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At least 487 records · Page 27

Oxidation of Al2O3 continuous fiber-reinforced/NiAl composites

The 1200 C and 1300 C isothermal and cyclic oxidation behavior of Al2O3 continuous fiber-reinforced/NiAl composites were studied. Oxidation resulted in formation of Al2O3 external scales in a similar manner as scales formed on monolithic NiAl. The isothermal oxidation of an Al2O3/NiAl composite resulted in oxidation of the matrix along the fiber/matrix interface near the fiber ends. This oxide acted as a wedge between the fiber and the matrix, and, under cyclic oxidation conditions, led to further oxidation along the fiber lengths and eventual cracking of the composite. The oxidation behavior of composites in which the Al2O3 fibers were sputter coated with nickel prior to processing was much more severe. This was attributed to open channels around the fibers which formed during processing, most likely as a result of the diffusion of the nickel coating into the matrix.

Doychak, J.↗

Space environmental effects on LDEF composites: A leading edge coated graphite epoxy panel

The electronics module cover for the leading edge (Row D 9) experiment M0003-8 was fabricated from T300 graphite/934 epoxy unidirectional prepreg tape in a (O(sub 2), +/- 45, O(sub 2), +/- 45, 90, 0)(sub s) layup. This 11.75 in x 16.75 in panel was covered with thermal control coatings in three of the four quadrants with the fourth quadrant uncoated. The composite panel experienced different thermal cycling extremes in each quadrant due to the different optical properties of the coatings and bare composite. The panel also experienced ultraviolet (UV) and atomic oxygen (AO) attack as well as micrometeoroid and space debris impacts. An AO reactivity of 0.99 x 10(exp -24) cm(sup 3)/atom was calculated for the bare composite based on thickness loss. The white urethane thermal control coatings (A276 and BMS 1060) prevented AO attack of the composite substrate. However, the black urethane thermal control coating (Z306) was severely eroded by AO, allowing some AO attack of the composite substrate. An interesting banding pattern on the AO eroded bare composite surface was investigated and found to match the dimensions of the graphite fiber tow widths as prepregged. Also, erosion depths were greater in the darker bands. Five micrometeoroid/space debris impacts were cross sectioned to investigate possible structural damage as well as impact/AO interactions. Local crushing and delaminations were found to some extent in all of the impacts. No signs of coating undercutting were observed despite the extensive AO erosion patterns seen in the exposed composite material at the impact sites. An extensive microcrack study was performed on the panel along with modeling of the thermal environment to estimate temperature extremes and thermal shock. The white coated composite substrate displayed almost no microcracking while the black coated and bare composite showed extensive microcracking. Significant AO erosion was seen in many of the cracks in the bare composite.

George, Pete E.↗

A mean field homogenization model for the mechanical response of ceramic matrix composites

SiC/SiC composites offer exceptional mechanical stability at high temperatures and under irradiation. These ceramic matrix composites are therefore strong candidate materials for future nuclear energy applications. Their mechanical response, which exhibits pseudo-plasticity, is mediated by matrix cracking, fiber debonding, and fiber pull-out due to slip. Here, this study introduces a mechanistic model for the behavior of unidirectionally reinforced SiC/SiC composites. Specifically a mean field homogenization approach is proposed to account for all deformation and degradation modes during mechanical deformation. The homogenization scheme relies on a Mori Tanaka method that is extended to consider the effects of the coating’s elasto-plastic response on the development of micromechanical fields. Further, the model proposed introduces a method to effectively account for the role of localized damage (i.e., cracks) on mechanical fields within both the fiber and the matrix. Upon validating the model against experimental data, the roles of interface sliding, coating dimensions and intrinsic elastic response, as well as of microstructure (e.g. porosity, fiber volume fraction) are discussed.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

The Application of Poly(3-hexylthiophene-2,5-diyl) as a Protective Coating for High Rate Cathode Materials

Poly (3-hexylthiophene-2,5-diyl) (P3HT), a conducting polymer studied extensively for its optoelectronic devices, offers a number of advantageous properties when used as a conductive binder for lithium-ion battery cathode materials. By mixing with carbon nanotubes (CNT), P3HTCNT serves as a surface coating for the cathode material LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA). Oxidation of the P3HT enables high electronic and ionic conductivity to be achieved over the potential range where the NCA is electrochemically active. In addition to the conductivity benefits from electrochemical doping, the P3HT-CNT coating suppresses electrolyte breakdown, thus inhibiting growth of the solid electrolyte interphase (SEI) layer and preventing intergranular cracking in the NCA particles. In conclusion, The use of the P3HT-CNT binder system leads to improved cycling for NCA at high power density with capacities of 80 mAh g -1 obtained after 1000 cycles at 16C, a value that is 4 times greater than what is achieved in the control electrode.

