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At least 217 records · Page 12

Calorimetry, activity, and micro-FTIR analysis of CO chemisorption, titration, and oxidation on supported Pt

The value of in situ analysis on CO chemisorption, titration and oxidation over supported Pt catalysts using calorimetry, catalytic and micro-FTIR methods is illustrated using silica- and titania-supported samples. Isothermal CO-O and O2-CO titrations have not been widely used on metal surfaces and may be complicated if some oxide supports are reduced by CO titrant. However, they can illuminate the kinetics of CO oxidation on metal/oxide catalysts since during such titrations all O and CO coverages are scanned as a function of time. There are clear advantages in following the rates of the catalyzed CO oxidation via calorimetry and gc-ms simultaneously. At lower temperatures the evidence they provide is complementary. CO oxidation and its catalysis of CO oxidation have been extensively studied with hysteresis and oscillations apparent, and the present results suggest the benefits of a combined approach. Silica support porosity may be important in defining activity-temperature hysteresis. FTIR microspectroscopy reveals the chemical heterogeneity of the catalytic surfaces used; it is interesting that the evidence with regard to the dominant CO surface species and their reactivities with regard to surface oxygen for present oxide-supported Pt are different from those seen on graphite-supported Pt.

Sermon, Paul A.↗

Effects of a noncoplanar biphenyldiamine on the processing and properties of addition polyimides

Addition curing polyimides, prepared from noncoplanar 2,2'-bis(trifluoromethyl) 4,4' diaminobiphenyl (BTDB) with various dianhydrides were evaluated as high temperature polymer matrix materials. T sub g of these polymers were measured by mechanical methods as well as by thermal mechanical analysis. Physical and mechanical properties as well as the thermo-oxidative stability of neat resins and the corresponding G40-600 graphite fiber reinforced composites were compared to that of PMR-II-50 and V-CAP-75.

Chuang, Kathy C.↗

Soft-Bake Purification of SWCNTs Produced by Pulsed Laser Vaporization

The "soft-bake" method is a simple and reliable initial purification step first proposed by researchers at Rice University for single-walled carbon nanotubes (SWCNT) produced by high-pressure carbon mon oxide disproportionation (HiPco). Soft-baking consists of annealing as-produced (raw) SWCNT, at low temperatures in humid air, in order to degrade the heavy graphitic shells that surround metal particle impurities. Once these shells are cracked open by the expansion and slow oxidation of the metal particles, the metal impurities can be digested through treatment with hydrochloric acid. The soft-baking of SWCNT produced by pulsed-laser vaporization (PLV) is not straightforward, because the larger average SWCNT diameters (.1.4 nm) and heavier graphitic shells surrounding metal particles call for increased temperatures during soft-bake. A part of the technology development focused on optimizing the temperature so that effective cracking of the graphitic shells is balanced with maintaining a reasonable yield, which was a critical aspect of this study. Once the ideal temperature was determined, a number of samples of raw SWCNT were purified using the soft-bake method. An important benefit to this process is the reduced time and effort required for soft-bake versus the standard purification route for SWCNT. The total time spent purifying samples by soft-bake is one week per batch, which equates to a factor of three reduction in the time required for purification as compared to the standard acid purification method. Reduction of the number of steps also appears to be an important factor in improving reproducibility of yield and purity of SWCNT, as small deviations are likely to get amplified over the course of a complicated multi-step purification process.

