as confirmed by XRD and FTIR analysis. Our data reveal that the hydration state of magnesium perchlorate has a significant effect on decomposition temperature, with differing temperature releases of oxygen corresponding to different perchlorate hydration states. We find that the peak temperature of oxygen release increases from 500 to 600°C as the proportion of the tetrahydrate form in the sample increases and the hexahydrate form decreases. It was known previously that cation chemistry can affect the temperature of oxygen release and now our work shows that the hydration state of these salts can lead to similar variations. Consequently, incorrect identification of perchlorate species may occur if hydration state is not taken into account and a mixture of metastable hydration states (of one type of perchlorate) may be mistaken for a mixture of perchlorate salts. Our findings are important for Mars as the hydration state of salts in the regolith may change throughout the Martian year due to large variations in humidity and temperature.

Formation of "Chemically Pure" Magnetite from Mg-Fe-Carbonates Implications for the Exclusively Inorganic Origin of Magnetite and Sulfides in Martian Meteorite ALH84001

NASA Technical Reports Server (NTRS)

Golden, D. C.; Ming, Douglas W.; Lauer, H. V., Jr.; Morris, R. V.; Trieman, A. H.; McKay, G. A.

2006-01-01

Magnetite and sulfides in the black rims of carbonate globules in Martian meteorite ALH84001 have been studied extensively because of the claim by McKay et al. that they are biogenic in origin. However, exclusively inorganic (abiotic) processes are able to account for the occurrence of carbonate-sulfide-magnetite assemblages in the meteorite. We have previously precipitated chemically zoned and sulfide-bearing carbonate globules analogous to those in ALH84001 (at less than or equal to 150 C) from multiple fluxes of variable-composition Ca-Mg-Fe-CO2-S-H2O solutions. Brief heating of precipitated globules to approx. 470 C produced magnetite and pyrrhotite within the globules by thermal decomposition of siderite and pyrite, respectively. We have also shown that morphology of magnetite formed by inorganic thermal decomposition of Fe-rich carbonate is similar to the morphology of so-called biogenic magnetite in the carbonate globules of ALH84001. Magnetite crystals in the rims of carbonate globules in ALH84001 are chemically pure [Note: "Chemically pure" is defined here as magnetite with Mg at levels comparable or lower than Mg detected by [8] in ALH84001 magnetite]. A debate continues on whether or not chemically pure magnetite can form by the thermal decomposition of mixed Mg-Fe-carbonates that have formed under abiotic conditions. Thomas-Keprta et al. argue that it is not possible to form Mg-free magnetite from Mg-Fe-carbonate based on thermodynamic data. We previously suggested that chemically pure magnetite could form by the thermal decomposition of relatively pure siderite in the outer rims of the globules. Mg-Fe-carbonates may also thermally decompose under conditions conducive for formation of chemically pure magnetite. In this paper we show through laboratory experiments that chemically pure magnetite can form by an inorganic process from mixed Mg-Fe-carbonates.

Post-irradiation hardness development, chemical softening, and thermal stability of bulk-fill and conventional resin-composites.

PubMed

Alshali, Ruwaida Z; Salim, Nesreen A; Satterthwaite, Julian D; Silikas, Nick

2015-02-01

To measure bottom/top hardness ratio of bulk-fill and conventional resin-composite materials, and to assess hardness changes after dry and ethanol storage. Filler content and kinetics of thermal decomposition were also tested using thermogravimetric analysis (TGA). Six bulk-fill (SureFil SDR, Venus bulk fill, X-tra base, Filtek bulk fill flowable, Sonic fill, and Tetric EvoCeram bulk-fill) and eight conventional resin-composite materials (Grandioso flow, Venus Diamond flow, X-flow, Filtek Supreme Ultra Flowable, Grandioso, Venus Diamond, TPH Spectrum, and Filtek Z250) were tested (n=5). Initial and 24h (post-cure dry storage) top and bottom microhardness values were measured. Microhardness was re-measured after the samples were stored in 75% ethanol/water solution. Thermal decomposition and filler content were assessed by TGA. Results were analysed using one-way ANOVA and paired sample t-test (α=0.05). All materials showed significant increase of microhardness after 24h of dry storage which ranged from 100.1% to 9.1%. Bottom/top microhardness ratio >0.9 was exhibited by all materials. All materials showed significant decrease of microhardness after 24h of storage in 75% ethanol/water which ranged from 14.5% to 74.2%. The extent of post-irradiation hardness development was positively correlated to the extent of ethanol softening (R(2)=0.89, p<0.001). Initial thermal decomposition temperature assessed by TGA was variable and was correlated to ethanol softening. Bulk-fill resin-composites exhibit comparable bottom/top hardness ratio to conventional materials at recommended manufacturer thickness. Hardness was affected to a variable extent by storage with variable inorganic filler content and initial thermal decomposition shown by TGA. The manufacturer recommended depth of cure of bulk-fill resin-composites can be reached based on the microhardness method. Characterization of the primary polymer network of a resin-composite material should be considered when evaluating its stability in the aqueous oral environment. Copyright © 2014 Elsevier Ltd. All rights reserved.

Nature of catalytic activities of CoO nanocrystals in thermal decomposition of ammonium perchlorate.

PubMed

Li, Liping; Sun, Xuefei; Qiu, Xiaoqing; Xu, Jiaoxing; Li, Guangshe

2008-10-06

This work addresses the chemical nature of the catalytic activity of X-ray "pure" CoO nanocrystals. All samples were prepared by a solvothermal reaction route. X-ray diffraction indicates the formation of CoO in a cubic rock-salt structure, while infrared spectra and magnetic measurements demonstrate the coexistence of CoO and Co 3O 4. Therefore, X-ray "pure" CoO nanocrystals are a unique composite structure with a CoO core surrounded by an extremely thin Co 3O 4 surface layer, which is likely a consequence of the surface passivation of CoO nanocrystals from the air oxidation at room temperature. The CoO core shows a particle size of 22 or 280 nm, depending on the types of the precursors used. This composite nanostructure was initiated as a catalytic additive to promote the thermal decomposition of ammonium perchlorate (AP). Our preliminary investigations indicate that the maximum decomposition temperature of AP is significantly reduced in the presence of CoO/Co 3O 4 composite nanocrystals and that the maximum decomposition peak shifts toward lower temperatures as the loading amount of the composite nanocrystals increases. These findings are different from the literature reports when using many nanoscale oxide additives. Finally, the decomposition heat for the low-temperature decomposition stages of AP was calculated and correlated to the chemical nature of the CoO/Co 3O 4 composite nanostructures.

Partial differential equation-based approach for empirical mode decomposition: application on image analysis.

PubMed

Niang, Oumar; Thioune, Abdoulaye; El Gueirea, Mouhamed Cheikh; Deléchelle, Eric; Lemoine, Jacques

2012-09-01

The major problem with the empirical mode decomposition (EMD) algorithm is its lack of a theoretical framework. So, it is difficult to characterize and evaluate this approach. In this paper, we propose, in the 2-D case, the use of an alternative implementation to the algorithmic definition of the so-called "sifting process" used in the original Huang's EMD method. This approach, especially based on partial differential equations (PDEs), was presented by Niang in previous works, in 2005 and 2007, and relies on a nonlinear diffusion-based filtering process to solve the mean envelope estimation problem. In the 1-D case, the efficiency of the PDE-based method, compared to the original EMD algorithmic version, was also illustrated in a recent paper. Recently, several 2-D extensions of the EMD method have been proposed. Despite some effort, 2-D versions for EMD appear poorly performing and are very time consuming. So in this paper, an extension to the 2-D space of the PDE-based approach is extensively described. This approach has been applied in cases of both signal and image decomposition. The obtained results confirm the usefulness of the new PDE-based sifting process for the decomposition of various kinds of data. Some results have been provided in the case of image decomposition. The effectiveness of the approach encourages its use in a number of signal and image applications such as denoising, detrending, or texture analysis.

Thermal Stability of Fluorinated Polydienes Synthesized by Addition of Difluorocarbene

DTIC Science & Technology

2012-01-01

polydienes proceeds through a two-stage decomposition involving chain scission, crosslinking, dehydrogenation, and dehalogenation . The pyrolysis leads...polydienes proceeds through a two-stage decomposition involving chain scission, crosslinking, dehydrogenation, and dehalogenation . The pyrolysis leads to... dehalogenation . The pyrolysis leads to graphite-like residues, whereas their polydiene precursors decompose completely under the same conditions. The

Electrochemical and Infrared Absorption Spectroscopy Detection of SF₆ Decomposition Products.

PubMed

Dong, Ming; Zhang, Chongxing; Ren, Ming; Albarracín, Ricardo; Ye, Rixin

2017-11-15

Sulfur hexafluoride (SF₆) gas-insulated electrical equipment is widely used in high-voltage (HV) and extra-high-voltage (EHV) power systems. Partial discharge (PD) and local heating can occur in the electrical equipment because of insulation faults, which results in SF₆ decomposition and ultimately generates several types of decomposition products. These SF₆ decomposition products can be qualitatively and quantitatively detected with relevant detection methods, and such detection contributes to diagnosing the internal faults and evaluating the security risks of the equipment. At present, multiple detection methods exist for analyzing the SF₆ decomposition products, and electrochemical sensing (ES) and infrared (IR) spectroscopy are well suited for application in online detection. In this study, the combination of ES with IR spectroscopy is used to detect SF₆ gas decomposition. First, the characteristics of these two detection methods are studied, and the data analysis matrix is established. Then, a qualitative and quantitative analysis ES-IR model is established by adopting a two-step approach. A SF₆ decomposition detector is designed and manufactured by combining an electrochemical sensor and IR spectroscopy technology. The detector is used to detect SF₆ gas decomposition and is verified to reliably and accurately detect the gas components and concentrations.

Direct observation of nanowire growth and decomposition.

PubMed

Rackauskas, Simas; Shandakov, Sergey D; Jiang, Hua; Wagner, Jakob B; Nasibulin, Albert G

2017-09-26

Fundamental concepts of the crystal formation suggest that the growth and decomposition are determined by simultaneous embedding and removal of the atoms. Apparently, by changing the crystal formation conditions one can switch the regimes from the growth to decomposition. To the best of our knowledge, so far this has been only postulated, but never observed at the atomic level. By means of in situ environmental transmission electron microscopy we monitored and examined the atomic layer transformation at the conditions of the crystal growth and its decomposition using CuO nanowires selected as a model object. The atomic layer growth/decomposition was studied by varying an O 2 partial pressure. Three distinct regimes of the atomic layer evolution were experimentally observed: growth, transition and decomposition. The transition regime, at which atomic layer growth/decomposition switch takes place, is characterised by random nucleation of the atomic layers on the growing {111} surface. The decomposition starts on the side of the nanowire by removing the atomic layers without altering the overall crystal structure, which besides the fundamental importance offers new possibilities for the nanowire manipulation. Understanding of the crystal growth kinetics and nucleation at the atomic level is essential for the precise control of 1D crystal formation.

On the extensible viscoelastic beam

NASA Astrophysics Data System (ADS)

Giorgi, Claudio; Pata, Vittorino; Vuk, Elena

2008-04-01

This work is focused on the equation \\[ \\begin{eqnarray*}\\fl {\\partial_{tt}} u+\\partial_{xxxx}u +\\int_0^\\infty \\mu(s) \\partial_{xxxx}[u(t)-u(t-s)]\\,\\rmd s\\\\ - \\big(\\beta+\\|\\partial_x u\\|_{L^2(0,1)}^2\\big)\\partial_{xx}u= f\\end{eqnarray*} \\] describing the motion of an extensible viscoelastic beam. Under suitable boundary conditions, the related dynamical system in the history space framework is shown to possess a global attractor of optimal regularity. The result is obtained by exploiting an appropriate decomposition of the solution semigroup, together with the existence of a Lyapunov functional.

The Effect of Body Mass on Outdoor Adult Human Decomposition.

PubMed

Roberts, Lindsey G; Spencer, Jessica R; Dabbs, Gretchen R

2017-09-01

Forensic taphonomy explores factors impacting human decomposition. This study investigated the effect of body mass on the rate and pattern of adult human decomposition. Nine males and three females aged 49-95 years ranging in mass from 73 to 159 kg who were donated to the Complex for Forensic Anthropology Research between December 2012 and September 2015 were included in this study. Kelvin accumulated degree days (KADD) were used to assess the thermal energy required for subjects to reach several total body score (TBS) thresholds: early decomposition (TBS ≥6.0), TBS ≥12.5, advanced decomposition (TBS ≥19.0), TBS ≥23.0, and skeletonization (TBS ≥27.0). Results indicate no significant correlation between body mass and KADD at any TBS threshold. Body mass accounted for up to 24.0% of variation in decomposition rate depending on stage, and minor differences in decomposition pattern were observed. Body mass likely has a minimal impact on postmortem interval estimation. © 2017 American Academy of Forensic Sciences.

Testing the Use of Pigs as Human Proxies in Decomposition Studies.

PubMed

Connor, Melissa; Baigent, Christiane; Hansen, Eriek S

2017-12-28

Pigs are a common human analogue in taphonomic study, yet data comparing the trajectory of decomposition between the two groups are lacking. This study compared decomposition rate and gross tissue change in 17 pigs and 22 human remains placed in the Forensic Investigation Research Station in western Colorado between 2012 and 2015. Accumulated degree days (ADD) were used to assess the number of thermal units required to reach a given total body score (TBS) (1) which was used as the measure of decomposition. A comparison of slopes in linear mixed effects model indicated that decomposition rates significantly differed between human donors and pig remains χ 2 (1) = 5.662, p = 0.017. Neither the pig nor the human trajectory compared well to the TBS model. Thus, (i) pigs are not an adequate proxy for human decomposition studies, and (ii) in the semiarid environment of western Colorado, there is a need to develop a regional decomposition model. © 2017 American Academy of Forensic Sciences.

Latent fingermark detection for NaYF4:Er3+/Yb3+ upconversion phosphor synthesized by thermal decomposition route

NASA Astrophysics Data System (ADS)

Maurya, S. K.; Tiwari, S. P.; Kumar, A.; Kumar, K.

2018-04-01

The synthesis and spectroscopy of the upconverting nanoparticles, cubic NaYF4:Er3+/Yb3+ phosphor is developed for latent fingermark detection. The cubic phase of NaYF4: Er3+/Yb3+ phosphor is synthesized by thermal decomposition method using trifluoroacetate precursor with coordinating ligand octadecene and oleic acid in a mixture of technical grade. The synthesized samples showed intense green emission using 976 nm diode laser as an excitation source. Because of excellent property of luminescence in green regime the sample is used to detect the latent fingermark on a porous glass surface.

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.

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.

S-matrix decomposition, natural reaction channels, and the quantum transition state approach to reactive scattering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Manthe, Uwe, E-mail: uwe.manthe@uni-bielefeld.de; Ellerbrock, Roman, E-mail: roman.ellerbrock@uni-bielefeld.de

2016-05-28

A new approach for the quantum-state resolved analysis of polyatomic reactions is introduced. Based on the singular value decomposition of the S-matrix, energy-dependent natural reaction channels and natural reaction probabilities are defined. It is shown that the natural reaction probabilities are equal to the eigenvalues of the reaction probability operator [U. Manthe and W. H. Miller, J. Chem. Phys. 99, 3411 (1993)]. Consequently, the natural reaction channels can be interpreted as uniquely defined pathways through the transition state of the reaction. The analysis can efficiently be combined with reactive scattering calculations based on the propagation of thermal flux eigenstates. Inmore » contrast to a decomposition based straightforwardly on thermal flux eigenstates, it does not depend on the choice of the dividing surface separating reactants from products. The new approach is illustrated studying a prototypical example, the H + CH{sub 4} → H{sub 2} + CH{sub 3} reaction. The natural reaction probabilities and the contributions of the different vibrational states of the methyl product to the natural reaction channels are calculated and discussed. The relation between the thermal flux eigenstates and the natural reaction channels is studied in detail.« less

Superior Thermostability, Good Detonation Properties, Insensitivity, and the Effect on the Thermal Decomposition of Ammonium Perchlorate for a New Solvent-Free 3D Energetic PbII -MOF.

PubMed

Yang, Qi; Yang, Guoli; Zhang, Wendou; Zhang, Sheng; Yang, Zhaohui; Xie, Gang; Wei, Qing; Chen, Sanping; Gao, Shengli

2017-07-06

A new solvent-free energetic MOF, [Pb(HBTI)] n (1) (H 3 BTI=4,5-bis(1H-tetrazole)-1H-imidazole), has been synthesized under hydrothermal and acidic conditions. It was characterized by elemental analysis, IR, thermogravimetric, differential scanning calorimetry (DSC) and SEM. Single crystal X-ray diffraction analysis revealed that 1 features a rigid 3D framework architecture free of solvent molecules. Thermal analysis demonstrated that the thermostability of 1 was up to 325 °C. Non-isothermal kinetic and apparent thermodynamic parameters of exothermic decomposition process of 1 were determined by Kissinger's and Ozawa's methods. Through oxygen-bomb combustion calorimetry, the standard molar enthalpy of formation of 1 was determined. The calculated detonation properties (heat of detonation, detonation velocity and detonation pressure) and sensitivity tests of 1 were carried out. In addition, 1 was explored as combustion promoter to accelerate the thermal decompositions of ammonium perchlorate (AP) by differential scanning calorimetry. Experimental results indicated that 1 possesses potential application prospects in the field of explosives and propellants. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermodynamic studies of studtite thermal decomposition pathways via amorphous intermediates UO 3, U 2O 7, and UO 4

DOE PAGES

Guo, Xiaofeng; Wu, Di; Xu, Hongwu; ...

