Chemical kinetics of the thermal degradation of hydrocarbon fuels
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Wong, E. L.↗
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Results for “THERMAL DEGRADATION”
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Potential health hazards from thermal degradation events - Particulate vs. gas phase effects
The effect of instillation of ultrafine TiO2 particles (10-nm anatase-TiO2 and 12-nm rutile-TiO2 (administered in doses from 60 to 1000 microg/rat and 500 microg/rat, respectively) on the respiratory tract of exposed rats was compared to the effects of larger (250 nm anatase-TiO2 and 220-nm rutile-TiO2 particles (given in doses 500 or 1000 microg/rat and 500 microg/rat, respectively). These effects were also compared to the effects of inhalation of 20-nm and 250-nm anatase-TiO2 particles and inhalation with surrogate gas phase components (HF and HCl). It was found that ultrafine TiO2 particles induced greater inflammatory reaction in the lung, had greater adverse effect on alveolar macrophage-mediated clearance function, and had a greater potential to induce mediators which can adversely affect other lung cells than did larger-sized particles. Inhalation of surrogate gas phase components caused injury only to the upper respiratory tract, in contrast to the ultrafine particles, which affected the deep lung.
Oberdorster, Gunter↗
Ultrasonic Evaluation of Thermal Degradation in Adhesive Bonds
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ultrasonic nondestructive evaluation technique hea↗
Anisotropic thermal-conductivity degradation in the phase-field method accounting for crack directionality
Dynamic loads applied to metals may lead to brittle or ductile fracture depending on the imposed strain rates, material properties, and specimen geometry. With an increase in the applied velocity, brittle to ductile failure mode transition may also be observed. Furthermore, at high strain rates, ductile fracture may be preceded by shear bands, which are narrow bands of intense plastic deformation, typically accompanied by a significant rise in temperature. Reliable models are needed to predict the response of metals subject to dynamic loads. In particular, capturing the interplay between heat conduction and crack propagation using the phase-field fracture method is still an open research field. To accurately capture the heat transfer physics across crack surfaces, damage models degrading thermal-conductivity are necessary. While isotropic thermal-conductivity degradation models were proposed, they may lead to errors as they are indifferent to crack directionality. In our current work, a new anisotropic approach is proposed in which thermal-conductivity, which depends on the phase-field gradient, is degraded solely across the crack. Here, it is shown that this approach improves the near-field approximation of temperature and heat flux compared with isotropic degradation, when taking the discontinuous crack solutions as reference. Additionally, the anisotropic degradation approach is implemented in a unified dynamic fracture model and a couple of examples demonstrate the viability of this approach.
42 ENGINEERING↗
Thermal radiation degradation analysis of Surveyor III material
Lunar dust reflectance degradation of thermal control paint on Surveyor 3 TV camera, separating solar radiation effects by analytical model
Anderson, D. L.↗
Key Degradation Products in Nitroplasticizer Thermal Aging
Upon thermal aging, nitroplasticizer (NP) can thermally degrade and release numerous degradation products depending on aging conditions. In this report, we summarize our recent findings, a library of key degradation products in the NP thermal aging is provided. The library contains 25 identified species with their corresponding MS/MS spectrum and intensity profiles, which are derived from our 44-month thermal aging experiment of NP conducted in air, nitrogen, and water at room temperature (RT), 38, 45, 55, and 64°C. To provide a comprehensive yet simplified overview of NP degradation, we summarized the proposed mechanisms of HONO elimination and decomposition, acid generation, PBNA nitrosation and nitration, acid-catalyzed hydrolyses of NP and polynitrated PBNAs, as well as the formation of NP degradants. As the last part of a series of publications and reports on the investigation of NP degradation mechanisms, this work further unfolds complex chemistry that occurs in the entire aging process of NP.