Yowell, Leonard↗

Effect of fiber reinforcement on thermo-oxidative stability and mechanical properties of polymer matrix composites

A number of studies have investigated the thermooxidative behavior of polymer matrix composites. Two significant observations have been made from these research efforts: (1) fiber reinforcement has a significant effect on composite thermal stability; and (2) geometric effects must be considered when evaluating thermal aging data. The polyimide PMR-15 was the matrix material used in these studies. The control composite material was reinforced with Celion 6000 graphite fiber. T-4OR graphite fibers, along with some very stable ceramic fibers were selected as reinforcing fibers because of their high thermal stability. The ceramic fibers were Nicalon (silicon carbide) and Nextel 312 (alumina-silica-boron oxide). The mechanical properties of the two graphite fiber composites were significantly different, probably owing to variations in interfacial bonding between the fibers and the polyimide matrix. Three oxidation mechanisms were observed: (1) the preferential oxidation of the Celion 6000 fiber ends at cut surfaces, leaving a surface of matrix material with holes where the fiber ends were originally situated; (2) preferential oxidation of the composite matrix; and (3) interfacial degradation by oxidation. The latter two mechanisms were also observed on fiber end cut surfaces. The fiber and interface attacks appeared to initiate interfiber cracking along these surfaces.

Bowles, K. J.↗

An evaluation of candidate oxidation resistant materials

Ground based testing of materials considered for Kapton solar array blanket protection, graphite epoxy structural member protection, and high temperature radiators was performed in an RF plasma asher. Ashing rates for Kapton were correlated with rates measured on STS-8 to determine the exposure time equivalent to one year in low Earth orbit (LEO) at a constant density space station orbital flux. Protective coatings on Kapton from Tekmat, Andus Corporation, and LeRC were evaluated in the plasma asher and mass loss rates per unit area were measured for each sample. All samples evaluated provided some protection to the underlying surface but ion beam sputter deposited samples of SiO2 and SiO2 with 8% polytetrafluoroethylene (PTFE) showed no evidence of degradation after 47 hours of exposure. Mica paint was evaluated as a protective coating for graphite epoxy structural members. Mica appears to be resistant to attack by atomic oxygen but only offers some limited protection as a paint because the paint vehicles evaluated to date were not resistant to atomic oxygen. Four materials were selected for evaluation as candidate radiator materials: stainless steel, copper, niobium-1% zirconium, and titanium-6% aluminum-4% vanadium. These materials were surface textured by various means to improve their emittance. Emittances as high as 0.93 at 2.5 microns for stainless steel and 0.89 at 2.5 microns for Nb-1 Zr were obtained from surface texturing. There were no significant changes in emittance after asher exposure.

Rutledge, Sharon↗

AGR Fuel Oxidation Testing Summary and Plans

This presentation describes the goals, scope, and plans for oxidation testing of (primarily irradiated) AGR TRISO fuels and related materials (such as graphite and graphitic matrix material). This presentation will be given at the annual program review meeting for the Gas-cooled Reactor program hosted at INL starting on July 16.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Thermally stable polyimides from solutions of monomeric reactants

A method for preparing thermally stable resin-fiber-reinforced composites by using solutions of appropriate monomers is described. Solutions containing a dimethyl ester of an aryl tetracarboxylic acid, the monomethyl ester of nadic acid, and an aryl diamine were used to impregnate graphite fibers. Composites fabricated from these prepregs exhibited excellent thermo-oxidative stability and retention of mechanical properties at 315 C (600 F). These results compare favorably to those obtained from composites made from amide-acid prepolymers capped with reactive alicyclic rings. Monomeric solutions provide excellent shelf life and improved solubility compared to amide-acid prepolymer solutions.

Serafini, T. T.↗

Specimen geometry effects on graphite/PMR-15 composites during thermo-oxidative aging

Studies were conducted to establish the effects of specimen geometry on the thermo-oxidative stability and the mechanical properties retention of unidirectional Celion 12000 graphite fiber reinforced PMR-15 polyimide composites. Weight loss, flexural strength and interlaminar shear strength are measured at isothermal aging times as long as 1639 hr at a temperature of 316 C for three different specimen geometries. It is found that the three different types of specimen surfaces exhibit different values of weight loss/unit area. The mechanical properties retention is also found to be dependent on geometry for these composites. The interlaminar shear strength decreases significantly over the complete range of aging times. The flexural strength retention starts showing geometric dependency after about 1000 hr of aging at 316C. Weight loss fluxes, associated with the three different types of exposed surfaces, are calculated and used to develop an empirical mathematical model for predicting the weight loss behavior of unidirectional composites of arbitrary geometries. Data are presented comparing experimentally determined weight loss with weight loss values predicted using the empirical model.