2016-09-01

The thermal decomposition of studtite (UO 2)O 2(H 2O) 2·2H 2O results in a series of intermediate X-ray amorphous materials with general composition UO 3+x (x = 0, 0.5, 1). As an extension of a structural study on U 2O 7, this work provides detailed calorimetric data on these amorphous oxygen-rich materials since their energetics and thermal stability are unknown. These were characterized in situ by thermogravimetry, and mass spectrometry. Ex situ X-ray diffraction and infrared spectroscopy characterized their chemical bonding and local structures. This detailed characterization formed the basis for obtaining formation enthalpies by high temperature oxide melt solutionmore » calorimetry. The thermodynamic data demonstrate the metastability of the amorphous UO 3+x materials, and explain their irreversible and spontaneous reactions to generate oxygen and form metaschoepite. Thus, formation of studtite in the nuclear fuel cycle, followed by heat treatment, can produce metastable amorphous UO 3+x materials that pose the risk of significant O 2 gas. Quantitative knowledge of the energy landscape of amorphous UO 3+x was provided for stability analysis and assessment of conditions for decomposition.« less

Structure disordering and thermal decomposition of manganese oxalate dihydrate, MnC2O4·2H2O

NASA Astrophysics Data System (ADS)

Puzan, Anna N.; Baumer, Vyacheslav N.; Lisovytskiy, Dmytro V.; Mateychenko, Pavel V.

2018-04-01

It is found that the known regular structures of MnC2O4·2H2O (I) do not allow to refine the powder X-ray pattern of (I) properly using the Rietveld method. Implementation of order-disorder scheme [28] via the including of appropriate displacement vector improves the refinement results. Also it is found that in the case of (I) the similar improvement may be achieved using the data on two phases of (I) obtained as result of decomposition MnC2O4·3H2O single crystal in the mother solution after growth. Thermal decomposition of (I) produce the anhydrous γ-MnC2O4 (II) the structure of which is differ from the known α- and β-modifications of VIIIb transition metal oxalates. The solved ab initio from the powder pattern structure (II) (space group Pmna, a = 7.1333 (1), b = 5.8787 (1), c = 9.0186 (2) Å, V = 378.19 (1) Å3, Z = 4 and Dx = 2.511 Mg m-3) contains seven-coordinated Mn atoms with Mn-O distances of 2.110-2.358 Å, and is not close-packed. Thermal decomposition of (II) in air flows via forming of amorphous MnO, the heating of which up to 723 K is accompanied by oxidation of MnO to Mn2O3 and further recrystallization of the latter.

Synthesis, characterization, vibrational spectroscopy, and factor group analysis of partially metal-doped phosphate materials.

PubMed

Sronsri, Chuchai; Boonchom, Banjong

2018-04-05

A simple precipitating method was used to synthesize effectively a partially metal-doped phosphate hydrate (Mn 0.9 Mg 0.1 HPO 4 ·3H 2 O), whereas the thermal decomposition process of the above hydrate precursor was used to obtain Mn 1.8 Mg 0.2 P 2 O 7 and LiMn 0.9 Mg 0.1 PO 4 compounds under different conditions. To separate the overlapping thermal decomposition peak, a deconvolution technique was used, and the separated peak was applied to calculate the water content. The factor group splitting analysis was used to exemplify their vibrational spectra obtained from normal vibrations of HPO 4 2- , H 2 O, P 2 O 7 4- and PO 4 3- functional groups. Further, the deconvoluted bending mode of water was clearly observed. Mn 0.9 Mg 0.1 HPO 4 ·3H 2 O was observed in the orthorhombic crystal system with the space group of Pbca (D 2h 15 ). The formula units per unit cell were found to be eight (Z = 8), and the site symmetric type of HPO 4 2- was observed as C s . For the HPO 4 2- unit, the correlation filed splitting analysis of type C 3v  - C s  - D 2h 15 was calculated and had 96 internal modes, whereas H 2 O in the above hydrate was symbolized as C 2v  - C s  - D 2h 15 and had 24 modes. The symbol C 2v  - C s  - C 2h 3 was used for the correlation filed splitting analysis of P 2 O 7 4- in Mn 1.8 Mg 0.2 P 2 O 7 (monoclinic, C2/m (C 2h 3 ), Z = 2, and 42 modes). Finally, the symbol T d  - C s  - D 2h 16 was used for the correlation filed splitting analysis of PO 4 3- in LiMn 0.9 Mg 0.1 PO 4 (orthorhombic, Pnma (D 2h 16 ), Z = 4, and 36 modes). Copyright © 2018 Elsevier B.V. All rights reserved.

The impact of shallow burial on differential decomposition to the body: a temperate case study.

PubMed

Schotsmans, Eline M J; Van de Voorde, Wim; De Winne, Joan; Wilson, Andrew S

2011-03-20

Extant literature contains a number of specific case studies on differential decomposition involving adipocere formation or desiccation, but few describe the co-occurrence of these features within a temperate climate. The case of a 65-year-old male, partially buried in a shallow grave for 7 months, is presented in which the soft tissues of the body were outwardly well preserved. The right leg was desiccated, some parts of the body were covered with adipocere (head, neck, right shoulder, upper torso and left leg) and other parts could be classified as in the early stages of decomposition. In this study the taphonomic variables resulting in differential decomposition with desiccation and adipocere formation are discussed. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

Infrared spectroscopy of radiation-chemical transformation of n-hexane on a beryllium surface

NASA Astrophysics Data System (ADS)

Gadzhieva, N. N.

2017-07-01

The radiation-chemical decomposition of n-hexane in a Be- n-hexane system under the effect of γ-irradiation at room temperature is studied by infrared reflection-absorption spectroscopy. In the absorbed dose range 5 kGy ≤ Vγ ≤ 50 kGy, intermediate surface products of radiation-heterogeneous decomposition of n-hexane (beryllium alkyls, π-olefin complexes, and beryllium hydrides) are detected. It is shown that complete radiolysis occurs at Vγ = 30 kGy; below this dose, decomposition of n-hexane occurs only partially, while higher doses lead to steady-state saturation. The radiation-chemical yield of the final decomposition product—molecular hydrogen—is determined to be G ads(H2) = 24.8 molecules/100 eV. A possible mechanism of this process is discussed.

Thermal Properties of FOX-7

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burnham, A K; Weese, R K; Wang, R

Much effort has been devoted to an ongoing search for more powerful, safer and environmentally friendly explosives. Since it was developed in the late 1990s, 1,1-diamino-2,2-dinitroethene (FOX-7), with lower sensitivity and comparable performance to RDX, has received increasing interest. Preliminary results on the physical and chemical characterization of FOX-7 have shown that it possesses good thermal and chemical stability. It is expected that FOX-7 will be a new important explosive ingredient in high performance, insensitive munition (IM) explosives. One of the major focuses in research on this novel energetic material is a study of its thermal properties. Oestmark et almore » have reported that DSC curves exhibit two minor endothermic peaks as well as two major exothermic peaks. Two endothermic peaks at {approx}116 and {approx}158 C suggest the presence of two solid-solid phase transitions. A third phase change below 100 C has also been reported based on a X-ray powder diffraction (XPD) study. The shapes, areas and observed temperatures of the two decomposition peaks at {approx}235 C and {approx}280 C vary with different batches and sources of the sample, and occasionally these two peaks are merged into one. The factors leading to this variation and a more complete investigation are in progress. Our laboratories have been interested in the thermal properties of energetic materials characterized by means of various thermal analysis techniques. This paper will present our results for the thermal behavior of FOX-7 including the phase changes, decomposition, kinetic analysis and the decomposition products using DSC, TG, ARC (Accelerating Rate Calorimetry), HFC (Heat Flow Calorimetry) and simultaneous TGDTA-FTIR (Fourier Transform Infrared Spectroscopy) Spectroscopy-MS (Mass) measurements.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scott, Sarah Nicole; Dodd, Amanda B.; Larsen, Marvin E.

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 resultmore » 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.« less

Modelling Behaviour of a Carbon Epoxy Composite Exposed to Fire: Part I-Characterisation of Thermophysical Properties.

PubMed

Tranchard, Pauline; Samyn, Fabienne; Duquesne, Sophie; Estèbe, Bruno; Bourbigot, Serge

2017-05-04

Thermophysical properties of a carbon-reinforced epoxy composite laminate (T700/M21 composite for aircraft structures) were evaluated using different innovative characterisation methods. Thermogravimetric Analysis (TGA), Simultaneous Thermal analysis (STA), Laser Flash analysis (LFA), and Fourier Transform Infrared (FTIR) analysis were used for measuring the thermal decomposition, the specific heat capacity, the anisotropic thermal conductivity of the composite, the heats of decomposition and the specific heat capacity of released gases. It permits to get input data to feed a three-dimensional (3D) model given the temperature profile and the mass loss obtained during well-defined fire scenarios (model presented in Part II of this paper). The measurements were optimised to get accurate data. The data also permit to create a public database on an aeronautical carbon fibre/epoxy composite for fire safety engineering.

Study of the Decomposition and Phase Transition of Uranium Nitride under UHV Conditions via TDS, XRD, SEM, and XPS.

PubMed

Wang, Xiaofang; Long, Zhong; Bin, Ren; Yang, Ruilong; Pan, Qifa; Li, Fangfang; Luo, Lizhu; Hu, Yin; Liu, Kezhao

2016-11-07

Uranium nitrides are among the most promising fuels for Generation IV nuclear reactors, but until now, very little has been known about their thermal stability properties under nonequilibrium conditions. In this work, thermal decomposition of nitrogen-rich uranium nitride (denoted as UN 2-x ) under ultrahigh-vacuum (UHV) conditions was investigated by thermal desorption spectroscopy (TDS). It has been shown that the nitrogen TDS spectrum consists of two peaks at about 723 and 1038 K. The X-ray diffraction, scanning electron microscopy, and X-ray photoelectron microscopy results indicate that UN 2-x (UN 2 phase) decomposed into the α-U 2 N 3 phase in the first step and the α-U 2 N 3 phase decomposed into the UN phase in the second step.

The thermal stability of sodium beta'-Alumina solid electrolyte ceramic in AMTEC cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Williams, Roger M.; Ryan, Margaret A.; Homer, Margie L.

1999-01-22

A critical component of alkali metal thermal-to electric converter (AMTEC) devices for long duration space missions is the beta'-alumina solid electrolyte ceramic (BASE), for which there exists no substitute. The temperature and environmental conditions under which BASE remains stable control operational parameters of AMTEC devices. We have used mass loss experiments in vacuum to 1573K to characterize the kinetics of BASE decomposition, and conductivity and exchange current measurements in sodium vapor filled exposure cells to 1223K to investigate changes in the BASE which affect its ionic conductivity. There is no clear evidence of direct thermal decomposition of BASE below 1273K,more » although limited soda loss may occur. Reactive metals such as Mn or Cr can react with BASE at temperatures at least as low as 1223K.« less

Effect of thermal treatment and light irradiation on the stability of lycopene with high Z-isomers content.

PubMed

Murakami, Kazuya; Honda, Masaki; Takemura, Ryota; Fukaya, Tetsuya; Wahyudiono; Kanda, Hideki; Goto, Motonobu

2018-06-01

The stability of lycopene with high Z-isomers content during thermal treatment and light irradiation was investigated. Purified (all-E)-lycopene was thermally isomerized to the Z-isomers in dichloromethane (CH 2 Cl 2 ) at 50 °C for 24 h. The total content of the Z-isomers of lycopene reached 56.1%. Then, the mixture of lycopene isomers was stored in the dark at 4, 25, and 40 °C for 30 days, and under light irradiation using a fluorescent light at 4 °C for 336 h. The degradation rate of lycopene during thermal treatment rose with increasing temperature and the activation energy for decomposition of the mixture of lycopene isomers was calculated to be 71.0 kJ mol -1 . The degradation rate of lycopene isomers was almost the same under thermal treatment. On the other hand, during light irradiation, isomerization was promoted rather than decomposition, i.e. (9Z)- and (13Z)-lycopene converted to the (all-E)-isomer. Copyright © 2018 Elsevier Ltd. All rights reserved.

Thermal oxidative degradation kinetics of agricultural residues using distributed activation energy model and global kinetic model.

PubMed

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

2018-08-01

The study concerned the thermal oxidative degradation kinetics of agricultural residues, peanut shell (PS) and sunflower shell (SS). The thermal behaviors were evaluated via thermogravimetric analysis and the kinetic parameters were determined by using distributed activation energy model (DAEM) and global kinetic model (GKM). Results showed that thermal oxidative decomposition of two samples processed in three zones; the ignition, burnout, and comprehensive combustibility between two agricultural residues were of great difference; and the combustion performance could be improved by boosting heating rate. The activation energy ranges calculated by the DAEM for the thermal oxidative degradation of PS and SS were 88.94-145.30 kJ mol -1 and 94.86-169.18 kJ mol -1 , respectively. The activation energy obtained by the GKM for the oxidative decomposition of hemicellulose and cellulose was obviously lower than that for the lignin oxidation at identical heating rate. To some degree, the determined kinetic parameters could acceptably simulate experimental data. Copyright © 2018 Elsevier Ltd. All rights reserved.

A highly efficient autothermal microchannel reactor for ammonia decomposition: Analysis of hydrogen production in transient and steady-state regimes

NASA Astrophysics Data System (ADS)

Engelbrecht, Nicolaas; Chiuta, Steven; Bessarabov, Dmitri G.

2018-05-01

The experimental evaluation of an autothermal microchannel reactor for H2 production from NH3 decomposition is described. The reactor design incorporates an autothermal approach, with added NH3 oxidation, for coupled heat supply to the endothermic decomposition reaction. An alternating catalytic plate arrangement is used to accomplish this thermal coupling in a cocurrent flow strategy. Detailed analysis of the transient operating regime associated with reactor start-up and steady-state results is presented. The effects of operating parameters on reactor performance are investigated, specifically, the NH3 decomposition flow rate, NH3 oxidation flow rate, and fuel-oxygen equivalence ratio. Overall, the reactor exhibits rapid response time during start-up; within 60 min, H2 production is approximately 95% of steady-state values. The recommended operating point for steady-state H2 production corresponds to an NH3 decomposition flow rate of 6 NL min-1, NH3 oxidation flow rate of 4 NL min-1, and fuel-oxygen equivalence ratio of 1.4. Under these flows, NH3 conversion of 99.8% and H2 equivalent fuel cell power output of 0.71 kWe is achieved. The reactor shows good heat utilization with a thermal efficiency of 75.9%. An efficient autothermal reactor design is therefore demonstrated, which may be upscaled to a multi-kW H2 production system for commercial implementation.

Fundamental Studies on Aluminum Fuels

DTIC Science & Technology

1944-12-01

Isooctr.no 200 C. Additives in the Syster. Aluminum Dilaur- r.te Cyclohexp.ne 201 2. Metathesis (Double Decomposition ) of Aluminum So^pc -ith...changes of hydrolysis -ire reduced (p»47). It has a sharp melting point (p. 88) and x-r:ty diffraotion pattern (p.71 ) and upon partial...of decomposition products. (In the same «ay as by distillation an acaotrope is often produoed and has a constant boiling point). It muat be noted

Decomposition of soil organic matter from boreal black spruce forest: environmental and chemical controls

Treesearch

Kimberly P. Wickland; Jason C. Neff

2007-01-01

Black spruce forests are a dominant covertype in the boreal forest region, and they inhabit landscapes that span a wide range of hydrologic and thermal conditions. These forests often have large stores of soil organic carbon. Recent increases in temperature at northern latitudes may be stimulating decomposition rates of this soil carbon. It is unclear, however, how...

Thermal Decomposition of Nitromethane and Reaction between CH3 and NO2.

PubMed

Matsugi, Akira; Shiina, Hiroumi

2017-06-08

The thermal decomposition of gaseous nitromethane and the subsequent bimolecular reaction between CH 3 and NO 2 have been experimentally studied using time-resolved cavity-enhanced absorption spectroscopy behind reflected shock waves in the temperature range 1336-1827 K and at a pressure of 100 kPa. Temporal evolution of NO 2 was observed following the pyrolysis of nitromethane (diluted to 80-140 ppm in argon) by monitoring the absorption around 400 nm. The primary objectives of the current work were to evaluate the rate constant for the CH 3 + NO 2 reaction (k 2 ) and to examine the contribution of the roaming isomerization pathway in nitromethane decomposition. The resultant rate constant can be expressed as k 2 = (9.3 ± 1.8) × 10 -10 (T/K) -0.5 cm 3 molecule -1 s -1 , which is in reasonable agreement with available literature data. The decomposition of nitromethane was found to predominantly proceed with the C-N bond fission process with the branching fraction of 0.97 ± 0.06. Therefore, the upper limit of the branching fraction for the roaming pathway was evaluated to be 0.09.

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. Copyright © 2013 Elsevier Ltd. All rights reserved.

Bulk and molecular-level characterization of laboratory-aged biomass burning organic aerosol from oak leaf and heartwood fuels

NASA Astrophysics Data System (ADS)

Fortenberry, Claire F.; Walker, Michael J.; Zhang, Yaping; Mitroo, Dhruv; Brune, William H.; Williams, Brent J.