36 MATERIALS SCIENCE↗
In situ observation of thermal-driven degradation and safety concerns of lithiated graphite anode
Abstract Graphite, a robust host for reversible lithium storage, enabled the first commercially viable lithium-ion batteries. However, the thermal degradation pathway and the safety hazards of lithiated graphite remain elusive. Here, solid-electrolyte interphase (SEI) decomposition, lithium leaching, and gas release of the lithiated graphite anode during heating were examined by in situ synchrotron X-ray techniques and in situ mass spectroscopy. The source of flammable gas such as H 2 was identified and quantitively analyzed. Also, the existence of highly reactive residual lithium on the graphite surface was identified at high temperatures. Our results emphasized the critical role of the SEI in anode thermal stability and uncovered the potential safety hazards of the flammable gases and leached lithium. The anode thermal degradation mechanism revealed in the present work will stimulate more efforts in the rational design of anodes to enable safe energy storage.
25 ENERGY STORAGE↗
The effects of metals and inhibitors on thermal oxidative degradation reactions of unbranched perfluoroalkylethers
Thermal oxidative degradation studies were performed on unbranched perfluoroalkylethers at 288 C in oxygen. Metals and alloys studied included Ti, Al, and Ti (4 Al, 4 Mn). The mechanism of degradation was by chain scission. Ti and Al promoted less degradation than Ti (4 Al, 4 Mn). The two inhibitors investigated (a perfluorophenyl phosphine and a phosphatriazine) reduced degradation rates by several orders of magnitude. Both inhibitors were effective for the same duration (75 to 100 hours). The phosphatriazine appeared to provide more surface protection.
Jones, W. R., Jr.↗
Influence of point defect accumulation on in-pile thermal conductivity degradation: Fuel rod defect distribution and deviation between in-pile and post irradiation thermal conductivity
As nuclear fuel burn-up increases, its thermal conductivity degrades due to the accumulation of defects that lead to increased phonon scattering rates. This results in a rise in the centerline temperature of the fuel rod, whereby heat generation must be decreased to avoid undesired behavior such as fuel melting and extensive fission gas release. Fuel performance codes are utilized to optimize the fuel's operational conditions; while they are based on established physical principles, their empirical nature limits their predictive capabilities. Recently, an effort has been made to develop predictive fuel performance codes for commonly used nuclear fuels, as well as accelerated qualification of advanced nuclear fuels. In this report, we elaborate on the importance of careful analysis of point defects’ impact on thermal conductivity in fuel performance analysis. Further, a model is presented where point defect concentration is estimated based on Rate Theory modeling and used as input to the Klemens-Callaway model to calculate their contribution to the degradation of thermal conductivity in UO 2 under prototypical irradiation conditions. This analysis suggests that point defect concentration is significant at the rim of the fuel pellet and neglecting this leads to underestimation of the centerline temperature, which may have consequences on fission gas behavior.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
The effects of metals and inhibitors on thermal oxidative degradation reactions of unbranched perfluoroalkyl ethers
Thermal oxidative degradation studies were performed on unbranched perfluoroalkylethers at 288 C in oxygen. Metals and alloys studied included Ti, Al, and Ti (4 Al, 4 Mn). The mechanism of degradation was by chain scission. Ti and Al promoted less degradation than Ti (4 Al, 4 Mn). The two inhibitors investigated (a perfluorophenyl phosphine and a phosphatriazine) reduced degradation rates by several orders of magnitude. Both inhibitors were effective for the same duration (75 to 100 hours). The phosphatriazine appeared to provide more surface protection.