Bowles, K. J.↗

Specimen geometry effects on graphite/PMR-15 composites during thermo-oxidative aging

Studies were conducted to establish the effects of specimen geometry on the thermo-oxidative stability and the mechanical properties retention of unidirectional Celion 12000 graphite fiber reinforced PMR-15 polyimide composites. Weight loss, flexural strength and interlaminar shear strength are measured at isothermal aging times as long as 1639 hr at a temperature of 316 C for three different specimen geometries. It is found that the three different types of specimen surfaces exhibit different values of weight loss/unit area. The mechanical properties retention is also found to be dependent on geometry for these composites. The interlaminar shear strength decreases significantly over the complete range of aging times. The flexural strength retention starts showing geometric dependency after about 1000 hr of aging at 316 C. Weight loss fluxes, associated with the three different types of exposed surfaces, are calculated and used to develop an empirical mathematical model for predicting the weight loss behavior of unidirectional composites of arbitrary geometries. Data are presented comparing experimentally determined weight loss with weight loss values predicted using the empirical model.

Bowles, K. J.↗

Creep Forming of Carbon-Reinforced Ceramic-Matrix Composites

A set of lecture slides describes an investigation of creep forming as a means of imparting desired curvatures to initially flat stock plates of carbon-reinforced ceramic-matrix composite (C-CMC) materials. The investigation is apparently part of a continuing effort to develop improved means of applying small CCMC repair patches to reinforced carbon-carbon leading edges of aerospace vehicles (e.g., space shuttles) prior to re-entry into the atmosphere of the Earth. According to one of the slides, creep forming would be an intermediate step in a process that would yield a fully densified, finished C-CMC part having a desired size and shape (the other steps would include preliminary machining, finish machining, densification by chemical vapor infiltration, and final coating). The investigation included experiments in which C-CMC disks were creep-formed by heating them to unspecified high temperatures for time intervals of the order of 1 hour while they were clamped into single- and double-curvature graphite molds. The creep-formed disks were coated with an oxidation- protection material, then subjected to arc-jet tests, in which the disks exhibited no deterioration after exposure to high-temperature test conditions lasting 490 seconds.

Vaughn, Wallace L.↗

HRTEM and EFTEM Observations of Matrix in the Oxidized CV3 Chondrite ALH 84028: Implications for the Origins of Matrix Olivines

The determination of the nature, distribution, and origin of organic material in carbonaceous chondrites is fundamental to understanding early solar nebular conditions and the origin of life. Using a variety of extraction techniques, followed by detailed chemical analysis, an extensive suite of organic compounds has been identified in carbonaceous chondrites. These data have provided key information on the diversity and isotopic composition of the organic component in chondrites. However, one disadvantage of extraction techniques is that all information regarding the spatial distribution of the organics on a fine scale is lost. This is especially important for the insoluble macromolecular carbon, which constitutes approximately 70% of the carbon in carbonaceous chondrites such as Murchison. The distribution and mineralogical associations may provide important constraints on the possible origins of the carbonaceous material. Our previous studies of the CV3 chondrites Allende and Vigarano have demonstrated that energy filtered transmission electron microscopy (EFTEM), combined with high resolution TEM (HRTEM) are powerful tools for the in situ characterization of insoluble organic matter in carbonaceous chondrites. In this study, we have used SEM and TEM techniques to characterize the matrix mineralogy of the CV3 chondrite ALH 84028 and examine the distribution and mineralogical associations of carbon. We are especially interested in establishing whether the occurrence of poorly graphitized carbon (PGC), observed in Allende matrix olivines, is common to all oxidized CV3 chondrites or is a unique feature of Allende.