2018-02-01

The chemical complexity of biomass burning organic aerosol (BBOA) greatly increases with photochemical aging in the atmosphere, necessitating controlled laboratory studies to inform field observations. In these experiments, BBOA from American white oak (Quercus alba) leaf and heartwood samples was generated in a custom-built emissions and combustion chamber and photochemically aged in a potential aerosol mass (PAM) flow reactor. A thermal desorption aerosol gas chromatograph (TAG) was used in parallel with a high-resolution time-of-flight aerosol mass spectrometer (AMS) to analyze BBOA chemical composition at different levels of photochemical aging. Individual compounds were identified and integrated to obtain relative decay rates for key molecules. A recently developed chromatogram binning positive matrix factorization (PMF) technique was used to obtain mass spectral profiles for factors in TAG BBOA chromatograms, improving analysis efficiency and providing a more complete determination of unresolved complex mixture (UCM) components. Additionally, the recently characterized TAG decomposition window was used to track molecular fragments created by the decomposition of thermally labile BBOA during sample desorption. We demonstrate that although most primary (freshly emitted) BBOA compounds deplete with photochemical aging, certain components eluting within the TAG thermal decomposition window are instead enhanced. Specifically, the increasing trend in the decomposition m/z 44 signal (CO2+) indicates formation of secondary organic aerosol (SOA) in the PAM reactor. Sources of m/z 60 (C2H4O2+), typically attributed to freshly emitted BBOA in AMS field measurements, were also investigated. From the TAG chemical speciation and decomposition window data, we observed a decrease in m/z 60 with photochemical aging due to the decay of anhydrosugars (including levoglucosan) and other compounds, as well as an increase in m/z 60 due to the formation of thermally labile organic acids within the PAM reactor, which decompose during TAG sample desorption. When aging both types of BBOA (leaf and heartwood), the AMS data exhibit a combination of these two contributing effects, causing limited change to the overall m/z 60 signal. Our observations demonstrate the importance of chemically speciated data in fully understanding bulk aerosol measurements provided by the AMS in both laboratory and field studies.

Application of FTIR spectroscopy to study the thermal stability of magnesium aspartate-arginine

NASA Astrophysics Data System (ADS)

Hacura, Andrzej; Marcoin, Wacława; Pasterny, Karol

2012-03-01

FTIR spectroscopy has been applied to study the thermal stability of magnesium aspartatearginine. An attempt has been made, using theoretically predicted IR spectra, to relate the changes in the experimental spectra with the decomposition process of the studied magnesium complex.

Simultaneous determination of α-asarone and β-asarone in Acorus tatarinowii using excitation-emission matrix fluorescence coupled with chemometrics methods

NASA Astrophysics Data System (ADS)

Bai, Xue-Mei; Liu, Tie; Liu, De-Long; Wei, Yong-Ju

2018-02-01

A chemometrics-assisted excitation-emission matrix (EEM) fluorescence method was proposed for simultaneous determination of α-asarone and β-asarone in Acorus tatarinowii. Using the strategy of combining EEM data with chemometrics methods, the simultaneous determination of α-asarone and β-asarone in the complex Traditional Chinese medicine system was achieved successfully, even in the presence of unexpected interferents. The physical or chemical separation step was avoided due to the use of ;mathematical separation;. Six second-order calibration methods were used including parallel factor analysis (PARAFAC), alternating trilinear decomposition (ATLD), alternating penalty trilinear decomposition (APTLD), self-weighted alternating trilinear decomposition (SWATLD), the unfolded partial least-squares (U-PLS) and multidimensional partial least-squares (N-PLS) with residual bilinearization (RBL). In addition, HPLC method was developed to further validate the presented strategy. Consequently, for the validation samples, the analytical results obtained by six second-order calibration methods were almost accurate. But for the Acorus tatarinowii samples, the results indicated a slightly better predictive ability of N-PLS/RBL procedure over other methods.

Structural, optical, electron paramagnetic, thermal and dielectric characterization of chalcopyrite.

PubMed

Prameena, B; Anbalagan, G; Gunasekaran, S; Ramkumaar, G R; Gowtham, B

2014-03-25

Chalcopyrite (CuFeS2) a variety of pyrite minerals was investigated through spectroscopic techniques and thermal analysis. The morphology and elemental analysis of the chalcopyrite have been done by high resolution SEM with EDAX. The lattice parameters were from the powder diffraction data (a=5.3003±0.0089 Å, c=10.3679±0.0289 Å; the volume of the unit cell=291.266 Å(3) with space group I42d (122)). The thermal decomposition behavior of chalcopyrite was studied by means of thermogravimetric analysis at three different heating rates 10, 15 and 20 °C/min. The values of effective activation energy (Ea), pre-exponential factor (ln A) for thermal decomposition have been measured at three different heating rates by employing Kissinger, Kim-Park and Flynn-Wall methods. Dielectric studies at different temperatures have also been carried out and it was found that both dielectric constant and dielectric loss decreases with the increase of frequency. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

Assessment of skeletal changes after post-mortem exposure to fire as an indicator of decomposition stage.

PubMed

Keough, N; L'Abbé, E N; Steyn, M; Pretorius, S

2015-01-01

Forensic anthropologists are tasked with interpreting the sequence of events from death to the discovery of a body. Burned bone often evokes questions as to the timing of burning events. The purpose of this study was to assess the progression of thermal damage on bones with advancement in decomposition. Twenty-five pigs in various stages of decomposition (fresh, early, advanced, early and late skeletonisation) were exposed to fire for 30 min. The scored heat-related features on bone included colour change (unaltered, charred, calcined), brown and heat borders, heat lines, delineation, greasy bone, joint shielding, predictable and minimal cracking, delamination and heat-induced fractures. Colour changes were scored according to a ranked percentage scale (0-3) and the remaining traits as absent or present (0/1). Kappa statistics was used to evaluate intra- and inter-observer error. Transition analysis was used to formulate probability mass functions [P(X=j|i)] to predict decomposition stage from the scored features of thermal destruction. Nine traits displayed potential to predict decomposition stage from burned remains. An increase in calcined and charred bone occurred synchronously with advancement of decomposition with subsequent decrease in unaltered surfaces. Greasy bone appeared more often in the early/fresh stages (fleshed bone). Heat borders, heat lines, delineation, joint shielding, predictable and minimal cracking are associated with advanced decomposition, when bone remains wet but lacks extensive soft tissue protection. Brown burn/borders, delamination and other heat-induced fractures are associated with early and late skeletonisation, showing that organic composition of bone and percentage of flesh present affect the manner in which it burns. No statistically significant difference was noted among observers for the majority of the traits, indicating that they can be scored reliably. Based on the data analysis, the pattern of heat-induced changes may assist in estimating decomposition stage from unknown, burned remains. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

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 2.7 K for entire image. Comparison with the evaluation DisTrad (E-DisTrad) and re-sampling methods for pixel decomposition also indicate that our DSPD has the lowest RMSE in all cases, including urban region, water bodies, and natural terrain. The obvious increase in spatial resolution remarkably uplifts the capability of the coarse MODIS LST images in highlighting the details of LST variation. Therefore it can be concluded that, in spite of complicated procedures, the proposed DSPD approach provides an alternative to improve the spatial resolution of MODIS LST image hence expand its applicability to the real world. PMID:25609048

Evaluation on the Photosensitivity of 2,2'-Azobis(2,4-Dimethyl)Valeronitrile with UV.

PubMed

Yang, Yi; Tsai, Yun-Ting

2017-12-14

Azo compounds have high exothermic characteristics and low thermal stability, which have caused many serious thermal accidents around the world. In general, different locations (e.g., equatorial or polar regions) have different UV intensities. If the azo compound exists in an inappropriately stored or transported condition, the decrease in thermal stability may cause a thermal hazard or ageing. 2,2'-Azobis(2,4-dimethyl)valeronitrile (ADVN) is investigated with respect to the thermal stability affected by UV exposure at 0, 6, 12, and 24 h. When ADVN is exposed to 24 h of UV (100 mW/m² and 254 nm), T ₀ is not only advanced, but the mass loss is also increased during the main decomposition stage. In addition, the apparent activation energy and integral procedural decomposition temperature ( IPDT ) of ADVN exposed to 24 h of UV is calculated by kinetic models. Therefore, the prevention mechanism, thermal characteristics, and kinetic parameters are established in our study. We should isolate UV contacting ADVN under any situations, avoiding ADVN being aged or leading to thermal runaway. This study provided significant information for a safer process under changing UV exposure times for ADVN. Furthermore, the research method may serve as an important benchmark for handling potentially hazardous chemicals, such as azo compounds described herein.

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}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nagai, Tsukasa; Japan Society for the Promotion of Science, 1-8 Chiyoda-ku, Tokyo 102-8472; Tamura, Shinji

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. -more » 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.« less

Thermal ablation for partial splenectomy hemostasis, spleen trauma, splenic metastasis and hypersplenism.

PubMed

Duan, Ya-Qi; Liang, Ping

2013-05-01

Many studies have been conducted on splenic thermal ablation for partial splenectomy hemostasis, spleen trauma, splenic metastasis and hypersplenism. In this article, we review the evolution and current status of radiofrequency and microwave ablation in the treatment of spleen diseases. All publications from 1990 to 2011 on radiofrequency and microwave ablation for partial splenectomy hemostasis, spleen trauma, splenic metastasis and hypersplenism were retrieved by searching PubMed. Thermal ablation in the spleen for partial splenectomy hemostasis, spleen trauma, splenic metastasis and hypersplenism can preserve part of the spleen and maintain splenic immunologic function. Thermal ablation for assisting hemostasis in partial splenectomy minimizes blood loss during operation. Thermal ablation for spleen trauma reduces the number of splenectomy and the amount of blood transfusion. Thermal ablation for splenic metastasis is minimally invasive and can be done under the guidance of an ultrasound, which helps shorten the recovery time. Thermal ablation for hypersplenism increases platelet (PLT) and white blood cell (WBC) counts and improves liver function. It also helps to maintain splenic immunologic function and even improves splenic immunologic function in the short-term. In conclusion, thermal ablative approaches are promising for partial splenectomy hemostasis, spleen trauma, splenic metastasis and hypersplenism. In order to improve therapeutic effects, directions for future studies may include standardized therapeutic indications, prolonged observation periods and enlarged sample sizes.

Partially Coherent Scattering in Stellar Chromospheres. Part 4; Analytic Wing Approximations

NASA Technical Reports Server (NTRS)

Gayley, K. G.

1993-01-01

Simple analytic expressions are derived to understand resonance-line wings in stellar chromospheres and similar astrophysical plasmas. The results are approximate, but compare well with accurate numerical simulations. The redistribution is modeled using an extension of the partially coherent scattering approximation (PCS) which we term the comoving-frame partially coherent scattering approximation (CPCS). The distinction is made here because Doppler diffusion is included in the coherent/noncoherent decomposition, in a form slightly improved from the earlier papers in this series.

Electrochemical and Infrared Absorption Spectroscopy Detection of SF6 Decomposition Products

PubMed Central

Dong, Ming; Ren, Ming; Ye, Rixin

2017-01-01

Sulfur hexafluoride (SF6) gas-insulated electrical equipment is widely used in high-voltage (HV) and extra-high-voltage (EHV) power systems. Partial discharge (PD) and local heating can occur in the electrical equipment because of insulation faults, which results in SF6 decomposition and ultimately generates several types of decomposition products. These SF6 decomposition products can be qualitatively and quantitatively detected with relevant detection methods, and such detection contributes to diagnosing the internal faults and evaluating the security risks of the equipment. At present, multiple detection methods exist for analyzing the SF6 decomposition products, and electrochemical sensing (ES) and infrared (IR) spectroscopy are well suited for application in online detection. In this study, the combination of ES with IR spectroscopy is used to detect SF6 gas decomposition. First, the characteristics of these two detection methods are studied, and the data analysis matrix is established. Then, a qualitative and quantitative analysis ES-IR model is established by adopting a two-step approach. A SF6 decomposition detector is designed and manufactured by combining an electrochemical sensor and IR spectroscopy technology. The detector is used to detect SF6 gas decomposition and is verified to reliably and accurately detect the gas components and concentrations. PMID:29140268

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

PubMed

Tsyshevsky, Roman V; Sharia, Onise; Kuklja, Maija M

2016-02-19

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

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

DOE PAGES

Tsyshevsky, Roman; Sharia, Onise; Kuklja, Maija

2016-02-19

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

Effects of biopretreatment of corn stover with white-rot fungus on low-temperature pyrolysis products.

PubMed

Yang, Xuewei; Ma, Fuying; Yu, Hongbo; Zhang, Xiaoyu; Chen, Shulin

2011-02-01

The thermal decomposition of biopretreated corn stover during the low temperature has been studied by using the Py-GC/MS analysis and thermogravimetric analysis with the distributed activation energy model (DAEM). Results showed that biopretreatment with white-rot fungus Echinodontium taxodii 2538 can improve the low-temperature pyrolysis of biomass, by increasing the pyrolysis products of cellulose, hemicellulose (furfural and sucrose increased up to 4.68-fold and 2.94-fold respectively) and lignin (biophenyl and 3,7,11,15-tetramethyl-2-hexadecen-1-ol increased 2.45-fold and 4.22-fold, respectively). Calculated by DAEM method, it showed that biopretreatment can decrease the activation energy during the low temperature range, accelerate the reaction rate and start the thermal decomposition with lower temperature. ATR-FTIR results showed that the deconstruction of lignin and the decomposition of the main linkages between hemicellulose and lignin could contribute to the improvement of the pyrolysis at low temperature. Copyright © 2010 Elsevier Ltd. All rights reserved.

Decomposition of Potassium Ferrate(VI) (K2FeO4) and Potassium Ferrate(III) (KFeO2): In-situ Mössbauer Spectroscopy Approach

NASA Astrophysics Data System (ADS)

Machala, Libor; Zboril, Radek; Sharma, Virender K.; Homonnay, Zoltan

2008-10-01

Mössbauer spectroscopy was shown to be very useful technique studying the mechanism of thermal decomposition or aging processes of the most known ferrate(VI), K2FeO4. In-situ Mössbauer spectroscopy approach was used to monitor the phase composition during the studied processes. The experimental set-up was designed to perform in-situ measurements at high temperatures and at different air humid conditions at room temperature. The potassium ferrate(III), KFeO2 was demonstrated to be the primary product of thermal decomposition of K2FeO4. The KFeO2 was unstable in a humid air at room temperature and reacted with components of air, H2O and CO2 to give Fe2O3 nanoparticles and KHCO3. The aging kinetics of K2FeO4 and KFeO2 under humid air were significantly dependent on the relative air humidity.

Effect of thermal radiation and chemical reaction on non-Newtonian fluid through a vertically stretching porous plate with uniform suction

NASA Astrophysics Data System (ADS)

Khan, Zeeshan; Khan, Ilyas; Ullah, Murad; Tlili, I.

2018-06-01

In this work, we discuss the unsteady flow of non-Newtonian fluid with the properties of heat source/sink in the presence of thermal radiation moving through a binary mixture embedded in a porous medium. The basic equations of motion including continuity, momentum, energy and concentration are simplified and solved analytically by using Homotopy Analysis Method (HAM). The energy and concentration fields are coupled with Dankohler and Schmidt numbers. By applying suitable transformation, the coupled nonlinear partial differential equations are converted to couple ordinary differential equations. The effect of physical parameters involved in the solutions of velocity, temperature and concentration profiles are discussed by assign numerical values and results obtained shows that the velocity, temperature and concentration profiles are influenced appreciably by the radiation parameter, Prandtl number, suction/injection parameter, reaction order index, solutal Grashof number and the thermal Grashof. It is observed that the non-Newtonian parameter H leads to an increase in the boundary layer thickness. It was established that the Prandtl number decreases thee thermal boundary layer thickness which helps in maintaining system temperature of the fluid flow. It is observed that the temperature profiles higher for heat source parameter and lower for heat sink parameter throughout the boundary layer. Fromm this simulation it is analyzed that an increase in the Schmidt number decreases the concentration boundary layer thickness. Additionally, for the sake of comparison numerical method (ND-Solve) and Adomian Decomposition Method are also applied and good agreement is found.

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.

Vapor phase growth technique of III-V compounds utilizing a preheating step

NASA Technical Reports Server (NTRS)

Olsen, Gregory Hammond (Inventor); Zamerowski, Thomas Joseph (Inventor); Buiocchi, Charles Joseph (Inventor)

1978-01-01

In the vapor phase epitaxy fabrication of semiconductor devices and in particular semiconductor lasers, the deposition body on which a particular layer of the laser is to be grown is preheated to a temperature about 40.degree. to 60.degree. C. lower than the temperature at which deposition occurs. It has been discovered that by preheating at this lower temperature there is reduced thermal decomposition at the deposition surface, especially for semiconductor materials such as indium gallium phosphide and gallium arsenide phosphide. A reduction in thermal decomposition reduces imperfections in the deposition body in the vicinity of the deposition surface, thereby providing a device with higher efficiency and longer lifetime.

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.

Preparation of α-Fe2O3 nanotubes via electrospinning and research on their catalytic properties

NASA Astrophysics Data System (ADS)

Shao, Hao; Zhang, Xuebin; Chen, Fanyan; Liu, Shasha; Ji, Yi; Zhu, Yajun; Feng, Yi

2012-09-01

In this paper, smooth α-Fe2O3 nanotubes have been successfully synthesized by electrospinning of ferric nitrate-polyvinyl alcohol solution followed by calcination in air. The morphologies and structures of the samples were characterized by transmission electron microscopy, scanning electron microscopy and X-ray diffraction. The catalytic properties were studied by differential thermal analysis and thermogravimetric analysis. The results indicated that the as-prepared α-Fe2O3 nanotubes showed a continuous morphology and an extremely high degree of crystallization. The average inner and outer diameters of the obtained α-Fe2O3 nanotubes were about 60 nm and 100 nm, respectively. The obtained α-Fe2O3 nanotubes were able to lower the temperature of the high-temperature thermal decomposition of ammonium perchlorate, while they had little effect on the crystallographic phase transformation and the low-temperature thermal decomposition.