36 MATERIALS SCIENCE↗

XPS and SAM studies of the surface chemistry of lunar impact glasses including 12054

We report and discuss quantitative X-ray photoemission (XPS) analyses of mm size areas and qualitative scanning Auger microprobe (SAM) analyses of micron size areas on the surfaces of impact glass coatings found on fragments in the 14161 coarse fines and on the top surface, and a reentrant crack surface of rock 12054. The data suggest that some segregation occurs during impact glass formation leading to surface enrichments in Si and depletions in Mg, Al, Ca, and Ti. The magnitude of the effect appears fairly small, although the complexity of the surfaces severely complicates the data analysis. Because of the complexity of the surfaces, both XPS and SAM data were essential. A search for direct evidence of either solar wind sputter erosion or vapor deposition on the exposed top surface of 12054 provided interesting results which we cannot yet fully interpret. Both this surface and the surface from the re-entrant crack showed enrichments of more than a factor of two in Fe with respect to the bulk.

Housley, R. M.↗

Thermal fatigue behavior of H-13 die steel for aluminum die casting with various ion sputtered coatings

Sputtered coatings of Mo, W, Pt, Ag, Au, Co, Cr, Ni, Ag + Cu, Mo + Pt, Si3N4, A1N, Cr3C2, Ta5Si3, and ZrO2 were applied to a 2-inch-square, 7-inch-long thermal fatigue test specimen which was then internally water cooled and alternately immersed in molten aluminum and cooled in air. After 15,000 cycles the thermal fatigue cracks at the specimen corners were measured. Results indicate that a significant improvement in thermal fatigue resistance was obtained with platinum, molybdenum, and tungsten coatings. Metallographic examination indicates that the improvement in thermal fatigue resistance resulted from protection of the surface of the die steel from oxidation. The high yield strength and ductility of molybdenum and tungsten contributed to the better thermal fatigue resistance.

Nieh, C. Y.↗

Melting temperature, emissivity, and thermal conductivity of rare-earth silicates for thermal and environmental barrier coatings

In recent years, rare-earth silicates have become the industry standard for coating state-of-the-art SiC ceramic matrix composite (CMC) gas turbine engine components, due to their low volatility, high melting point, and thermal shock resistance. Current research is focused on designing rare-earth silicate based thermal-environmental barrier coatings (T/EBCs) with improved resistance to CMAS (CaO-MgO-Al 2 O 3 -SiO 2 ), steam, and crack formation, while maintaining high temperature performance and stability. Here, in this work we compare the high temperature performance of a variety of single and multi-component rare-earth mono- and disilicates (MS, DS) and rare earth apatites by measuring their melting points and spectrally averaged visible emissivities using laser heating and radiation pyrometry. We also report room temperature thermal conductivity measured by time-domain thermoreflectance (TDTR).

Environmental barrier coatings↗

Copper extraction from coarsely ground printed circuit boards using moderate thermophilic bacteria in a rotating-drum reactor

Highlights: • Copper bioleaching from PCB (20 mm) by moderate thermophiles was demonstrated. • Larger PCB sheets enable a cost reduction due to the elimination of fine grinding. • Crushing generated cracks in PCB increasing the copper extraction. • A pre-treatment step was necessary to remove the lacquer coating. • High copper extractions (85%) were possible with pulp density of up to 25.0 g/L. - Abstract: The current work reports on a new approach for copper bioleaching from Printed Circuit Board (PCB) by moderate thermophiles in a rotating-drum reactor. Initially leaching of PCB was carried out in shake flasks to assess the effects of particle size (−208 μm + 147 μm), ferrous iron concentration (1.25–10.0 g/L) and pH (1.5–2.5) on copper leaching using mesophile and moderate thermophile microorganisms. Only at a relatively low solid content (10.0 g/L) complete copper extraction was achieved from the particle size investigated. Conversely, high copper extractions were possible from coarse-ground PCB (20 mm-long) working with increased solids concentration (up to 25.0 g/L). Because there was as the faster leaching kinetics at 50 °C Sulfobacillus thermosulfidooxidans was selected for experiments in a rotating-drum reactor with the coarser-sized PCB sheets. Under optimal conditions, copper extraction reached 85%, in 8 days and microscopic observations by SEM–EDS of the on non-leached and leached material suggested that metal dissolution from the internal layers was restricted by the fact that metal surface was not entirely available and accessible for the solution in the case of the 20 mm-size sheets.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A uranium bed with ceramic body for tritium storage