Abreu, Neyda M.↗

Correlations of norbornenyl crosslinked polyimide resin structures with resin thermo-oxidative stability, resin glass transition temperature and composite initial mechanical properties

PMR (polymerization of monomeric reactants) methodology was used to prepare 70 different polyimide oligomeric resins and 30 different unidirectional graphite fiber/polyimide composites. Monomeric composition as well as chain length between sites of crosslinks were varied to examine their effects on resin thermo-oxidative stability and glass transition temperature (Tg) of the cured/postcured resins. A linear correlation of decreasing 316 C resin weight loss/surface area versus (1) decreasing aliphatic content, or (2) increasing benzylic/aliphatic content stoichiometry ratio over a wide range of resin compositions was observed. An almost linear correlation of Tg versus molecular distance between the crosslinks was also observed. An attempt was made to correlate Tg with initial composite mechanical properties (flexural strength and interlaminar shear strength). However, the scatter in mechanical strength data prevented obtaining a clear correlation. Instead, only a range of composite mechanical properties was obtained at 25, 288, and 316 C. Perhaps more importantly, what did become apparent during the correlation study was (1) the PMR methodology could be used to prepare composites from resins containing a wide variety of monomer modifications, (2) that these composites almost invariably provided satisfactory initial mechanical properties as long as the resins formulated exhibited satisfactory processing flow, and (3) that PMR resins exhibited predictable rates of 316 C weight loss/surface area based on their benzylic/aliphatic stoichiometery ratio.

Alston, William B.↗

An evaluation of candidate oxidation resistant materials for space applications in LEO

Ground based testing of materials considered for polyimide (Kapton) solar array blanket protection and graphite-epoxy stroctural member protection was performed in an RF plasma asher. Protective coatings on Kapton from various commercial sources and from NASA Lewis Research Center were exposed to the air plasma; and mass loss per unit area was measured for each sample. All samples evaluated provided some protection to the underlying surface, but metal-oxide-fluoropolymer coatings provided the best protection by exhibiting very little degradation after 47 hr of asher exposure. Mica paint was evaluated as a protective coating for graphite-epoxy structural members. Mica appeared to be resistant to attack by atomic oxygen, but only offered limited protection as a paint. this is believed to be due to the paint vehicle ashing underneath the mica leaving unattached mica flakes lying on the surface. The protective coatings on Kapton evaluated so far are promising but further research on protection of graphite-epoxy support structures is needed.

Rutledge, Sharon↗

Structural studies on carbon materials for advanced space technology. Part 1: Structure and oxidation behavior of some carbon/carbon composite materials

The microstructure and some microstructural effects of oxidation have been investigated for laminar carbon fiber cloth/cloth binder matrix composite materials. It was found that cloth wave is important in determining the macrostructure of the composites X-ray diffraction analysis showed that the composites were more graphitic than the constituent fiber phases, indicating a graphitic binder matrix phase. Various tests which were conducted to investigate specific properties of the material are described. It was learned that under the moderate temperature and oxidant flow conditions studied, C-700, 730 materials exhibit superior oxidation resistance primarily because of the inhibiting influence of the graphitized binder matrix.

Fischbach, D. B.↗

Update on Activities Related to the Library of Graphite Microstructures

This report provides an overview and update of the ongoing efforts to create a comprehensive library of microstructures for nuclear graphite and carbon-based materials under consideration for nuclear applications. The library includes data on microstructural characterization of unirradiated graphite materials, a guide to the techniques used to analyze graphite (which complements the ASME guidelines and ASTM standards), a summary of characterization data for neutron-irradiated or oxidized material, and a compendium of microstructural information for carbon-based materials. These efforts are being conducted at various length scales for the filler and binder phases in graphite to better understand graphite’s local structure and property relationships. This report is a follow-up to the previous milestone report titled Report on initial development of a database of nuclear graphite characteristics based on microstructural characterization, ORNL/TM/-2023/2992, published in July 2023.The effort to develop the library of microstructures supports the US Department of Energy Office of Advanced Reactor Technologies program objectives of aiding the material selection, licensing, management, and core assessments of a graphite core by documenting the unirradiated microstructure of relevant grades or characterizing the microstructure’s evolution under the reactor environment. Additionally, this project aims to provide (1) information and guidelines for the characterizing of graphite and (2) a protocol to assess a nuclear graphite grade.