Modelling Behaviour of a Carbon Epoxy Composite Exposed to Fire: Part I—Characterisation of Thermophysical Properties

PubMed Central

Tranchard, Pauline; Samyn, Fabienne; Duquesne, Sophie; Estèbe, Bruno; Bourbigot, Serge

2017-01-01

Thermophysical properties of a carbon-reinforced epoxy composite laminate (T700/M21 composite for aircraft structures) were evaluated using different innovative characterisation methods. Thermogravimetric Analysis (TGA), Simultaneous Thermal analysis (STA), Laser Flash analysis (LFA), and Fourier Transform Infrared (FTIR) analysis were used for measuring the thermal decomposition, the specific heat capacity, the anisotropic thermal conductivity of the composite, the heats of decomposition and the specific heat capacity of released gases. It permits to get input data to feed a three-dimensional (3D) model given the temperature profile and the mass loss obtained during well-defined fire scenarios (model presented in Part II of this paper). The measurements were optimised to get accurate data. The data also permit to create a public database on an aeronautical carbon fibre/epoxy composite for fire safety engineering. PMID:28772854

Comparative analysis of polychlorinated biphenyl decomposition processes in air or argon (+oxygen) thermal plasma.

PubMed

Kostic, Z G; Stefanovic, P L; Pavlović, P B

2000-07-10

Thermal plasmas may solve one of the biggest toxic waste disposal problems. The disposal of polychlorinated biphenyls (PCBs) is a long standing problem which will get worse in the coming years, when 180000 tons of PCB-containing wastes are expected to accumulate in Europe (Hot ions break down toxic chemicals, New Scientist, 16 April 1987, p. 24.). The combustion of PCBs in ordinary incinerators (at temperature T approximately 1100 K, as measured near the inner wall of the combustion chamber (European Parliament and Council Directive on Incineration of Waste (COM/99/330), Europe energy, 543, Sept. 17, 1999, 1-23.)) can cause more problems than it solves, because highly toxic dioxins and dibenzofurans are formed if the combustion temperature is too low (T<1400 K). The paper presents a thermodynamic consideration and comparative analysis of PCB decomposition processes in air or argon (+oxygen) thermal plasmas.

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

Energetics of lithium ion battery failure.

PubMed

Lyon, Richard E; Walters, Richard N

2016-11-15

The energy released by failure of rechargeable 18-mm diameter by 65-mm long cylindrical (18650) lithium ion cells/batteries was measured in a bomb calorimeter for 4 different commercial cathode chemistries over the full range of charge using a method developed for this purpose. Thermal runaway was induced by electrical resistance (Joule) heating of the cell in the nitrogen-filled pressure vessel (bomb) to preclude combustion. The total energy released by cell failure, ΔHf, was assumed to be comprised of the stored electrical energy E (cell potential×charge) and the chemical energy of mixing, reaction and thermal decomposition of the cell components, ΔUrxn. The contribution of E and ΔUrxn to ΔHf was determined and the mass of volatile, combustible thermal decomposition products was measured in an effort to characterize the fire safety hazard of rechargeable lithium ion cells. Published by Elsevier B.V.

Explosive decomposition of hydrazine by rapid compression of a gas volume

NASA Technical Reports Server (NTRS)

Bunker, R. L.; Baker, D. L.; Lee, J. H. S.

1991-01-01

In the present investigation of the initiation mechanism and the explosion mode of hydrazine decomposition, a 20 cm-long column of liquid hydrazine was accelerated into a column of gaseous nitrogen, from which it was separated by a thin Teflon diaphragm, in a close-ended cylindrical chamber. Video data obtained reveal the formation of a froth generated by the acceleration of hydrazine into nitrogen at the liquid hydrazine-gaseous nitrogen interface. The explosive hydrazine decomposition had as its initiation mechanism the formation of a froth at a critical temperature; the explosion mode of hydrazine is a confined thermal runaway reaction.

The Enhancement of Gas Pressure Diagnostics in the P-ODTX System

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hsu, Peter C.; Jones, Aaron; Tesillo, Lynda

The One Dimensional Time to Explosion (ODTX) system at the Lawrence Livermore National Laboratory is a useful tool for thermal safety assessment of energetic material. It has been used since 1970s to measure times to explosion, threshold thermal explosion temperature, thermal explosion violence, and determine decomposition kinetic parameters of energetic materials. ODTX data obtained for the last 40 years can be found elsewhere.

Intramolecular distribution of stable nitrogen and oxygen isotopes of nitrous oxide emitted during coal combustion.

PubMed

Ogawa, Mitsuteru; Yoshida, Naohiro

2005-11-01

The intramolecular distribution of stable isotopes in nitrous oxide that is emitted during coal combustion was analyzed using an isotopic ratio mass spectrometer equipped with a modified ion collector system (IRMS). The coal was combusted in a test furnace fitted with a single burner and the flue gases were collected at the furnace exit following removal of SO(x), NO(x), and H2O in order to avoid the formation of artifact nitrous oxide. The nitrous oxide in the flue gases proved to be enriched in 15N relative to the fuel coal. In air-staged combustion experiments, the staged air ratio was controlled over a range of 0 (unstaged combustion), 20%, and 30%. As the staged air ratio increased, the delta15N and delta18O of the nitrous oxide in the flue gases became depleted. The central nitrogen of the nitrous oxide molecule, N(alpha), was enriched in 15N relative to that occupying the end position of the molecule, N(beta), but this preference, expressed as delta15N(alpha)-delta15N(beta), decreased with the increase in the staged air ratio. Thermal decomposition and hydrogen reduction experiments carried out using a tube reactor allowed qualitative estimates of the kinetic isotope effects that occurred during the decomposition of the nitrous oxide and quantitative estimates of the extent to which the nitrous oxide had decomposed. The site preference of nitrous oxide increased with the extent of the decomposition reactions. Assuming that no site preference exists in nitrous oxide before decomposition, the behavior of nitrous oxide in the test combustion furnace was analyzed using the Rayleigh equation based on a single distillation model. As a result, the extent of decomposition of nitrous oxide was estimated as 0.24-0.26 during the decomposition reaction governed by the thermal decomposition and as 0.35-0.38 during the decomposition reaction governed by the hydrogen reduction in staged combustion. The intramolecular distribution of nitrous oxide can be a valuable parameter to estimate the extent of decomposition reaction and to understand the reaction pathway of nitrous oxide at the high temperature.

Thermal decomposition of gaseous ammonium nitrate at low pressure: kinetic modeling of product formation and heterogeneous decomposition of nitric acid.

PubMed

Park, J; Lin, M C

2009-12-03

The thermal decomposition of ammonium nitrate, NH(4)NO(3) (AN), in the gas phase has been studied at 423-56 K by pyrolysis/mass spectrometry under low-pressure conditions using a Saalfeld reactor coated with boric acid. The sublimation of NH(4)NO(3) at 423 K was proposed to produce equal amounts of NH(3) and HNO(3), followed by the decomposition reaction of HNO(3), HNO(3) + M --> OH + NO(2) + M (where M = third-body and reactor surface). The absolute yields of N(2), N(2)O, H(2)O, and NH(3), which can be unambiguously measured and quantitatively calibrated under a constant pressure at 5-6.2 torr He are kinetically modeled using the detailed [H,N,O]-mechanism established earlier for the simulation of NH(3)-NO(2) (Park, J.; Lin, M. C. Technologies and Combustion for a Clean Environment. Proc. 4th Int. Conf. 1997, 34-1, 1-5) and ADN decomposition reactions (Park, J.; Chakraborty, D.; Lin, M. C. Proc. Combust. Inst. 1998, 27, 2351-2357). Since the homogeneous decomposition reaction of HNO(3) itself was found to be too slow to account for the consumption of reactants and the formation of products, we also introduced the heterogeneous decomposition of HNO(3) in our kinetic modeling. The heterogeneous decomposition rate of HNO(3), HNO(3) + (B(2)O(3)/SiO(2)) --> OH + NO(2) + (B(2)O(3)/SiO(2)), was determined by varying its rate to match the modeled result to the measured concentrations of NH(3) and H(2)O; the rate could be represented by k(2b) = 7.91 x 10(7) exp(-12 600/T) s(-1), which appears to be consistent with those reported by Johnston and co-workers (Johnston, H. S.; Foering, L.; Tao, Y.-S.; Messerly, G. H. J. Am. Chem. Soc. 1951, 73, 2319-2321) for HNO(3) decomposition on glass reactors at higher temperatures. Notably, the concentration profiles of all species measured could be satisfactorily predicted by the existing [H,N,O]-mechanism with the heterogeneous initiation process.

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.

Study of insect succession and rate of decomposition on a partially burned pig carcass in an oil palm plantation in Malaysia.

PubMed

Heo, Chong Chin; Mohamad, Abdullah Marwi; Ahmad, Firdaus Mohd Salleh; Jeffery, John; Kurahashi, Hiromu; Omar, Baharudin

2008-12-01

Insects found associated with corpse can be used as one of the indicators in estimating postmortem interval (PMI). The objective of this study was to compare the stages of decomposition and faunal succession between a partially burnt pig (Sus scrofa Linnaeus) and natural pig (as control). The burning simulated a real crime whereby the victim was burnt by murderer. Two young pigs weighed approximately 10 kg were used in this study. Both pigs died from pneumonia and immediately placed in an oil palm plantation near a pig farm in Tanjung Sepat, Selangor, Malaysia. One pig was partially burnt by 1-liter petrol while the other served as control. Both carcasses were visited twice per day for the first week and once thereafter. Adult flies and larvae on the carcasses were collected and later processed in a forensic entomology laboratory. Results showed that there was no significant difference between the rate of decomposition and sequence of faunal succession on both pig carcasses. Both carcasses were completely decomposed to remain stage after nine days. The species of flies visiting the pig carcasses consisted of blow flies (Chrysomya megacephala, Chrysomya rufifacies, Hemipyrellia ligurriens), flesh fly (Sarcophagidae.), muscid fly (Ophyra spinigera), soldier fly (Hermetia illucens), coffin fly (Phoridae) and scavenger fly (Sepsidae). The only difference noted was in the number of adult flies, whereby more flies were seen in the control carcass. Faunal succession on both pig carcasses was in the following sequence: Calliphoridae, Sarcophagidae, Muscidae, Phoridae and lastly Stratiomyidae. However, there was overlap in the appearance of members of these families. Blowflies continued to oviposit on both carcasses. Hence postmortem interval (PMI) can still be estimated from the partially burnt pig carcass.

Catalytic effects of inorganic acids on the decomposition of ammonium nitrate.

PubMed

Sun, Jinhua; Sun, Zhanhui; Wang, Qingsong; Ding, Hui; Wang, Tong; Jiang, Chuansheng

2005-12-09

In order to evaluate the catalytic effects of inorganic acids on the decomposition of ammonium nitrate (AN), the heat releases of decomposition or reaction of pure AN and its mixtures with inorganic acids were analyzed by a heat flux calorimeter C80. Through the experiments, the different reaction mechanisms of AN and its mixtures were analyzed. The chemical reaction kinetic parameters such as reaction order, activation energy and frequency factor were calculated with the C80 experimental results for different samples. Based on these parameters and the thermal runaway models (Semenov and Frank-Kamenestkii model), the self-accelerating decomposition temperatures (SADTs) of AN and its mixtures were calculated and compared. The results show that the mixtures of AN with acid are more unsteady than pure AN. The AN decomposition reaction is catalyzed by acid. The calculated SADTs of AN mixtures with acid are much lower than that of pure AN.

Azadirachta indica plant-assisted green synthesis of Mn3O4 nanoparticles: Excellent thermal catalytic performance and chemical sensing behavior.

PubMed

Sharma, Jitendra Kumar; Srivastava, Pratibha; Ameen, Sadia; Akhtar, M Shaheer; Singh, Gurdip; Yadava, Sudha

2016-06-15

The leaf extract of Azadirachta indica (Neem) plant was utilized as reducing agent for the green synthesis of Mn3O4 nanoparticles (NPs). The crystalline analysis demonstrated the typical tetragonal hausmannite crystal structure of Mn3O4, which confirmed the formation of Mn3O4 NPs without the existence of other oxides. Green synthesized Mn3O4 NPs were applied for the catalytic thermal decomposition of ammonium perchlorate (AP) and as working electrode for fabricating the chemical sensor. The excellent catalytic effect for the thermal decomposition of AP was observed by decreasing the decomposition temperature by 175 °C with single decomposing step. The fabricated chemical sensor based on green synthesized Mn3O4 NPs displayed high, reliable and reproducible sensitivity of ∼569.2 μA mM(-1) cm(-2) with reasonable limit of detection (LOD) of ∼22.1 μM and the response time of ∼10 s toward the detection of 2-butanone chemical. A relatively good linearity in the ranging from ∼20 to 160 μM was detected for Mn3O4 NPs electrode based 2-butanone chemical sensor. Copyright © 2016 Elsevier Inc. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

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

PubMed

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

2013-09-15

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

Unraveling the Decomposition Process of Lead(II) Acetate: Anhydrous Polymorphs, Hydrates, and Byproducts and Room Temperature Phosphorescence.

PubMed

Martínez-Casado, Francisco J; Ramos-Riesco, Miguel; Rodríguez-Cheda, José A; Cucinotta, Fabio; Matesanz, Emilio; Miletto, Ivana; Gianotti, Enrica; Marchese, Leonardo; Matěj, Zdeněk

2016-09-06

Lead(II) acetate [Pb(Ac)2, where Ac = acetate group (CH3-COO(-))2] is a very common salt with many and varied uses throughout history. However, only lead(II) acetate trihydrate [Pb(Ac)2·3H2O] has been characterized to date. In this paper, two enantiotropic polymorphs of the anhydrous salt, a novel hydrate [lead(II) acetate hemihydrate: Pb(Ac)2·(1)/2H2O], and two decomposition products [corresponding to two different basic lead(II) acetates: Pb4O(Ac)6 and Pb2O(Ac)2] are reported, with their structures being solved for the first time. The compounds present a variety of molecular arrangements, being 2D or 1D coordination polymers. A thorough thermal analysis, by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), was also carried out to study the behavior and thermal data of the salt and its decomposition process, in inert and oxygenated atmospheres, identifying the phases and byproducts that appear. The complex thermal behavior of lead(II) acetate is now solved, finding the existence of another hydrate, two anhydrous enantiotropic polymorphs, and some byproducts. Moreover, some of them are phosphorescent at room temperature. The compounds were studied by TGA, DSC, X-ray diffraction, and UV-vis spectroscopy.

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

PubMed

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

2017-12-01

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

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

PubMed

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

2010-07-01

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

Mixture design and treatment methods for recycling contaminated sediment.

PubMed

Wang, Lei; Kwok, June S H; Tsang, Daniel C W; Poon, Chi-Sun

2015-01-01

Conventional marine disposal of contaminated sediment presents significant financial and environmental burden. This study aimed to recycle the contaminated sediment by assessing the roles and integration of binder formulation, sediment pretreatment, curing method, and waste inclusion in stabilization/solidification. The results demonstrated that the 28-d compressive strength of sediment blocks produced with coal fly ash and lime partially replacing cement at a binder-to-sediment ratio of 3:7 could be used as fill materials for construction. The X-ray diffraction analysis revealed that hydration products (calcium hydroxide) were difficult to form at high sediment content. Thermal pretreatment of sediment removed 90% of indigenous organic matter, significantly increased the compressive strength, and enabled reuse as non-load-bearing masonry units. Besides, 2-h CO2 curing accelerated early-stage carbonation inside the porous structure, sequestered 5.6% of CO2 (by weight) in the sediment blocks, and acquired strength comparable to 7-d curing. Thermogravimetric analysis indicated substantial weight loss corresponding to decomposition of poorly and well crystalline calcium carbonate. Moreover, partial replacement of contaminated sediment by various granular waste materials notably augmented the strength of sediment blocks. The metal leachability of sediment blocks was minimal and acceptable for reuse. These results suggest that contaminated sediment should be viewed as useful resources. Copyright © 2014 Elsevier B.V. All rights reserved.

Investigation of Molecular Structure and Thermal Properties of Thermo-Oxidative Aged SBS in Blends and Their Relations

PubMed Central

Xu, Xiong; Yu, Jianying; Xue, Lihui; Zhang, Canlin; Zha, Yagang; Gu, Yi

2017-01-01

Tri-block copolymer styrene–butadiene (SBS) is extensively applied in bituminous highway construction due to its high elasticity and excellent weather resistance. With the extension of time, tri-block structural SBS automatically degrades into bi-block structural SB- with some terminal oxygen-containing groups under the comprehensive effects of light, heat, oxygen, etc. In this paper, the effects of aging temperature, aging time and oxygen concentration on the molecular structure of thermo-oxidative aged SBS were mainly investigated using Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS), and the correlation between oxygen-containing groups and thermal properties (TG–DTG) was further discussed. The FTIR and XPS results show that rapid decomposition of SBS will occur with increments of aging temperature, aging time and oxygen concentration, and a large number of oxygen-containing groups such as –OH, C=O, –COOH, etc. will be formed during thermo-oxidative aging. In short-term aging, changes in aging temperature and oxygen concentration have a significant impact on the structural damage of SBS. However, in long-term aging, it has no further effect on the molecular structure of SBS or on increasing oxygen concentration. The TG and DTG results indicate that the concentration of substances with low molecular weight gradually increases with the improvement of the degree of aging of the SBS, while the initial decomposition rate increases at the beginning of thermal weightlessness and the decomposition rate slows down in comparison with neat SBS. From the relation between the XPS and TG results, it can be seen that the initial thermal stability of SBS rapidly reduces as the relative concentration of the oxygen-containing groups accumulates around 3%, while the maximum decomposition temperature slowly decreases when the relative concentration of the oxygen-containing groups is more than 3%, due to the difficult damage to strong bonds on the molecular structure of aged SBS. PMID:28773124

Investigation of Molecular Structure and Thermal Properties of Thermo-Oxidative Aged SBS in Blends and Their Relations.