Jones, W. R., Jr.↗
Outgassing of casted and 3D printed silicones
Outgassing of 3D printed and casted silica-filled silicones was studied using a standard ASTM E-595 procedure and a modified Soreq’s method that allows very sensitive measurements of the outgassing kinetics even at low temperatures, 20 – 50 °C. We studied three different silica-filled silicones, non-porous cased M9787, and 3D printed LL50 and 40P materials. The present report shows that vacuum outgassing products of polysiloxane-based materials include multiple species. In addition to chemisorbed and physisorbed water outgassing, previously studied by TPD, polymer fragments of varying sizes evaporate as well. The chemical composition of the condensable volatile species collected on a Germanium substrate, was analyzed by FTIR. It was shown that all studied materials produce mostly PDMS-based outgassing products that form stable droplet-like structure on the Ge substrate. The highest amount of the condensable volatile species was measured for LL50. Isothermal TGA in nitrogen atmosphere of the LL50 material was compared to the standard vacuum outgassing. The results of TGA showed lower mass loss and higher water regain. The kinetics of the outgassing at relatively low temperatures of 20, 30 and 50 °C was studied using Thermoelectric Quartz Crystal Microbalance (TQCM). The TQCM surface was held at -10 °C to enhance condensation of the outgassed moisture. The analysis presented here, when combined with the extensive previous work on moisture outgassing, provides a better understanding of the aging mechanism of polysiloxane-based materials. In this work we show that outgassing techniques, usually applied for qualification of polymers for space-related applications, may be used as a complementary method to study thermal degradation and aging of silica-based silicones. Our results indicate that the long-term degradation mechanics and thermal degradation products depend primarily on the chemical composition of silicone-based material and only slightly affected by the manufacturing process. Surprisingly, the surface-to-volume ratio of the 3D printed vs. casted/molded materials showed only minor effect on the outgassing kinetic parameters.
36 MATERIALS SCIENCE↗
Thermal oxidative degradation reactions of perfluoroalkylethers
The mechanisms operative in thermal oxidative degradation of Fomblin Z and hexafluoropropene oxide derived fluids and the effect of alloys and additives upon these processes are investigated. The nature of arrangements responsible for the inherent thermal oxidative instability of the Fomblin Z fluids is not established. It was determined that this behavior is not associated with hydrogen end groups or peroxy linkages. The degradation rate of these fluids at elevated temperatures in oxidizing atmospheres is dependent on the surface/volume ratio. Once a limiting ratio is reached, a steady rate appears to be attained. Based on elemental analysis and oxygen consumption data, CF2OCF2CF2O2, no. CF2CF2O, is one of the major arrangements present. The action of the M-50 and Ti(4 Al, 4 Mn) alloys is much more drastic in the case of Fomblin Z fluids than that observed for the hexafluoropropene derived materials. The effectiveness of antioxidation anticorrosion additives, P-3 and phospha-s-triazine, in the presence of metal alloys is very limited at 316 C; at 288 C the additives arrested almost completely the fluid degradation. The phospha-s-triazine appears to be at least twice as effective as the P-3 compound; it also protected the coupon better. The Ti(4 Al, 4 Mn) alloy degraded the fluid mainly by chain scission processes this takes place to a much lesser degree with M-50.
Paciorek, K. L.↗
Degradation of thermal control coatings by vacuum ultraviolet irradiation
Vacuum UV degradation of thermal control coatings on ATS-1 satellite, comparing with laboratory simulation
Donohoe, M. J.↗
Global Kinetic Constants for Thermal Oxidative Degradation of a Cellulosic Paper
Values of global kinetic constants for pyrolysis, thermal oxidative degradation, and char oxidation of a cellulosic paper were determined by a derivative thermal gravimetric study. The study was conducted at heating rates of 0.5, 1, 1.5, 3, and 5 C/min in ambient atmospheres of nitrogen, 0.28, 1.08, 5.2 percent oxygen concentrations, and air. Sample weight loss rate, concentrations of CO, CO2, and H2O in the degradation products, and oxygen consumption were continuously measured during the experiment. Values of activation energy, preexponential factor, orders of reaction, and yields of CO, CO2, H2O, total hydrocarbons, and char for each degradation reaction were derived from the results. Heat of reaction for each reaction was determined by differential scanning calorimetry. A comparison of the calculated CO, CO2, H2O, total hydrocarbons, sample weight loss rate, and oxygen consumption was made with the measured results using the derived kinetic constants, and the accuracy of the values of kinetic constants was discussed.