It is widely recognized that ceramic coatings provide an attractive solution to lower tritium permeation in structural materials. Alumina based ceramic coatings have the highest permeation reduction factor for hydrogen. For this reason an attempt was made to apply crack-free low porous ceramics as a structural material of a bed body for tritium storage in a setup used for hydrogenating neutron tube targets at VNIIA. The present article introduces the design of the bed. This bed possesses essentially a lower hydrogen permeation factor than traditionally beds with stainless steel body. Bed heating in order to recover hydrogen from the bed is suggested to be implemented by high frequency induction means. Inductive heating allows decreasing the time necessary for tritium release from the bed as well as power consumption. Both of these factors mean less thermal power release into glove box where a setup for tritium handling is installed and thus causes fewer problems with pressure regulations inside the glove box. Inductive heating allows raising tritium sorbent material temperature up to melting point. The latter allows achieving nearly full tritium recovery.

36 MATERIALS SCIENCE↗

Microstructure and Tensile Properties of BN/SiC Coated Hi-Nicalon, and Sylramic SiC Fiber Preforms

Batch to batch and within batch variations, and the influence of fiber architecture on room temperature physical and tensile properties of BN/SiC coated Hi-Nicalon and Sylramic SiC fiber preform specimens were determined. The three fiber architectures studied were plain weave (PW), 5-harness satin (5HS), and 8-harness satin (8HS). Results indicate that the physical properties vary up to 10 percent within a batch, and up to 20 percent between batches of preforms. Load-reload (Hysteresis) and acoustic emission methods were used to analyze damage accumulation occurring during tensile loading. Early acoustic emission activity, before observable hysteretic behavior, indicates that the damage starts with the formation of nonbridged tunnel cracks. These cracks then propagate and intersect the load bearing "0 deg" fibers giving rise to hysteretic behavior. For the Hi-Nicalon preform specimens, the onset of "0 deg" bundle cracking stress and strain appeared to be independent of the fiber architecture. Also, the "0 deg" fiber bundle cracking strain remained nearly the same for the preform specimens of both fiber types. TEM analysis indicates that the CVI BN interface coating is mostly amorphous and contains carbon and oxygen impurities, and the CVI SiC coating is crystalline. No reaction exists between the CVI BN and SiC coating.

Bhatt, Ramakrishna T.↗

In situ characterization of foreign object damage (FOD) in environmental-barrier-coated silicon carbide (SiC) ceramic

Environmental barrier coatings (EBCs) protect advanced ceramics and ceramic matrix composites (CMCs) from oxidation and corrosion in gas turbine engine environments. Foreign object damage (FOD), where debris impact the protective coatings, is a critical hazard which limits the turbine durability. Despite previous efforts to understand FOD in EBCs, a detailed understanding of the fundamental transient damage mechanisms is still lacking. In the current work, the real-time FOD behavior of a Mullite / Silicon EBC was visualized via a dynamic synchrotron X-ray source in phase contrast imaging (PCI) configuration. Prior to the in situ FOD experiments, the microstructure and composition of the coating were respectively characterized using a scanning electron microscope (SEM) and X-ray diffraction (XRD). The variation in the properties of the debris was modeled by ~ 1.5 mm diameter Partially Stabilized Zirconia (PSZ) and Silicon Nitride (Si 3 N 4 ) spheres. A modified light-gas gun setup, synchronized with the X-ray beam, was used to propel the projectiles at velocities ranging between 300 and 355 m·s -1 . Coated samples were impacted under a fully backed support configuration and at normal incidence. Coating penetration and delamination, as well as projectile deformation at the bond coat resulted for FOD by PSZ spheres. Comparatively, projectile fracture, with subsequent rebound of fragments, as well as complete coating penetration and delamination at the substrate interface occurred for FOD by Si 3 N 4 spheres. It should be noted that only cone cracking was observed for FOD by PSZ spheres while back surface cracking was present for both projectile types. Qualitative understanding of the driving forces for the observed damage mechanisms were provided.