PubMed

Xu, Xiong; Yu, Jianying; Xue, Lihui; Zhang, Canlin; Zha, Yagang; Gu, Yi

2017-07-07

Tri-block copolymer styrene-butadiene (SBS) is extensively applied in bituminous highway construction due to its high elasticity and excellent weather resistance. With the extension of time, tri-block structural SBS automatically degrades into bi-block structural SB- with some terminal oxygen-containing groups under the comprehensive effects of light, heat, oxygen, etc. In this paper, the effects of aging temperature, aging time and oxygen concentration on the molecular structure of thermo-oxidative aged SBS were mainly investigated using Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS), and the correlation between oxygen-containing groups and thermal properties (TG-DTG) was further discussed. The FTIR and XPS results show that rapid decomposition of SBS will occur with increments of aging temperature, aging time and oxygen concentration, and a large number of oxygen-containing groups such as -OH, C=O, -COOH, etc. will be formed during thermo-oxidative aging. In short-term aging, changes in aging temperature and oxygen concentration have a significant impact on the structural damage of SBS. However, in long-term aging, it has no further effect on the molecular structure of SBS or on increasing oxygen concentration. The TG and DTG results indicate that the concentration of substances with low molecular weight gradually increases with the improvement of the degree of aging of the SBS, while the initial decomposition rate increases at the beginning of thermal weightlessness and the decomposition rate slows down in comparison with neat SBS. From the relation between the XPS and TG results, it can be seen that the initial thermal stability of SBS rapidly reduces as the relative concentration of the oxygen-containing groups accumulates around 3%, while the maximum decomposition temperature slowly decreases when the relative concentration of the oxygen-containing groups is more than 3%, due to the difficult damage to strong bonds on the molecular structure of aged SBS.

A study of the effect of gamma and laser irradiation on the thermal, optical and structural properties of CR-39 nuclear track detector

NASA Astrophysics Data System (ADS)

Nouh, S. A.; Atta, M. R.; El-Melleegy, W. M.

2004-08-01

A comparative study of the effect of gamma and laser irradiation on the thermal, optical and structural properties of the CR-39 diglycol carbonate solid state nuclear track detector has been carried out. Samples from CR-39 polymer were classified into two main groups: the first group was irradiated by gamma rays with doses at levels between 20 and 300 kGy, whereas the second group was exposed to infrared laser radiation with energy fluences at levels between 0.71 and 8.53 J/cm(2). Non-isothermal studies were carried out using thermogravimetry, differential thermogravimetry and differential thermal analysis to obtain activation energy of decomposition and transition temperatures for the non-irradiated and all irradiated CR-39 samples. In addition, optical and structural property studies were performed on non-irradiated and irradiated CR-39 samples using refractive index and X-ray diffraction measurements. Variation in the onset temperature of decomposition T-o, activation energy of decomposition E-a, melting temperature T-m, refractive index n and the mass fraction of the amorphous phase after gamma and laser irradiation were studied. It was found that many changes in the thermal, optical and structural properties of the CR-39 polymer could be produced by gamma irradiation via degradation and cross-linking mechanisms. Also, the gamma dose has an advantage of increasing the correlation between thermal stability of the CR-39 polymer and bond formation created by the ionizing effect of gamma radiation. On the other hand, higher laser-energy fluences in the range 4.27-8.53 J/cm(2) decrease the melting temperature of the CR-39 polymer and this is most suitable for applications requiring molding of the polymer at lower temperatures.

Thermochemical properties of nanometer CL-20 and PETN fabricated using a mechanical milling method

NASA Astrophysics Data System (ADS)

Song, Xiaolan; Wang, Yi; An, Chongwei

2018-06-01

2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) and pentaerythritol tetranitrate (PETN), with mean sizes of 73.8 nm and 267.7 nm, respectively, were fabricated on a high-energy ball-mill. Scanning electron microscope (SEM) analysis was used to image the micron-scale morphology of nano-explosives, and the particle size distribution was calculated using the statistics of individual particle sizes obtained from the SEM images. Analyses, such as X-ray diffractometer (XRD), infrared spectroscopy (IR), and X-ray photoelectron spectroscopy (XPS), were also used to confirm whether the crystal phase, molecular structure, and surface elements changed after a long-term milling process. The results were as expected. Thermal analysis was performed at different heating rates. Parameters, such as the activation energy (ES), activation enthalpy (ΔH≠), activation free energy (ΔG≠), activation entropy (ΔS≠), and critical temperature of thermal explosion (Tb), were calculated to determine the decomposition courses of the explosives. Moreover, the thermal decomposition mechanisms of nano CL-20 and nano PETN were investigated using thermal-infrared spectrometry online (DSC-IR) analysis, by which their gas products were also detected. The results indicated that nano CL-20 decomposed to CO2 and N2O and that nano PETN decayed to NO2, which implied a remarkable difference between the decomposition mechanisms of the two explosives. In addition, the mechanical sensitivities of CL-20 and PETN were tested, and the results revealed that nano-explosives were more insensitive than raw ones, and the possible mechanism for this was discussed. Thermal sensitivity was also investigated with a 5 s bursting point test, from which the 5 s bursting point (T5s) and the activation of the deflagration were obtained.

Influence of thermal treatment on the formation of zirconia nanostructured powder by thermal decomposition of different precursors

NASA Astrophysics Data System (ADS)

Stoia, Marcela; Barvinschi, Paul; Barbu-Tudoran, Lucian; Negrea, Adina; Barvinschi, Floricica

2013-10-01

The paper presents some results concerning the preparation of zirconia powders starting from ZrOCl2·8H2O by using two synthesis methods: (a) precipitation with NH3, at 90 °C, and (b) thermal decomposition of carboxylate precursors, obtained in the reaction of zirconium nitrate and two different alcohols, 1,3-propanediol (PD) and poly(vinyl alcohol) (PVA), at 150 °C. The precursors obtained at different temperatures have been characterized by thermal analysis (TG, DTA) and FT-IR spectroscopy. DTA analysis evidenced very clearly the transition temperatures between zirconia crystalline phases. The precursors have been annealed at different temperatures in order to obtain zirconia powders and the as obtained powders have been characterized by means of X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), and Scanning Electron Microscopy (SEM). In case of precipitation method the presence of the tetragonal phase was observed at 400 °C, while the monoclinic phase appears at temperatures higher than 400 °C, becoming major crystalline phase starting with 700 °C. In case of the powders prepared by thermal decomposition of carboxylate precursors, the tetragonal phase was formed at temperatures below 700 °C, when the monoclinic phase begin to crystallize as secondary phase, in a higher proportion for the samples synthesized with 1,3-propanediol. All powders annealed at 1200 °C are pure monoclinic zirconia. SEM images have evidenced for the zirconia powders annealed at 1000 °C particles with diameters up to 150 nm, agglomerated in micrometer-sized aggregates, more individualized and homogenous than that obtained in the case of zirconia powder synthesized with poly(vinyl alcohol).

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. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Thermochemistry, Tautomerism, and Thermal Decomposition of 1,5-Diaminotetrazole: A High-Level ab Initio Study.

PubMed

Shakhova, Margarita V; Muravyev, Nikita V; Gritsan, Nina P; Kiselev, Vitaly G

2018-04-19

Thermochemistry, kinetics, and mechanism of thermal decomposition of 1,5-diaminotetrazole (DAT), a widely used "building block" of nitrogen-rich energetic compounds, were studied theoretically at a high and reliable level of theory (viz., using the explicitly correlated CCSD(T)-F12/aug-cc-pVTZ procedure). Quantum chemical calculations provided detailed insight into the thermolysis mechanism of DAT missing in the existing literature. Moreover, several contradictory assumptions on the mechanism and key intermediates of thermolysis were resolved. The unimolecular primary decomposition reactions of the seven isomers of DAT were studied in the gas phase and in the melt using a simplified model of the latter. The two-step reaction of N 2 elimination from the diamino tautomer was found to be the primary decomposition process of DAT in the gas phase and melt. The effective Arrhenius parameters of this process were calculated to be E a = 43.4 kcal mol -1 and log( A/s -1 ) = 15.2 in a good agreement with the experimental values. Contrary to the existing literature data, all other decomposition channels of DAT isomers turned out to be kinetically unimportant. Apart from this, a new primary decomposition channel yielding N 2 , cyanamide, and 1,1-diazene was found for some H-bonded dimers of DAT. We also determined a reliable and mutually consistent set of thermochemical values for DAT (Δ f H solid 0 = 74.5 ± 1.5 kcal·mol -1 ) by combining theoretically calculated (W1 multilevel procedure along with an isodesmic reaction) gas phase enthalpy of formation (Δ f H gas 0 = 100.7 ± 1.0 kcal·mol -1 ) and experimentally measured sublimation enthalpy (Δ sub H 0 = 26.2 ± 0.5 kcal·mol -1 ).

Identification of faulty sensor using relative partial decomposition via independent component analysis

NASA Astrophysics Data System (ADS)

Wang, Z.; Quek, S. T.

2015-07-01

Performance of any structural health monitoring algorithm relies heavily on good measurement data. Hence, it is necessary to employ robust faulty sensor detection approaches to isolate sensors with abnormal behaviour and exclude the highly inaccurate data in the subsequent analysis. The independent component analysis (ICA) is implemented to detect the presence of sensors showing abnormal behaviour. A normalized form of the relative partial decomposition contribution (rPDC) is proposed to identify the faulty sensor. Both additive and multiplicative types of faults are addressed and the detectability illustrated using a numerical and an experimental example. An empirical method to establish control limits for detecting and identifying the type of fault is also proposed. The results show the effectiveness of the ICA and rPDC method in identifying faulty sensor assuming that baseline cases are available.

Preparation, characterization and thermolysis of phenylenediammonium dinitrate salts.

PubMed

Kapoor, Inder Pal Singh; Srivastava, Pratibha; Singh, Gurdip

2008-02-11

Four phenylenediammonium dinitrate salts were prepared and characterized by elemental, Infrared spectroscopy (IR), Ultraviolet spectroscopy (UV) and gravimetric methods. These dinitrates find application in propellant, explosives and pyrotechnics. Their thermal decomposition has been studied using thermogravimetry (TG) and simultaneous thermogravimetry-differential scanning calorimetry (TG-DSC). Kinetics parameters were evaluated by model fitting and isoconversional methods. Their thermolytic pathways have also been suggested, which involves decomposition followed by ignition.

Developing Battery Computer Aided Engineering Tools for Military Vehicles

DTIC Science & Technology

2013-12-01

Task 1.b Modeling Bullet penetration. The purpose of Task 1.a was to extend the chemical kinetics models of CoO2 cathodes developed under CAEBAT to...lithium- ion batteries. The new finite element model captures swelling/shrinking in cathodes /anodes due to thermal expansion and lithium intercalation...Solid Electrolyte Interphase (SEI) layer decomposition 80 2 Anode — electrolyte 100 3 Cathode — electrolyte 130 4 Electrolyte decomposition 180

Evaluation of spacecraft toxic gas removal agents

NASA Technical Reports Server (NTRS)

1972-01-01

A study of the decomposition of various compounds adsorbed on charcoal was made, with a view toward providing a critical appraisal of previous data from charcoal adsorption studies. It was found that thermal decomposition occurs at temperature lower than previously suspected during the charcoal stripping process. A discussion is presented dealing with the various types of reactions found. A rough, quantitative scheme for correcting previous analytical results is developed and presented.

Decomposition of a Mixed-Valence [2Fe-2S] Cluster to Linear Tetra-Ferric and Ferrous Clusters

PubMed Central

Saouma, Caroline T.; Kaminsky, Werner; Mayer, James M.

2012-01-01

Despite the ease of preparing di-ferric [2Fe-2S] clusters, preparing stable mixed-valence analogues remains a challenge, as these clusters have limited thermal stability. Herein we identify two decomposition products of the mixed-valence thiosalicylate-ligated [2Fe-2S] cluster, [Fe2S2(SArCOO)2]3− ((SArCOO)2− = thiosalicylate). PMID:23976815

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

2014-06-07

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

Quantitative analysis of microbial biomass yield in aerobic bioreactor.

PubMed

Watanabe, Osamu; Isoda, Satoru

2013-12-01

We have studied the integrated model of reaction rate equations with thermal energy balance in aerobic bioreactor for food waste decomposition and showed that the integrated model has the capability both of monitoring microbial activity in real time and of analyzing biodegradation kinetics and thermal-hydrodynamic properties. On the other hand, concerning microbial metabolism, it was known that balancing catabolic reactions with anabolic reactions in terms of energy and electron flow provides stoichiometric metabolic reactions and enables the estimation of microbial biomass yield (stoichiometric reaction model). We have studied a method for estimating real-time microbial biomass yield in the bioreactor during food waste decomposition by combining the integrated model with the stoichiometric reaction model. As a result, it was found that the time course of microbial biomass yield in the bioreactor during decomposition can be evaluated using the operational data of the bioreactor (weight of input food waste and bed temperature) by the combined model. The combined model can be applied to manage a food waste decomposition not only for controlling system operation to keep microbial activity stable, but also for producing value-added products such as compost on optimum condition. Copyright © 2013 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Thermal energy storage – overview and specific insight into nitrate salts for sensible and latent heat storage

PubMed Central

Bauer, Thomas; Martin, Claudia; Eck, Markus; Wörner, Antje

2015-01-01

Summary Thermal energy storage (TES) is capable to reduce the demand of conventional energy sources for two reasons: First, they prevent the mismatch between the energy supply and the power demand when generating electricity from renewable energy sources. Second, utilization of waste heat in industrial processes by thermal energy storage reduces the final energy consumption. This review focuses mainly on material aspects of alkali nitrate salts. They include thermal properties, thermal decomposition processes as well as a new method to develop optimized salt systems. PMID:26199853

Thermal energy storage - overview and specific insight into nitrate salts for sensible and latent heat storage.

PubMed

Pfleger, Nicole; Bauer, Thomas; Martin, Claudia; Eck, Markus; Wörner, Antje

2015-01-01

Thermal energy storage (TES) is capable to reduce the demand of conventional energy sources for two reasons: First, they prevent the mismatch between the energy supply and the power demand when generating electricity from renewable energy sources. Second, utilization of waste heat in industrial processes by thermal energy storage reduces the final energy consumption. This review focuses mainly on material aspects of alkali nitrate salts. They include thermal properties, thermal decomposition processes as well as a new method to develop optimized salt systems.

(Ca,Mg)-Carbonate and Mg-Carbonate at the Phoenix Landing Site: Evaluation of the Phoenix Lander's Thermal Evolved Gas Analyzer (TEGA) Data Using Laboratory Simulations

NASA Technical Reports Server (NTRS)

Sutter, B.; Ming, D. W.; Boynton, W. V.; Niles, P. B.; Morris, R. V.

2011-01-01

Calcium carbonate (4.5 wt. %) was detected in the soil at the Phoenix Landing site by the Phoenix Lander s The Thermal and Evolved Gas Analyzer [1]. TEGA operated at 12 mbar pressure, yet the detection of calcium carbonate is based on interpretations derived from thermal analysis literature of carbonates measured under ambient (1000 mbar) and vacuum (10(exp -3) mbar) conditions [2,3] as well as at 100 and 30 mbar [4,5] and one analysis at 12 mbar by the TEGA engineering qualification model (TEGA-EQM). Thermodynamics (Te = H/ S) dictate that pressure affects entropy ( S) which causes the temperature (Te) of mineral decomposition at one pressure to differ from Te obtained at another pressure. Thermal decomposition analyses of Fe-, Mg-, and Ca-bearing carbonates at 12 mbar is required to enhance the understanding of the TEGA results at TEGA operating pressures. The objectives of this work are to (1) evaluate the thermal and evolved gas behavior of a suite of Fe-, Mg-, Ca-carbonate minerals at 1000 and 12 mbar and (2) discuss possible emplacement mechanisms for the Phoenix carbonate.

Mechanical property degradation and microstructural evolution of cast austenitic stainless steels under short-term thermal aging

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lach, Timothy G.; Byun, Thak Sang; Leonard, Keith J.

We performed mechanical testing and microstructural characterization on short-term thermally aged cast austenitic stainless steels (CASS) to understand the severity and mechanisms of thermal-aging degradation experienced during extended operation of light water reactor (LWR) coolant systems. Four CASS materials–CF3, CF3M, CF8, and CF8M–were thermally aged for 1500 h at 290 °C, 330 °C, 360 °C, and 400 °C. All four alloys experienced insignificant change in strength and ductility properties but a significant reduction in absorbed impact energy. The primary microstructural and compositional changes during thermal aging were spinodal decomposition of the δ-ferrite into α/α', precipitation of G-phase in the δ-ferrite,more » segregation of solute to the austenite/ferrite interphase boundary, and growth of M 23C 6 carbides on the austenite/ferrite interphase boundary. These changes were shown to be highly dependent on chemical composition, particularly the concentration of C and Mo, and aging temperature. Finally, the low C, high Mo CF3M alloys experienced the most spinodal decomposition and G-phase precipitation coinciding the largest reduction in impact properties.« less

Mechanical property degradation and microstructural evolution of cast austenitic stainless steels under short-term thermal aging

NASA Astrophysics Data System (ADS)

Lach, Timothy G.; Byun, Thak Sang; Leonard, Keith J.