Kashiwagi, Takashi↗
Thermal oxidative degradation reactions of linear perfluoroalkyl ethers
Thermal and thermal oxidative stability studies were performed on linear perfluoroalkyl ether fluids. The effect on degradation by metal catalysts and degradation inhibitors is reported. The linear perfluoroalkyl ethers are inherently unstable at 316 C in an oxidizing atmosphere. The metal catalysts greatly increased the rate of degradation in oxidizing atmospheres. In the presence of these metals in an oxidizing atmosphere, the degradation inhibitors were highly effective in arresting degradation at 288 C. However, the inhibitors had only limited effectiveness at 316 C. The metals promote degradation by chain scission. Based on elemental analysis and oxygen consumption data, the linear perfluoroalkyl ether fluids have a structural arrangement based on difluoroformyl and tetrafluoroethylene oxide units, with the former predominating. Previously announced in STAR as N82-26468
Jones, W. R., Jr.↗
Thermal oxidative degradation reactions of linear perfluoroalky lethers
Thermal and thermal oxidative stability studies were performed on linear perfluoro alkyl ether fluids. The effect on degradation by metal catalysts and degradation inhibitors are reported. The liner perfluoro alkylethers are inherently unstable at 316 C in an oxidizing atmosphere. The metal catalysts greatly increased the rate of degradation in oxidizing atmospheres. In the presence of these metals in an oxidizing atmosphere, the degradation inhibitors were highly effective in arresting degradation at 288 C. However, the inhibitors had only limited effectiveness at 316 C. The metals promote degradation by chain scission. Based on elemental analysis and oxygen consumption data, the linear perfluoro alkylether fluids have a structural arrangement based on difluoroformyl and tetrafluoroethylene oxide units, with the former predominating.
Jones, W. R., Jr.↗
Oxygen Solubility in Aqueous Amine Solvents with Common Additives Used for CO 2 Chemical Absorption
Major sources of anthropogenic CO 2 are power generation and transportation industries where researcher continue to explore CO 2 emission mitigation strategies as applied to these CO 2 sources through carbon capture, utilization, and sequestration (CCUS). The most mature CO 2 capture technology is post-combustion carbon capture (PCCC) using aqueous amine solutions/solvents, however solvent degradation and regeneration costs are slowing the widespread adoption of PCCC. Solvent degradation of the aqueous amine solutions is mainly caused from the temperature gradient between the absorber and stripper columns and common flue gas components such as SOx, NOx, and oxygen (O 2 ). The two main classifications of solvent degradation are thermal degradation, occurring when the amine reacts with itself at elevated temperatures and anaerobic conditions and oxidative degradation. Oxidative degradation reactions can occur from oxygen mass transfer and free radical oxidation. Metals, such as iron from the corrosion of steel structures used in industrial applications such as PCCC, can help to catalyze these reactions. Various oxidative degradation studies have shown how O 2 concentrations in flue gas and, to a lesser extent, temperature influence the extent of oxidative degradation. Accurately measuring the O 2 solubility, commonly referred to as dissolved oxygen (DO), in a quick, continuous, and efficient manner in aqueous amine solvents should contribute to determine the effectiveness of mitigation strategies for oxidative degradation. Knowing that commercial PCCC amine solvents contain components beyond water, amine, carbonate species and CO 2 , this investigation was conducted to determine the oxygen solubility changes of common aqueous amines solutions with commonly used and published solvent additives. The impact of carbon loadings with and without the additives was also examined. A commercial dissolved oxygen probe was used to measure the DO concentrations and compared them against standard Winkler Method titration values. The results show that antifoam shows minimal change in [DO]. MBT yielded lower DO values, and NaVO 3 showed a higher DO concentration due to interferences. These results indicate that most common amine solvent additives should be expected to minimally impact oxygen solubility and amine oxidative degradation.
60 APPLIED LIFE SCIENCES↗