36 MATERIALS SCIENCE↗

Fracture resistance of a TiB2 particle/SiC matrix composite at elevated temperature

The fracture resistance of a commercial TiB 2 particle/SiC matrix composite was evaluated at temperatures ranging from 20 to 1400 °C. A laser interferometric strain gauge (LISG) was used to continuously monitor the crack mouth opening displacement (CMOD) of the chevron-notched and straight-notched, three-point bend specimens used. Crack growth resistance curves (R-curves) were determined from the load versus displacement curves and displacement calibrations. Fracture toughness, work-of-fracture, and R-curve levels were found to decrease with increasing temperature. Microstructure, fracture surface, and oxidation coat were examined to explain the fracture behavior.

Fracture↗

Development of Self-Healing Zirconium-Silicide Coatings for Improved Performance Zirconium-Alloy Fuel Cladding

Zirconium-alloy fuel claddings have been used successfully in Light Water Reactors (LWR) for over four decades. However, under high temperature accident conditions, zirconium-alloys fuel claddings exhibit profuse exothermic oxidation accompanied by release of hydrogen gas due to the reaction with water/steam. Additionally, the ZrO 2 layer can undergo monoclinic to tetragonal to cubic phase transformations at high temperatures which can induce stresses and cracking. These events were unfortunately borne out in the Fukushima-Daiichi accident in in Japan in 2011. In reaction to such accident, protective oxidation-resistant coatings for zirconium-alloy fuel claddings has been extensively investigated to enhance safety margins in accidents as well as fuel performance under normal operation conditions. Such surface modification could also beneficially affect fuel rod heat transfer characteristics. Zirconium-silicide, a candidate coating material, is particularly attractive because zirconium-silicide coating is expected to bond strongly to zirconium-alloy substrate. Intermetallic compound phases of zirconium-silicide have high melting points and oxidation of zirconium silicide produces highly corrosion resistant glassy zircon (ZrSiO 4 ) and silica (SiO 2 ) which possessing self-healing qualities. Given the long-term goal of developing such coatings for use with nuclear reactor fuel cladding, this work describes results of oxidation and corrosion behavior of bulk zirconium-silicide and fabrication of zirconium-silicide coatings on zirconium-alloy test flats, tube configurations, and SiC test flats. In addition, boiling heat transfer of these modified surfaces (including ZrSi 2 coating) during clad quenching experiments is discussed in detail.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Oxygen diffusion barrier coating

A method for coating a titanium panel or foil with aluminum and amorphous silicon to provide an oxygen barrier abrogating oxidation of the substrate metal is developed. The process is accomplished with known inexpensive procedures common in materials research laboratories, i.e., electron beam deposition and sputtering. The procedures are conductive to treating foil gage titanium and result in submicron layers which virtually add no weight to the titanium. There are no costly heating steps. The coatings blend with the substrate titanium until separate mechanical properties are subsumed by those of the substrate without cracking or spallation. This method appreciably increases the ability of titanium to mechanically perform in high thermal environments such as those witnessed on structures of space vehicles during re-entry

Unnam, Jalaiah↗

Conformal PEDOT Coating Enables Ultra-High-Voltage and High-Temperature Operation for Single-Crystal Ni-Rich Cathodes

Single-crystal Ni-rich Li[Ni x Mn y Co 1-x-y ]O 2 (SC-NMC) cathodes represent a promising approach to mitigate the cracking issue of conventional polycrystalline cathodes. However, many reported SC-NMC cathodes still suffer from unsatisfactory cycling stability, particularly under high charge cutoff voltage and/or elevated temperature. Herein, we report an ultraconformal and durable poly(3,4-ethylenedioxythiophene) (PEDOT) coating for SC-NMC cathodes using an oxidative chemical vapor deposition (oCVD) technique, which significantly improves their high-voltage (4.6 V) and high-temperature operation resiliency. The PEDOT coated SC LiNi 0.83 Mn 0.1 Co 0.07 O 2 (SC-NMC83) delivers an impressive capacity retention rate of 96.7% and 89.5% after 100 and 200 cycles, respectively. Significantly, even after calendar aging at 45 degrees C and 4.6 V, the coated cathode can still retain 85.3% (in comparison with 59.6% for the bare one) of the initial capacity after 100 cycles at a 0.5 C rate. Synchrotron X-ray experiments and interface characterization collectively reveal that the conformal PEDOT coating not only effectively stabilizes the crystallographic structure and maintains the integrity of the particles but also significantly suppresses the electrolyte's corrosion, resulting in improved electrochemical/thermal stability. Our findings highlight the promise of an oCVD PEDOT coating for single-crystal Ni-rich cathodes to meet the grand challenge of high-energy batteries under extreme conditions.