2017-12-01

Mechanical testing and microstructural characterization were performed on short-term thermally aged cast austenitic stainless steels (CASS) to understand the severity and mechanisms of thermal-aging degradation experienced during extended operation of light water reactor (LWR) coolant systems. Four CASS materials-CF3, CF3M, CF8, and CF8M-were thermally aged for 1500 h at 290 °C, 330 °C, 360 °C, and 400 °C. All four alloys experienced insignificant change in strength and ductility properties but a significant reduction in absorbed impact energy. The primary microstructural and compositional changes during thermal aging were spinodal decomposition of the δ-ferrite into α/α‧, precipitation of G-phase in the δ-ferrite, segregation of solute to the austenite/ferrite interphase boundary, and growth of M23C6 carbides on the austenite/ferrite interphase boundary. These changes were shown to be highly dependent on chemical composition, particularly the concentration of C and Mo, and aging temperature. The low C, high Mo CF3M alloys experienced the most spinodal decomposition and G-phase precipitation coinciding the largest reduction in impact properties.

Mechanical property degradation and microstructural evolution of cast austenitic stainless steels under short-term thermal aging

DOE PAGES

Lach, Timothy G.; Byun, Thak Sang; Leonard, Keith J.

2017-07-31

We performed mechanical testing and microstructural characterization on short-term thermally aged cast austenitic stainless steels (CASS) to understand the severity and mechanisms of thermal-aging degradation experienced during extended operation of light water reactor (LWR) coolant systems. Four CASS materials–CF3, CF3M, CF8, and CF8M–were thermally aged for 1500 h at 290 °C, 330 °C, 360 °C, and 400 °C. All four alloys experienced insignificant change in strength and ductility properties but a significant reduction in absorbed impact energy. The primary microstructural and compositional changes during thermal aging were spinodal decomposition of the δ-ferrite into α/α', precipitation of G-phase in the δ-ferrite,more » segregation of solute to the austenite/ferrite interphase boundary, and growth of M 23C 6 carbides on the austenite/ferrite interphase boundary. These changes were shown to be highly dependent on chemical composition, particularly the concentration of C and Mo, and aging temperature. Finally, the low C, high Mo CF3M alloys experienced the most spinodal decomposition and G-phase precipitation coinciding the largest reduction in impact properties.« less

Synthesis and thermal stability of carborane containing phosphazenes

NASA Technical Reports Server (NTRS)

Fewell, L. L.; Basi, R. J.; Parker, J. A.

1983-01-01

Carborane substituted polyphosphazenes were prepared by the thermal polymerization of phenyl-carboranyl penta chlorocyclotriphosphazene. Successive isothermal vacuum pyrolyses were conducted on the polymer and examined for structural changes by infrared spectroscopy. The degradation products were ascertained by gas chromatography-mass spectrometric analysis. It was found that the presence of the carborane group improves the thermal stability of the polymer by retarding the ring chain equilibrium processes of decomposition.

Structural Evolution of Silicon Oxynitride Fiber Reinforced Boron Nitride Matrix Composite at High Temperatures

NASA Astrophysics Data System (ADS)

Zou, Chunrong; Li, Bin; Zhang, Changrui; Wang, Siqing; Xie, Zhengfang; Shao, Changwei

2016-02-01

The structural evolution of a silicon oxynitride fiber reinforced boron nitride matrix (Si-N-Of/BN) wave-transparent composite at high temperatures was investigated. When heat treated at 1600 °C, the composite retained a favorable bending strength of 55.3 MPa while partially crystallizing to Si2N2O and h-BN from the as-received amorphous structure. The Si-N-O fibers still performed as effective reinforcements despite the presence of small pores due to fiber decomposition. Upon heat treatment at 1800 °C, the Si-N-O fibers already lost their reinforcing function and rough hollow microstructure formed within the fibers because of the accelerated decomposition. Further heating to 2000 °C led to the complete decomposition of the reinforcing fibers and only h-BN particles survived. The crystallization and decomposition behaviors of the composite at high temperatures are discussed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hermann, Andrew T.; Wiley, John B.

The thermal stability and decomposition pathways of six Dion-Jacobson-related double-layered perovskites, ALaNb{sub 2}O{sub 7} (A = H, Li, Na, Ag) and (ACl)LaNb{sub 2}O{sub 7} (A = Fe, Cu), are investigated. These compounds are made by low temperature (<400 deg. C) ion exchange reactions from RbLaNb{sub 2}O{sub 7}. All the compounds are low temperature phases with some of them exhibiting decomposition exotherms consistent with metastability. Decomposition temperatures and reactions pathways vary with the identity of A with most decompositions resulting in the formation of a niobate (containing A) and LaNbO{sub 4}. Results from differential scanning calorimetry and high temperature X-ray powdermore » diffraction studies are presented and structural parameters pertinent to compound stability discussed.« less

NMR study of methane + ethane structure I hydrate decomposition.

PubMed

Dec, Steven F; Bowler, Kristen E; Stadterman, Laura L; Koh, Carolyn A; Sloan, E Dendy

2007-05-24

The thermally activated decomposition of methane + ethane structure I hydrate was studied with use of 13C magic-angle spinning (MAS) NMR as a function of composition and temperature. The observed higher decomposition rate of large sI cages initially filled with ethane gas can be described in terms of a model where a distribution of sI unit cells exists such that a particular unit cell contains zero, one, or two methane molecules in the unit cell; this distribution of unit cells is combined to form the observed equilibrium composition. In this model, unit cells with zero methane molecules are the least stable and decompose more rapidly than those populated with one or two methane molecules leading to the observed overall faster decomposition rate of the large cages containing ethane molecules.

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

USDA-ARS?s Scientific Manuscript database

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...

Enhanced thermal and combustion resistance of cotton linked to natural inorganic salt components

USDA-ARS?s Scientific Manuscript database

Cotton is most commonly scoured or scoured and bleached before being used for commercial purposes, but, due to its propensity to burn, cotton's use is limited and protective chemistry is needed in applications where resistance to heat and flame is required. A comparison of the thermal decomposition ...

Temperature imaging with ultrasonic transmission tomography for treatment control

NASA Astrophysics Data System (ADS)

Chu, Zheqi; Pinter, Stephen. Z.; Yuan, Jie; Scarpelli, Matthew L.; Kripfgans, Oliver D.; Fowlkes, J. Brian; Duric, Neb; Carson, Paul L.

2017-03-01

Hyperthermia is a promising method to enhance chemo- or radiation therapy of breast cancer and the time-temperature profile in the target and surrounding areas is the primary monitoring method. Unlike with thermal ablation of lesions, in hyperthermia there are not good alternative treatment monitoring quantities. However, there is less problem with non-monotonic thermal coefficients of speed of sound used with ultrasonic imaging of temperature. This paper tests a long discussed but little investigated method of imaging temperature using speed of sound and proposes methods of reducing edge enhancement artifacts in the temperature image. Normally, when directly using the speed of sound to reconstruct the temperature image around the tumor, there will be an abnormal bipolar edge enhancement along the boundary between two materials with different speeds of sound at a given temperature. This due to partial volume effects and can be diminished by regularized, weighted deconvolution. An initial, manual deconvolution is shown, as well as an EMD (Empirical Mode Decomposition) method. Here we use the continuity and other constraints to choose the coefficient, reprocess the temperature field image and take the mean variations of the temperature in the adjacent pixels as the judgment criteria. Both methods effectively reduce the edge enhancement and produce a more precise image of temperature.

Completion of the Viking Labeled Release experiment on Mars

NASA Technical Reports Server (NTRS)

Levin, G. V.; Straat, P. A.

1979-01-01

The final Labeled Release (LR) cycle on each Viking lander tested a surface sample that had been stored for several months at approximately 10 C prior to the onset of the active sequence. At each lander site, activity was strongly diminished. This thermal sensitivity of the active agent on the surface of Mars is consistent with a biological explanation of the LR experiment. At the end of one of these cycles, the incubation mixture was heated to 50 C to release any radioactive gas trapped in the sample matrix. The results suggest that more than one carbon substrate is involved in the LR reaction on Mars. The thermal data from the stored samples, coupled with data from previous cycles, have formed the basis for evaluation of the thermal decomposition of the Mars active agent. The slope of the resulting Arrhenius plot has been used to test the fit of other flight data and to calculate the activation energy for thermal decomposition of the Mars agent. The results and their interpretation still leave unresolved the question of whether the Mars LR data were generated by biological or chemical activity.

Completion of the Viking labeled release experiment on Mars.

PubMed

Levin, G V; Straat, P A

1979-12-01

The final Labeled Release (LR) cycle on each Viking lander tested a surface sample that had been stored for several months at approximately 10 degrees C prior to the onset of the active sequence. At each lander site, activity was strongly diminished. This thermal sensitivity of the active agent on the surface of Mars is consistent with a biological explanation of the LR experiment. At the end of one of these cycles, the incubation mixture was heated to 50 degrees C to release any radioactive gas trapped in the sample matrix. The results suggest that more than one carbon substrate is involved in the LR reaction on Mars. The thermal data from the stored samples, coupled with data from previous cycles, have formed the basis for evaluation of the thermal decomposition of the Mars active agent. The slope of the resulting Arrhenius plot has been used to test the fit of other flight data and to calculate the activation energy for thermal decomposition of the Mars agent. The results and their interpretation still leave unresolved the question of whether the Mars LR data were generated by biological or chemical activity.

An investigation on microstructure and mechanical property of thermally aged stainless steel weld overlay cladding

NASA Astrophysics Data System (ADS)

Cao, X. Y.; Zhu, P.; Ding, X. F.; Lu, Y. H.; Shoji, T.

2017-04-01

Microstructural evolution and mechanical property change of E308L stainless steel weld overlay cladding aged at 400 °C for 400, 1000 and 5000 h were investigated by transmission electron microscope (TEM) and small punch test (SPT). The results indicated that thermal aging had no obvious effect on the volume fraction of ferrite, but can cause microstructural evolution by spinodal decomposotion and G-phase precipitation in the ferrite phase. Spinodal decomposition took place after aging up to 1000 h, while G-phase formed along dislocations, and growed up to 2-11 nm after aging for 5000 h. The total energy for inducing deformation and fracture by the small punch tests decreased with the increase of thermal aging time, and this decline was associated with spinodal decomposition and G-phase precipitation. Plastic deformation of the aged ferrite proceeded via formation of curvilinear slip bands. Nucleation of microcracks occurred at the δ/γ interface along the slip bands. The hardening of the ferrite and high stress concentration on δ/γ phase interface resulted in brittle fracture and phase boundary separation after thermal aging.

Analysis of the Sensitivity of K-Type Molecular Sieve-Deposited MWNTs for the Detection of SF6 Decomposition Gases under Partial Discharge

PubMed Central

Zhang, Xiaoxing; Li, Xin; Luo, Chenchen; Dong, Xingchen; Zhou, Lei

2015-01-01

Sulfur hexafluoride (SF6) is widely utilized in gas-insulated switchgear (GIS). However, part of SF6 decomposes into different components under partial discharge (PD) conditions. Previous research has shown that the gas responses of intrinsic and 4 Å-type molecular sieve-deposited multi-wall carbon nanotubes (MWNTs) to SOF2 and SO2F2, two important decomposition components of SF6, are not obvious. In this study, a K-type molecular sieve-deposited MWNTs sensor was developed. Its gas response characteristics and the influence of the mixture ratios of gases on the gas-sensing properties were studied. The results showed that, for sensors with gas mixture ratios of 5:1, 10:1, and 20:1, the resistance change rate increased by nearly 13.0% after SOF2 adsorption, almost 10 times that of MWNTs sensors, while the sensors’ resistance change rate with a mixture ratio of 10:1 reached 17.3% after SO2F2 adsorption, nearly nine times that of intrinsic MWNT sensors. Besides, a good linear relationship was observed between concentration of decomposition components and the resistance change rate of sensors. PMID:26569245

Analysis of the Sensitivity of K-Type Molecular Sieve-Deposited MWNTs for the Detection of SF₆ Decomposition Gases under Partial Discharge.

PubMed

Zhang, Xiaoxing; Li, Xin; Luo, Chenchen; Dong, Xingchen; Zhou, Lei

2015-11-11

Sulfur hexafluoride (SF6) is widely utilized in gas-insulated switchgear (GIS). However, part of SF6 decomposes into different components under partial discharge (PD) conditions. Previous research has shown that the gas responses of intrinsic and 4 Å-type molecular sieve-deposited multi-wall carbon nanotubes (MWNTs) to SOF2 and SO2F2, two important decomposition components of SF6, are not obvious. In this study, a K-type molecular sieve-deposited MWNTs sensor was developed. Its gas response characteristics and the influence of the mixture ratios of gases on the gas-sensing properties were studied. The results showed that, for sensors with gas mixture ratios of 5:1, 10:1, and 20:1, the resistance change rate increased by nearly 13.0% after SOF2 adsorption, almost 10 times that of MWNTs sensors, while the sensors' resistance change rate with a mixture ratio of 10:1 reached 17.3% after SO2F2 adsorption, nearly nine times that of intrinsic MWNT sensors. Besides, a good linear relationship was observed between concentration of decomposition components and the resistance change rate of sensors.

Evaluation of the energy transfer in the char zone during ablation. Part 2: In-depth response of ablative composites, volume 1. Ph.D. Thesis, 1975. Final Report

NASA Technical Reports Server (NTRS)

Pike, R. W.; Delvalle, E. G.

1974-01-01

The decomposition of ablative composites is described along with the transport phenomena of pyrolysis gases which result from the decomposition of these plastics as they flow through the porous char of char-forming ablators. The pyrolysis products are those formed by the thermal degradation of nylon-phenolic resin and silicone elastomer composites. Emphasis is placed on the nature and extent of chemical reactions of the pyrolysis products and the char, along with the energy absorbed by the combined pyrolysis and char zone. Chemical reactions with thermodynamically consistent kinetic data are determined in order to develop a realistic analysis for predicting the thermal performance of ablative heat shields.

Synthesis, X-ray crystallography, thermal studies, spectroscopic and electrochemistry investigations of uranyl Schiff base complexes.

PubMed

Asadi, Zahra; Shorkaei, Mohammad Ranjkesh

2013-03-15

Some tetradentate salen type Schiff bases and their uranyl complexes were synthesized and characterized by UV-Vis, NMR, IR, TG, C.H.N. and X-ray crystallographic studies. From these investigations it is confirmed that a solvent molecule occupied the fifth position of the equatorial plane of the distorted pentagonal bipyramidal structure. Also, the kinetics of complex decomposition by using thermo gravimetric methods (TG) was studied. The thermal decomposition reactions are first order for the studied complexes. To examine the properties of uranyl complexes according to the substitutional groups, we have carried out the electrochemical studies. The electrochemical reactions of uranyl Schiff base complexes in acetonitrile were reversible. Copyright © 2012 Elsevier B.V. All rights reserved.

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.

Mutagenicity of aerosols from the oxidative thermal decomposition of rigid polyurethane foam.

PubMed

Zitting, A; Falck, K; Skyttä, E

1980-01-01

The aerosol fraction of the oxidative thermal decomposition products (700 degrees C) of rigid polyurethane foam was collected on glass fiber filters and fractionated into either-soluble neutral, acidic, and basic fractions and water-soluble compounds. The fractions showed mutagenic activity in a bacterial fluctuation test with Salmonella typhimurium TA98 or Escherichia coli CM891 as the tester strains. All the fractions induced mutations in both strains after metabolic activation with rat liver S-9 mix. The basic and the water-soluble fractions were mutagenic for S. typhimurium TA 98 even without activation. Thin-layer chromatography showed the presence of several primary aromatic amines in the aerosol. Polycyclic aromatic hydrocarbons were not detected by glass capillary gas chromatogaphy.

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.

Determination of the thermal stability of fluids by tensimetry - Instrumentation and procedure

NASA Technical Reports Server (NTRS)

Helmick, Larry S.; Jones, William R., Jr.

1990-01-01

A computerized tensimeter and experimental procedure for determination of the thermal decomposition temperature (T sub d) of perfluoro alkylethers were developed and tested. Both the apparatus and the procedure are described in detail. Results of testing with bis(2-ethylhexyl) phthalate and trimethylolpropane triheptanoate demonstrate that the reciprocal of the decomposition temperature is a linear function of the logarithm of the gas volume/heated liquid volume ratio. The T sub d obtained for each compound at a gas volume/heated liquid volume ration of one was similar to the value previously reported using an isoteniscope technique. Results of testing with a polymer of hexafluoropropylene oxide demonstrate that this instrument and procedure can be used to determine the T sub d of perfluoro alkylethers.

Determination of the thermal stability of perfluoroalkylethers by tensimetry: Instrumentation and Procedure

NASA Technical Reports Server (NTRS)

Helmick, Larry S.; Jones, William R., Jr.

1989-01-01

A computerized tensimeter and experimental procedure for determination of the thermal decomposition temperature (T sub d) of perfluoro alkylethers were developed and tested. Both the apparatus and the procedure are described in detail. Results of testing with bis(2-ethylhexyl) phthalate and trimethylolpropane triheptanoate demonstrate that the reciprocal of the decomposition temperature is a linear function of the logarithm of the gas volume/heated liquid volume ratio. The T sub d obtained for each compound at a gas volume/heated liquid volume ration of one was similar to the value previously reported using an isoteniscope technique. Results of testing with a polymer of hexafluoropropylene oxide demonstrate that this instrument and procedure can be used to determine the T sub d of perfluoroalkylethers.

Domain decomposition: A bridge between nature and parallel computers

NASA Technical Reports Server (NTRS)

Keyes, David E.