36 MATERIALS SCIENCE↗

Rheological characterization of addition polyimide matrix resins and prepregs

Although graphite-reinforced polyimide matrix composites offer outstanding specific strength and stiffness, together with high thermal oxidative stability, processing problems connected with their rheological behavior remain to be addressed. The present rheological studies on neat polyimide resin systems encountered outgassing during cure. A staging technique has been developed which can successfully handle polyimide samples, and novel methods were applied to generate rheological curves for graphite-reinforced prepregs. The commercial graphite/polyimide systems studied were PRM 15, LARC 160, and V378A.

Maximovich, M. G.↗

Heterogeneous Combustion of Porous Graphite Particles in Microgravity

Recent theoretical investigations on graphite particle combustion have employed several levels of heterogeneous reaction models, ranging from global to elementary models, to describe the oxidation of carbon to gaseous products. Unlike the counterpart homogeneous reaction models, these heterogeneous reaction models are not well developed because of the difficulties associated with decoupling the physical characteristics of the solid (e.g. surface area taking part in combustion) from the chemical kinetic data. This is certainly true for porous graphite particle combustion, where heterogeneous and homogeneous reactions occur within the pores and play an important role in the overall oxidation process. As a result, there are considerable uncertainties of physical phenomena predicted using different heterogeneous kinetic models available in the literature. A good example, discussed later in this paper, is the predicted critical particle size below which the mass burning rate becomes exponentially small. The main goal of this study is to understand the basic mechanism controlling such rapid changes in burning rates, by developing a model where physical contributions are decoupled from chemical rate constants in a consistent manner. Another important goal of the proposed study is to develop a truly intrinsic, detailed heterogeneous reaction model for porous graphite combustion at high-temperatures, and to derive a systematically reduced heterogeneous reaction model in terms of the elementary reaction rate constants of the detailed model. The validation of chemical kinetic models describing the heterogeneous and homogeneous combustion in and around a spherically symmetric porous graphite particle can be considerably simplified by experimental measurements obtained under microgravity conditions. A vital component of this study is to conduct such supporting experiments on particle burning rate and surface temperature using NASA microgravity facilities, in close coordination with the theoretical effort. The basic understanding obtained and models developed as part of this project will be useful for optimal design of coal combustion devices. These models can also be extended to investigate the role of heterogeneous chemistry on pollutant formation pathways in combustion devices. The theoretical approach developed here, with pore diffusion effects decoupled from the chemical effects, can also be extended to understand the heterogeneous combustion of other porous fuels, for example, combustion of magnesium in a CO2 environment for propulsion in the Martian atmosphere.

Chelliah, Harsha K.↗

Upcycling Polyethylene Waste Into Advanced Carbon Materials Used for Energy Storage Applications

Upcycling plastic into advanced carbons, such as graphite and graphene, offers attractive options to manage waste streams by converting the plastic into carbon electrode materials for energy storage devices. However, polyethylene (PE) is notoriously difficult to upcycle because it decomposes into light gases at approximately 350-400 °C which prevents processing it at higher temperatures to convert it into advanced carbons. This work addresses this challenge by oxidatively functionalizing PE between 300-330 C which stabilizes it for higher temperature processing into graphite & graphene. In addition, the graphite & graphene are tested as lithium-ion battery or supercapacitor electrodes where their electrochemical performances outperform commercial materials.

graphene↗