25 ENERGY STORAGE↗

NASA Glenn/AADC Collaboration Optimized Erosion Coatings for Inlet Guide Vanes

There is a need for lightweight, durable materials and structures to reduce the weight of propulsion systems. Polymer matrix composites (PMC's) are promising materials for aerospace applications because of their high strength-to-weight ratio relative to metals. Unfortunately, they are limited to applications where they are not exposed to hightemperature oxidizing atmospheres and/or particulates from ingested air. This is because oxidation and erosion occur on the surface, leading to weight loss, nodulation, and/or cracking on the surface, and a consequent decline of mechanical properties over time. Although prior research has shown that oxidation can be slowed when metallic or ceramic coatings are applied onto PMC's, there remains a need for erosion-resistant coatings that protect PMC's from high-velocity particulates in the engine flow path. These erosionresistant coatings could extend the life of polymer composites. Polymer composites are heavily damaged without an erosion-resistant coating because they are not as hard as metallic engine structures. The effectiveness and life of the coatings depends on their inherent properties as well as on the interaction between the coating and the PMC. Since polymers, in general, have high thermal expansion coefficients in comparison to metals and ceramics, failure of the coatings often occurs at this interface. The objective of this research is to develop strategies to improve this interface and tailor overlays for erosion resistance. The bondcoat, which was developed at the NASA Glenn Research Center, is composed of zinc blended with polyimides to improve the compatibility between the PMC and the overlay material. Initial coating trials at AADC produced vanes that had poor bonding between the overlay and bondcoats. Subsequently, Glenn successfully demonstrated that high-quality plasma-sprayed erosion coating systems could be applied to these guide vanes. Inlet guide vanes from AE 3007 engines fiber composites were coated using a coating system composed of a bondcoat and a hard topcoat. Optimization of the plasma spray process has led to plans for future erosion testing in gas turbine engine environments.

Sutter, James K.↗

Eliminating chemo-mechanical degradation of lithium solid-state battery cathodes during >4.5 V cycling using amorphous Nb2O5 coatings

Abstract Lithium solid-state batteries offer improved safety and energy density. However, the limited stability of solid electrolytes (SEs), as well as irreversible structural and chemical changes in the cathode active material, can result in inferior electrochemical performance, particularly during high-voltage cycling (>4.3 V vs Li/Li + ). Therefore, new materials and strategies are needed to stabilize the cathode/SE interface and preserve the cathode material structure during high-voltage cycling. Here, we introduce a thin (~5 nm) conformal coating of amorphous Nb 2 O 5 on single-crystal LiNi 0.5 Mn 0.3 Co 0.2 O 2 cathode particles using rotary-bed atomic layer deposition (ALD). Full cells with Li 4 Ti 5 O 12 anodes and Nb 2 O 5 -coated cathodes demonstrate a higher initial Coulombic efficiency of 91.6% ± 0.5% compared to 82.2% ± 0.3% for the uncoated samples, along with improved rate capability (10x higher accessible capacity at 2C rate) and remarkable capacity retention during extended cycling (99.4% after 500 cycles at 4.7 V vs Li/Li + ). These improvements are associated with reduced cell polarization and interfacial impedance for the coated samples. Post-cycling electron microscopy analysis reveals that the Nb 2 O 5 coating remains intact and prevents the formation of spinel and rock-salt phases, which eliminates intra-particle cracking of the single-crystal cathode material. These findings demonstrate a potential pathway towards stable and high-performance solid-state batteries during high-voltage operation.

Science & Technology - Other Topics↗

Deformation and Tensile Cyclic Fatigue of Plasma-Sprayed ZrO2-8wt% Y2O3 Thermal Barrier Coatings

Deformation (constitutive relations) of free-standing, thick thermal barrier coatings of sprayed ZrO2-8Wt% Y2O3 was determined at ambient temperature in both pure tension and pure compression using cylindrical bar test specimens. The material exhibited both significant nonlinearity and hysteresis in its load-strain curves, The load-strain relations in four-point uniaxial flexure were determined from tension and compression sides and were compared with individual pure tension and compression constitutive data. Effect of sintering on deformation behavior was significant, resulting in a dramatic change in constitutive relation. Cyclic fatigue testing of the coating material in tension-tension at room temperature showed an insignificant susceptibility to fatigue, similar to the slow crack growth behavior of the material in flexure in 800 C air.

Choi, Sung R.↗