1992-01-01

Domain decomposition is an intuitive organizing principle for a partial differential equation (PDE) computation, both physically and architecturally. However, its significance extends beyond the readily apparent issues of geometry and discretization, on one hand, and of modular software and distributed hardware, on the other. Engineering and computer science aspects are bridged by an old but recently enriched mathematical theory that offers the subject not only unity, but also tools for analysis and generalization. Domain decomposition induces function-space and operator decompositions with valuable properties. Function-space bases and operator splittings that are not derived from domain decompositions generally lack one or more of these properties. The evolution of domain decomposition methods for elliptically dominated problems has linked two major algorithmic developments of the last 15 years: multilevel and Krylov methods. Domain decomposition methods may be considered descendants of both classes with an inheritance from each: they are nearly optimal and at the same time efficiently parallelizable. Many computationally driven application areas are ripe for these developments. A progression is made from a mathematically informal motivation for domain decomposition methods to a specific focus on fluid dynamics applications. To be introductory rather than comprehensive, simple examples are provided while convergence proofs and algorithmic details are left to the original references; however, an attempt is made to convey their most salient features, especially where this leads to algorithmic insight.

Thermal Analysis Study of Antihypertensive Drugs Telmisartan and Cilazapril

PubMed Central

Saber, Refaat Ahmed; Attia, Ali Kamal; Salem, Waheed Mohamed

2014-01-01

Purpose: The aim of the present work is to study the thermal analysis of telmisartan and cilazapril. Methods: Thermogravimetry (TGA), derivative thermogravimetry (DTG) and differential thermal analysis (DTA) were used through the work to achieve the thermal analysis study of some antihypertensive drugs, telmisartan and cilazapril. Results: The results led to thermal stability data and also to the interpretation concerning the thermal decomposition. Thermogravimetry data allowed determination of the kinetic parameters such as, activation energy and frequency factor. Conclusion: The simplicity, speed and low operational costs of thermal analysis justify its application in the quality control of pharmaceutical compounds for medications. PMID:24754013

Effect of preliminary thermal treatment on decomposition kinetics of austenite in low-alloyed pipe steel in intercritical temperature interval

NASA Astrophysics Data System (ADS)

Makovetskii, A. N.; Tabatchikova, T. I.; Yakovleva, I. L.; Tereshchenko, N. A.; Mirzaev, D. A.

2013-06-01

The decomposition kinetics of austenite that appears in the 13KhFA low-alloyed pipe steel upon heating the samples in an intercritical temperature interval (ICI) and exposure for 5 or 30 min has been studied by the method of high-speed dilatometry. The results of dilatometry are supplemented by the microstructure analysis. Thermokinetic diagrams of the decomposition of the γ phase are represented. The conclusion has been drawn that an increase in the duration of exposure in the intercritical interval leads to a significant increase in the stability of the γ phase.

Large scale synthesis of nanostructured zirconia-based compounds from freeze-dried precursors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gomez, A.; Villanueva, R.; Vie, D.

2013-01-15

Nanocrystalline zirconia powders have been obtained at the multigram scale by thermal decomposition of precursors resulting from the freeze-drying of aqueous acetic solutions. This technique has equally made possible to synthesize a variety of nanostructured yttria or scandia doped zirconia compositions. SEM images, as well as the analysis of the XRD patterns, show the nanoparticulated character of those solids obtained at low temperature, with typical particle size in the 10-15 nm range when prepared at 673 K. The presence of the monoclinic, the tetragonal or both phases depends on the temperature of the thermal treatment, the doping concentration and themore » nature of the dopant. In addition, Rietveld refinement of the XRD profiles of selected samples allows detecting the coexistence of the tetragonal and the cubic phases for high doping concentration and high thermal treatment temperatures. Raman experiments suggest the presence of both phases also at relatively low treatment temperatures. - Graphical abstract: Zr{sub 1-x}A{sub x}O{sub 2-x/2} (A=Y, Sc; 0{<=}x{<=}0.12) solid solutions have been prepared as nanostructured powders by thermal decomposition of precursors obtained by freeze-drying, and this synthetic procedure has been scaled up to the 100 g scale. Highlights: Black-Right-Pointing-Pointer Zr{sub 1-x}A{sub x}O{sub 2-x/2} (A=Y, Sc; 0{<=}x{<=}0.12) solid solutions have been prepared as nanostructured powders. Black-Right-Pointing-Pointer The synthetic method involves the thermal decomposition of precursors obtained by freeze-drying. Black-Right-Pointing-Pointer The temperature of the thermal treatment controls particle sizes. Black-Right-Pointing-Pointer The preparation procedure has been scaled up to the 100 g scale. Black-Right-Pointing-Pointer This method is appropriate for the large-scale industrial preparation of multimetallic systems.« less

Thermal oxidation of single crystal aluminum antimonide and materials having the same

DOEpatents

Sherohman, John William; Yee, Jick Hong; Coombs, III, Arthur William; Wu, Kuang Jen J.

2012-12-25

In one embodiment, a method for forming a non-conductive crystalline oxide layer on an AlSb crystal includes heat treating an AlSb crystal in a partial vacuum atmosphere at a temperature conducive for air adsorbed molecules to desorb, surface molecule groups to decompose, and elemental Sb to evaporate from a surface of the AlSb crystal and exposing the AlSb crystal to an atmosphere comprising oxygen to form a crystalline oxide layer on the surface of the AlSb crystal. In another embodiment, a method for forming a non-conductive crystalline oxide layer on an AlSb crystal includes heat treating an AlSb crystal in a non-oxidizing atmosphere at a temperature conducive for decomposition of an amorphous oxidized surface layer and evaporation of elemental Sb from the AlSb crystal surface and forming stable oxides of Al and Sb from residual surface oxygen to form a crystalline oxide layer on the surface of the AlSb crystal.

Measuring the concentration of carboxylic acid groups in torrefied spruce wood.

PubMed

Khazraie Shoulaifar, Tooran; Demartini, Nikolai; Ivaska, Ari; Fardim, Pedro; Hupa, Mikko

2012-11-01

Torrefaction is moderate thermal treatment (∼200-300°C) to improve the energy density, handling and storage properties of biomass fuels. In biomass, carboxylic sites are partially responsible for its hygroscopic. These sites are degraded to varying extents during torrefaction. In this paper, we apply methylene blue sorption and potentiometric titration to measure the concentration of carboxylic acid groups in spruce wood torrefied for 30min at temperatures between 180 and 300°C. The results from both methods were applicable and the values agreed well. A decrease in the equilibrium moisture content at different humidity was also measured for the torrefied wood samples, which is in good agreement with the decrease in carboxylic acid sites. Thus both methods offer a means of directly measuring the decomposition of carboxylic groups in biomass during torrefaction as a valuable parameter in evaluating the extent of torrefaction which provides new information to the chemical changes occurring during torrefaction. Copyright © 2012 Elsevier Ltd. All rights reserved.

Characterization of a bioflocculant produced by a consortium of Halomonas sp. Okoh and Micrococcus sp. Leo.

PubMed

Okaiyeto, Kunle; Nwodo, Uchechukwu U; Mabinya, Leonard V; Okoh, Anthony I

2013-10-16

The physicochemical and flocculating properties of a bioflocculant produced by a bacterial consortium composed of Halomonas sp. Okoh and Micrococcus sp. Leo were investigated. The purified bioflocculant was cation and pH dependent, and optimally flocculated kaolin clay suspension at a dosage of 0.1 mg/mL. The flocculating activity of the bioflocculant was stimulated in the presence of Ca2+, Mn2+, Al3+ and had a wide pH range of 2-10, with the highest flocculating activity of 86% at pH 8. The bioflocculant was thermostable and retained more than 70% of its flocculating activity after being heated at 80 °C for 30 min. Thermogravimetric analyses revealed a partial thermal decomposition of the biofloculant at 400 °C. The infrared spectrum showed the presence of hydroxyl, carboxyl and amino moieties as functional groups. The bioflocculant produced by the bacterial consortium appears to hold promising alternative to inorganic and synthetic organic flocculants that are widely used in wastewater treatment.

Characterization of a Bioflocculant Produced by a Consortium of Halomonas sp. Okoh and Micrococcus sp. Leo

PubMed Central

Okaiyeto, Kunle; Nwodo, Uchechukwu U.; Mabinya, Leonard V.; Okoh, Anthony I.

2013-01-01

The physicochemical and flocculating properties of a bioflocculant produced by a bacterial consortium composed of Halomonas sp. Okoh and Micrococcus sp. Leo were investigated. The purified bioflocculant was cation and pH dependent, and optimally flocculated kaolin clay suspension at a dosage of 0.1 mg/mL. The flocculating activity of the bioflocculant was stimulated in the presence of Ca2+, Mn2+, Al3+ and had a wide pH range of 2–10, with the highest flocculating activity of 86% at pH 8. The bioflocculant was thermostable and retained more than 70% of its flocculating activity after being heated at 80 °C for 30 min. Thermogravimetric analyses revealed a partial thermal decomposition of the biofloculant at 400 °C. The infrared spectrum showed the presence of hydroxyl, carboxyl and amino moieties as functional groups. The bioflocculant produced by the bacterial consortium appears to hold promising alternative to inorganic and synthetic organic flocculants that are widely used in wastewater treatment. PMID:24135818

An ammonia-stabilized mixed-cation borohydride: synthesis, structure and thermal decomposition behavior.

PubMed

Yang, Yanjing; Liu, Yongfeng; Wu, Hui; Zhou, Wei; Gao, Mingxia; Pan, Hongge

2014-01-07

We demonstrate the synthesis, crystal structure and thermal decomposition behavior of a novel ammonia-stabilized mixed-cation borohydride where the NH3 groups enable the coexistence of Li and Mg cations as an "assistant". Li2Mg(BH4)4·6NH3, which is comprised of orderly arranged Mg[NH3]6(2+) ammine complexes and Li2[BH4]4(2-) complex anions, was synthesized by the mechanochemical reaction between Mg(BH4)2·6NH3 and LiBH4. This novel compound crystallizes in a tetragonal P4(3)2(1)2 (No. 96) structure with lattice parameters a = b = 10.7656(8) Å and c = 13.843(1) Å with very short dihydrogen bonds, which determine a very low onset temperature of 80 °C for hydrogen release and are also responsible for the nucleation of Li2Mg(BH4)4·3NH3 as a decomposition intermediate. Mechanistic investigations on the thermal decomposition showed that the H(δ+)-H(δ-) combination in the ammonia-stabilized mixed-cation borohydride was significantly enhanced due to the strengthened Mg-N bonds. Upon heating, 11.02 moles of H2 (equivalent to 11.1 wt%) and 3.07 moles of NH3 are evolved from one mole of Li2Mg(BH4)4·6NH3 with a three-step reaction. The insights into the formation mechanism of ammonia-stabilized mixed-cation borohydride and the role played by NH3 group are very useful as a guideline for the design and synthesis of novel B-N-based materials with high hydrogen content.

Understanding Litter Input Controls on Soil Organic Matter Turnover and Formation are Essential for Improving Carbon-Climate Feedback Predictions for Arctic, Tundra Ecosystems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wallenstein, Matthew

The Arctic region stored vast amounts of carbon (C) in soils over thousands of years because decomposition has been limited by cold, wet conditions. Arctic soils now contain roughly as much C that is contained in all other soils across the globe combined. However, climate warming could unlock this oil C as decomposition accelerates and permafrost thaws. In addition to temperature-driven acceleration of decomposition, several additional processes could either counteract or augment warming-induced SOM losses. For example, increased plant growth under a warmer climate will increase organic matter inputs to soils, which could fuel further soil decomposition by microbes, butmore » will also increase the production of new SOM. Whether Arctic ecosystems store or release carbon in the future depends in part on the balance between these two counteracting processes. By differentiating SOM decomposition and formation and understanding the drivers of these processes, we will better understand how these systems function. We did not find evidence of priming under current conditions, defined as an increase in the decomposition of native SOM stocks. This suggests that decomposition is unlikely to be further accelerated through this mechanism. We did find that decomposition of native SOM did occur when nitrogen was added to these soils, suggesting that nitrogen limits decomposition in these systems. Our results highlight the resilience and extraordinary C storage capacity of these soils, and suggest shrub expansion may partially mitigate C losses from decomposition of old SOM as Arctic soils warm.« less

The Thermal Decomposition of Some Organic Lead Compounds

DTIC Science & Technology

1957-11-01

either of salicylic anhydride or of its pyrolysis fragments which are reported to be a mixture of carbon dioxide , phenol and phenyl salicylate. Other...7) have studied the decomposition of the mono-salicylate in vacuo at 400°C. and have found that one molecule of carbon dioxide is evolved per...of lead nitrate and nitrosalicylic acid, though seme of the latter is decarboxylated with evolution of carbon dioxide . These points are considered

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

DTIC Science & Technology

2011-05-03

18 . NUMBER OF PAGES 19a. NAME OF RESPONSIBLE PERSON Dr. Tommy W. Hawkins a. REPORT Unclassified b. ABSTRACT Unclassified c. THIS PAGE...branching using Rice-Ramsperger-Kassel-Marcus (RRKM) theory, 18 and finally to the analysis of inter-conversions of primary decomposition products...theory, 18 was employed to examine the properties of the reactant, intermediate complex and transition states as a function of the total internal energy

Preparation and Stoichiometry Effects on Microstructure and Properties of High Purity BaTiO3.

DTIC Science & Technology

1986-03-27

oxalate , citrate) salt solutions, from mixed alkoxide precursors or from hydrothermal solutions. Typical starting materials and reaction sequences...decomposition and calcination reactions to form the BaTiO compound. Both the oxalate and 3 hydrothermal processes show commnercial promise and are briefly...thermal decomposition of oxalates and by hydrothermal synthesis. As-received lots of mixed oxide and oxalate -derived powders had Ba:TI ratios of 0.997 and

Comparative Solid-State Stability of Perindopril Active Substance vs. Pharmaceutical Formulation

PubMed Central

Buda, Valentina; Andor, Minodora; Ledeti, Adriana; Ledeti, Ionut; Vlase, Gabriela; Vlase, Titus; Cristescu, Carmen; Voicu, Mirela; Suciu, Liana; Tomescu, Mirela Cleopatra

2017-01-01

This paper presents the results obtained after studying the thermal stability and decomposition kinetics of perindopril erbumine as a pure active pharmaceutical ingredient as well as a solid pharmaceutical formulation containing the same active pharmaceutical ingredient (API). Since no data were found in the literature regarding the spectroscopic description, thermal behavior, or decomposition kinetics of perindopril, our goal was the evaluation of the compatibility of this antihypertensive agent with the excipients in the tablet under ambient conditions and to study the effect of thermal treatment on the stability of perindopril erbumine. ATR-FTIR (Attenuated Total Reflectance Fourier Transform Infrared) spectroscopy, thermal analysis (thermogravimetric mass curve (TG—thermogravimetry), derivative thermogravimetric mass curve (DTG), and heat flow (HF)) and model-free kinetics were chosen as investigational tools. Since thermal behavior is a simplistic approach in evaluating the thermal stability of pharmaceuticals, in-depth kinetic studies were carried out by classical kinetic methods (Kissinger and ASTM E698) and later with the isoconversional methods of Friedman, Kissinger-Akahira-Sunose and Flynn-Wall-Ozawa. It was shown that the main thermal degradation step of perindopril erbumine is characterized by activation energy between 59 and 69 kJ/mol (depending on the method used), while for the tablet, the values were around 170 kJ/mol. The used excipients (anhydrous colloidal silica, microcrystalline cellulose, lactose, and magnesium stearate) should be used in newly-developed generic solid pharmaceutical formulations, since they contribute to an increased thermal stability of perindopril erbumine. PMID:28098840

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

PubMed

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

2017-09-20

The lightweight compound material NaNH 2 -NaBH 4 is regarded as a promising hydrogen storage composite due to the high hydrogen density. Mechanical ball milling was employed to synthesize the composite NaNH 2 -NaBH 4 (2/1 molar ratio), and the samples were investigated utilizing thermogravimetric-differential thermal analysis-mass spectroscopy (TG-DTA-MS), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) analyses. The full-spectrum test (range of the ratio of mass to charge: 0-200) shows that the released gaseous species contain H 2 , NH 3 , B 2 H 6 , and N 2 in the heating process from room temperature to 400 °C, and possibly the impurity gas B 6 H 12 also exists. The TG/DTA analyses show that the composite NaNH 2 -NaBH 4 (2/1 molar ratio) is conductive to generate hydrogen so that the dehydrogenation process can be finished before 400 °C. Moreover, the thermal decomposition process from 200 to 400 °C involves two-step dehydrogenation reactions: (1) Na 3 (NH 2 ) 2 BH 4 hydride decomposes into Na 3 BN 2 and H 2 (200-350 °C); (2) remaining Na 3 (NH 2 ) 2 BH 4 reacts with NaBH 4 and Na 3 BN 2 , generating Na, BN, NH 3 , N 2 , and H 2 (350-400 °C). The better mechanism understanding of the thermal decomposition pathway lays a foundation for tailoring the hydrogen storage performance of the composite complex hydrides system.

Insights: Teaching Stoichiometry.

ERIC Educational Resources Information Center

Figueira, Alvaro Rocha; And Others

1988-01-01

Examines the thermal decomposition of sodium bicarbonate to sodium carbonate. Encourages students to predict the end products and to use the stoichiometric results to determine if their predictions are correct. (MVL)

Thermogravimetric analysis and kinetic modeling of low-transition-temperature mixtures pretreated oil palm empty fruit bunch for possible maximum yield of pyrolysis oil.

PubMed

Yiin, Chung Loong; Yusup, Suzana; Quitain, Armando T; Uemura, Yoshimitsu; Sasaki, Mitsuru; Kida, Tetsuya

2018-05-01

The impacts of low-transition-temperature mixtures (LTTMs) pretreatment on thermal decomposition and kinetics of empty fruit bunch (EFB) were investigated by thermogravimetric analysis. EFB was pretreated with the LTTMs under different duration of pretreatment which enabled various degrees of alteration to their structure. The TG-DTG curves showed that LTTMs pretreatment on EFB shifted the temperature and rate of decomposition to higher values. The EFB pretreated with sucrose and choline chloride-based LTTMs had attained the highest mass loss of volatile matter (78.69% and 75.71%) after 18 h of pretreatment. For monosodium glutamate-based LTTMs, the 24 h pretreated EFB had achieved the maximum mass loss (76.1%). Based on the Coats-Redfern integral method, the LTTMs pretreatment led to an increase in activation energy of the thermal decomposition of EFB from 80.00 to 82.82-94.80 kJ/mol. The activation energy was mainly affected by the demineralization and alteration in cellulose crystallinity after LTTMs pretreatment. Copyright © 2018 Elsevier Ltd. All rights reserved.

Enhancing the quality of bio-oil and selectivity of phenols compounds from pyrolysis of anaerobic digested rice straw.

PubMed

Liang, Jiajin; Lin, Yunqin; Wu, Shubin; Liu, Chao; Lei, Ming; Zeng, Chao

2015-04-01

This study investigated the thermal decomposition characteristics and pyrolytic products of anaerobic digested rice straw (ADRS) by thermogravimetric (TG) and pyrolysis-gas chromatograph/mass spectrometry (Py-GC/MS) analysis. Compared with the raw rice straw (RS), the thermal decomposition temperature of ADRS was shifted to higher temperature zone and the second decomposition zone of cellulose (Toffset(c)-Tpeak) became narrower (14 °C less), which indicated that the composition of rice straw were changed significantly by the anaerobic digestion pretreatment. Py-GC/MS analysis showed that the quality of the bio-oil and the selectivity of pyrolytic products could be obviously improved by anaerobic digestion. The total yields of alcohols, acids, aldehydes, furans, anhydrosugars, and ketones pyrolysis substances decreased, while the yield of phenols increased. The yield of 4-Vinylphenol (4-VP) increased from 29.33%, 8.21% and 5.76% to 34.93%, 12.46% and 7.68% at 330, 450 and 650 °C, respectively, after anaerobic digestion. Copyright © 2015 Elsevier Ltd. All rights reserved.

A Possible Organic Contribution to the Low Temperature CO2 Release Seen in Mars Phoenix Thermal and Evolved Gas Analyzer Data

NASA Technical Reports Server (NTRS)

Archer, P. D. Jr.; Lauer, H. V., Jr.; Sutter, B.; Ming, D. W.; Niles, P. B.; Boynton, W. V.

2012-01-01

Two of the most important discoveries of the Phoenix Mars Lander were the discovery of approx.0.6% perchlorate [1] and 3-5% carbonate [2] in the soils at the landing site in the martian northern plains. The Thermal and Evolved Gas Analyzer (TEGA) instrument was one of the tools that made this discovery. After soil samples were delivered to TEGA and transferred into small ovens, the samples could be heated up to approx.1000 C and the gases that evolved during heating were monitored by a mass spectrometer. A CO2 signal was detected at high temperature (approx.750 C) that has been attributed to calcium carbonate decomposition. In addition to this CO2 release, a lower temperature signal was seen. This lower temperature CO2 release was postulated to be one of three things: 1) desorption of CO2, 2) decomposition of a different carbonate mineral, or 3) CO2 released due to organic combustion. Cannon et al. [3] present another novel hypothesis involving the interaction of decomposition products of a perchlorate salt and calcium carbonate.

Decomposition of Potassium Ferrate(VI)(K{sub 2}FeO{sub 4}) and Potassium Ferrate(III)(KFeO{sub 2}): In-situ Moessbauer Spectroscopy Approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Machala, Libor; Zboril, Radek; Sharma, Virender K.

2008-10-28

Moessbauer spectroscopy was shown to be very useful technique studying the mechanism of thermal decomposition or aging processes of the most known ferrate(VI), K{sub 2}FeO{sub 4}. In-situ Moessbauer spectroscopy approach was used to monitor the phase composition during the studied processes. The experimental set-up was designed to perform in-situ measurements at high temperatures and at different air humid conditions at room temperature. The potassium ferrate(III), KFeO{sub 2} was demonstrated to be the primary product of thermal decomposition of K{sub 2}FeO{sub 4}. The KFeO{sub 2} was unstable in a humid air at room temperature and reacted with components of air, H{submore » 2}O and CO{sub 2} to give Fe{sub 2}O{sub 3} nanoparticles and KHCO{sub 3}. The aging kinetics of K{sub 2}FeO{sub 4} and KFeO{sub 2} under humid air were significantly dependent on the relative air humidity.« less

Basis adaptation and domain decomposition for steady partial differential equations with random coefficients

DOE PAGES

Tipireddy, R.; Stinis, P.; Tartakovsky, A. M.

2017-09-04

In this paper, we present a novel approach for solving steady-state stochastic partial differential equations (PDEs) with high-dimensional random parameter space. The proposed approach combines spatial domain decomposition with basis adaptation for each subdomain. The basis adaptation is used to address the curse of dimensionality by constructing an accurate low-dimensional representation of the stochastic PDE solution (probability density function and/or its leading statistical moments) in each subdomain. Restricting the basis adaptation to a specific subdomain affords finding a locally accurate solution. Then, the solutions from all of the subdomains are stitched together to provide a global solution. We support ourmore » construction with numerical experiments for a steady-state diffusion equation with a random spatially dependent coefficient. Lastly, our results show that highly accurate global solutions can be obtained with significantly reduced computational costs.« less

Basis adaptation and domain decomposition for steady-state partial differential equations with random coefficients

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tipireddy, R.; Stinis, P.; Tartakovsky, A. M.

We present a novel approach for solving steady-state stochastic partial differential equations (PDEs) with high-dimensional random parameter space. The proposed approach combines spatial domain decomposition with basis adaptation for each subdomain. The basis adaptation is used to address the curse of dimensionality by constructing an accurate low-dimensional representation of the stochastic PDE solution (probability density function and/or its leading statistical moments) in each subdomain. Restricting the basis adaptation to a specific subdomain affords finding a locally accurate solution. Then, the solutions from all of the subdomains are stitched together to provide a global solution. We support our construction with numericalmore » experiments for a steady-state diffusion equation with a random spatially dependent coefficient. Our results show that highly accurate global solutions can be obtained with significantly reduced computational costs.« less

Suppression of the Thermal Decomposition Reaction of Forest Combustible Materials in Large-Area Fires

NASA Astrophysics Data System (ADS)

Volkov, R. S.; Zhdanova, A. O.; Kuznetsov, G. V.; Strizhak, P. A.

2018-05-01

Experimental investigations on the characteristic time of suppression of the thermal decomposition reaction of typical forest combustible materials (aspen twigs, birch leaves, spruce needles, pine chips, and a mixture of these materials) and the volume of water required for this purpose have been performed for model fire hotbeds of different areas: SFCM = 0.0003-0.007 m2 and SFCM = 0.045-0.245 m2. In the experiments, aerosol water flows with droplets of size 0.01-0.25 mm were used for the spraying of model fire hotbeds, and the density of spraying was 0.02 L/(m2·s). It was established that the characteristics of suppression of a fire by an aerosol water flow are mainly determined by the sizes of the droplets in this flow. Prognostic estimates of changes in the dispersivity of a droplet cloud, formed from large (as large as 0.5 L) "drops" (water agglomerates) thrown down from a height, have been made. It is shown that these changes can influence the conditions and characteristics of suppression of a forest fire. Dependences, allowing one to forecast the characteristics of suppression of the thermal decomposition of forest combustible materials with the use of large water agglomerates thrown down from an aircraft and aerosol clouds formed from these agglomerates in the process of their movement to the earth, are presented.

Suppression of the Thermal Decomposition Reaction of Forest Combustible Materials in Large-Area Fires

NASA Astrophysics Data System (ADS)

Volkov, R. S.; Zhdanova, A. O.; Kuznetsov, G. V.; Strizhak, P. A.

2018-03-01

Experimental investigations on the characteristic time of suppression of the thermal decomposition reaction of typical forest combustible materials (aspen twigs, birch leaves, spruce needles, pine chips, and a mixture of these materials) and the volume of water required for this purpose have been performed for model fire hotbeds of different areas: SFCM = 0.0003-0.007 m2 and SFCM = 0.045-0.245 m2. In the experiments, aerosol water flows with droplets of size 0.01-0.25 mm were used for the spraying of model fire hotbeds, and the density of spraying was 0.02 L/(m2·s). It was established that the characteristics of suppression of a fire by an aerosol water flow are mainly determined by the sizes of the droplets in this flow. Prognostic estimates of changes in the dispersivity of a droplet cloud, formed from large (as large as 0.5 L) "drops" (water agglomerates) thrown down from a height, have been made. It is shown that these changes can influence the conditions and characteristics of suppression of a forest fire. Dependences, allowing one to forecast the characteristics of suppression of the thermal decomposition of forest combustible materials with the use of large water agglomerates thrown down from an aircraft and aerosol clouds formed from these agglomerates in the process of their movement to the earth, are presented.

Evaluation of a Nonlinear Finite Element Program - ABAQUS.

DTIC Science & Technology

1983-03-15

anisotropic properties. * MATEXP - Linearly elastic thermal expansions with isotropic, orthotropic and anisotropic properties. * MATELG - Linearly...elastic materials for general sections (options available for beam and shell elements). • MATEXG - Linearly elastic thermal expansions for general...decomposition of a matrix. * Q-R algorithm • Vector normalization, etc. Obviously, by consolidating all the utility subroutines in a library, ABAQUS has

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.

Study of Selected Composites Copper Concentrate-Plastic Waste Using Thermal Analysis

NASA Astrophysics Data System (ADS)

Szyszka, Danuta

2017-12-01

The paper presents thermal analysis of selected composites (copper concentrate, plastic waste) in two stages. The first stage consisted in thermogravimetric analysis and differential thermal analysis on the applied plastic waste and copper concentrate, and subsequently, a comparative study has been carried out on products obtained, constituting composites of those materials. As a result of analyses, it was found that up to ca. 400 °C composites show high thermal stability, whereas above that temperature, a thermal decomposition of the composite occurs, resulting in emissions of organic compounds, i.e. hydrocarbon compounds and organic oxygenate derivatives.

Optimizing LX-17 Thermal Decomposition Model Parameters with Evolutionary Algorithms

NASA Astrophysics Data System (ADS)

Moore, Jason; McClelland, Matthew; Tarver, Craig; Hsu, Peter; Springer, H. Keo

2017-06-01

We investigate and model the cook-off behavior of LX-17 because this knowledge is critical to understanding system response in abnormal thermal environments. Thermal decomposition of LX-17 has been explored in conventional ODTX (One-Dimensional Time-to-eXplosion), PODTX (ODTX with pressure-measurement), TGA (thermogravimetric analysis), and DSC (differential scanning calorimetry) experiments using varied temperature profiles. These experimental data are the basis for developing multiple reaction schemes with coupled mechanics in LLNL's multi-physics hydrocode, ALE3D (Arbitrary Lagrangian-Eulerian code in 2D and 3D). We employ evolutionary algorithms to optimize reaction rate parameters on high performance computing clusters. Once experimentally validated, this model will be scalable to a number of applications involving LX-17 and can be used to develop more sophisticated experimental methods. Furthermore, the optimization methodology developed herein should be applicable to other high explosive materials. This work was performed under the auspices of the U.S. DOE by LLNL under contract DE-AC52-07NA27344. LLNS, LLC.

Copolymerization modification of poly (butylene itaconate)

NASA Astrophysics Data System (ADS)

Gao, Chuanhui; Wang, Jing; Han, Shijian; Hu, Zunfu; Liu, Yuetao

2017-08-01

A series of copolyesters-poly (butylene itaconate) (PBI) was synthesized by melt polycondensation from itaconic acid (IA) and 1,4-butanediol (BDO). On this basis, dimethyl terephthalate (DMT), adipic acid (AP) and sebacic acid (SA), respectively, was selected as the third comonomer component to modify PBI to poly (butylene itaconate-co-butylene terephthalate) (PBIT), poly (butylene itaconate-co-butylene adipate) (PBIA) and (butylene itaconate-co-butylene sebacate) (PBIS), of which structure and physical properties were characterized by FT-IR, 1H-NMR, GPC, DSC and TG. The results showed that PBI was amorphous material, and the molecular weight and the initial thermal decomposition temperature of PBI were 1108, 244°C, respectively. Compared to PBI, the molecular weight and the thermal stability of copolyesters (PBIA, PBIT and PBIS) could be increased by this treatment. Particularly, the molecular weight of PBIS was increased to 12,321, 12 times more than PBI, the initial thermal decomposition temperature was improved to 336°C, and PBIS had good crystallization performance.

Mechanisms of propylene glycol and triacetin pyrolysis.

PubMed

Laino, Teodoro; Tuma, Christian; Moor, Philippe; Martin, Elyette; Stolz, Steffen; Curioni, Alessandro

2012-05-10

Propylene glycol and triacetin are chemical compounds, commonly used as food additives. Though the usage of the pure chemicals is not considered harmful when used as dietary supplements, little is known about the nature of their thermal degradation products and the impact they may have on human health. For these reasons, in this manuscript we investigate the thermal decomposition mechanisms of both neutral propylene glycol and triacetin in the gas phase by a novel simulation framework. This is based on a free energy sampling methodology followed by an accurate energy refinement. Structures, Gibbs free energy barriers, and rate constants at 800 K were computed for the different steps involved in the two pyrolytic processes. The thermal decomposition mechanisms found theoretically for propylene glycol and triacetin were validated by a qualitative experimental investigation using gas-phase chromatography-mass spectroscopy, with excellent agreement. The results provide a validation of the novel simulation framework and shed light on the potential hazard to the health that propylene glycol and triacetin may have when exposed to high temperatures.

Thermochemical and trace element behavior of coal gangue, agricultural biomass and their blends during co-combustion.

PubMed

Zhou, Chuncai; Liu, Guijian; Cheng, Siwei; Fang, Ting; Lam, Paul Kwan Sing

2014-08-01

The thermal decomposition behavior of coal gangue, peanut shell, wheat straw and their blends during combustion were determined via thermogravimetric analysis. The coal gangue/agricultural biomass blends were prepared in four weight ratios and oxidized under dynamic conditions from room temperature to 1000 °C by various heating rates. Kinetic models were carried out to evaluate the thermal reactivity. The overall mass balance was performed to assess the partition behavior of coal gangue, peanut shell and their blends during combustion in a fixed bed reactor. The decomposition processes of agricultural biomass included evaporation, release of volatile matter and combustion as well as char oxidation. The thermal reactivity of coal gangue could be improved through the addition of agricultural biomass in suitable proportion and subsequent appropriate heating rate during combustion. In combination with the heating value and base/acid ratio limitations, a blending ratio of 30% agricultural biomass is conservatively selected as optimum blending. Copyright © 2014 Elsevier Ltd. All rights reserved.

Characterization of corncob-derived biochar and pyrolysis kinetics in comparison with corn stalk and sawdust.

PubMed

Liu, Xuan; Zhang, Yang; Li, Zifu; Feng, Rui; Zhang, Yaozhong

2014-10-01

In this study, thermal and physicochemical characterization results of corncob (CC) and its derived biochars were analyzed and differentiated from sawdust (SD) and cornstalk (CS). The pyrolysis temperature shows the largest effect on the yield of biochar produced compare with residing time, heating rate, and feedstock particle size. The CC-derived biochars produced at temperatures ranging from 300 to 600°C were analyzed. The CC was thermochemically altered to a stable biochar when the pyrolysis temperature was set to over 500°C. To deduce the reaction mechanism of the CC during the major thermal decomposition stage, 16 mechanisms in solid-state reactions were applied. The reaction order and nucleation mechanisms described the thermal decomposition of the CC. By using the best-fitted mechanisms, the kinetic parameters were calculated. The weight active energy of the CC was 122.42kJ/mol, which was the lowest value compared to those of CS and SD. Copyright © 2014 Elsevier Ltd. All rights reserved.

Thermal decomposition pathway of undoped and doped zinc layered gallate nanohybrid with Fe 3+, Co 2+ and Ni 2+ to produce mesoporous and high pore volume carbon material

NASA Astrophysics Data System (ADS)

Ghotbi, Mohammad Yeganeh; bin Hussein, Mohd Zobir; Yahaya, Asmah Hj; Abd Rahman, Mohd Zaki

2009-12-01

A series of brucite-like materials, undoped and doped zinc layered hydroxide nitrate with 2% (molar) Fe 3+, Co 2+ and Ni 2+ were synthesized. Organic-inorganic nanohybrid material with gallate anion as a guest, and zinc hydroxide nitrate, as an inorganic layered host was prepared by the ion-exchange method. The nanohybrid materials were heat-treated at various temperatures, 400-700 °C. X-ray diffraction, thermal analysis and also Fourier transform infrared results showed that incorporation of the doping agents within the zinc layered hydroxide salt layers has enhanced the heat-resistivity of the nanohybrid materials in the thermal decomposition pathway. Porous carbon materials can be obtained from the heat-treating the nanohybrids at 600 and 700 °C. Calcination of the nanohybrids at 700 °C under nitrogen atmosphere produces mesoporous and high pore volume carbon materials.