Search NASA⌕ Search

SEARCH · Search NASA

Results for “reaction sintering”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 73 records · Page 4

Cyclic Failure Mechanisms of Thermal and Environmental Barrier Coating Systems Under Thermal Gradient Test Conditions

Plasma-sprayed ZrO2-8wt%Y2O3 and mullite+BSAS/Si multilayer thermal and environmental barrier coating (TBC-EBC) systems on SiC/SiC ceramic matrix composite (CMC) substrates were thermally cyclic tested under high thermal gradients using a laser high-heat-flux rig in conjunction with furnace exposure in water-vapor environments. Coating sintering and interface damage were assessed by monitoring the real-time thermal conductivity changes during the laser heat-flux tests and by examining the microstructural changes after exposure. Sintering kinetics of the coating systems were also independently characterized using a dilatometer. It was found that the coating failure involved both the time-temperature dependent sintering and the cycle frequency dependent cyclic fatigue processes. The water vapor environments not only facilitated the initial coating conductivity increases due to enhanced sintering and interface reaction, but also promoted later conductivity reductions due to the accelerated coating cracking and delamination. The failure mechanisms of the coating systems are also discussed based on the cyclic test results and are correlated to the sintering and thermal stress behavior under the thermal gradient test conditions.

Zhu, Dongming↗

Solid-state reaction mediated microstructural evolution in a spark plasma sintered in situ Ti–B 4 C composite

For this study, a novel porosity-free in situ Ti–B 4 C composite was fabricated via spark plasma sintering (SPS). Detailed analysis of the phase evolution, coupling results from XRM, XRD and SEM-EBSD-EDS, indicate that primarily TiB 2 precipitates formed due to the in-situ reactions between the boron-carbide and titanium powders. The precipitation of TiB 2 resulted in the formation of a graphitic C-rich thin layer circumscribing the partially reacted B 4 C particles. Further progression of the in-situ reaction leads to the out-diffusion of the excess carbon from the B 4 C particles, across the graphite and TiB 2 phases, forming TiC upon reacting with the titanium matrix. Therefore, the final microstructure primarily consisted of TiB 2 , TiC, and partially reacted B 4 C phases, with small amounts of TiB, α-Ti, and graphite. Furthermore, the microstructure in these SPS processed in situ composites appeared to be the product of a solid-state Ti–B 4 C diffusion couple, substantially different from their fusion-based additively manufactured counterparts. Nano-indentation tests revealed a remarkably high average hardness of ~25 GPa for this SPS-processed Ti–B 4 C composite and comparable (with literature) phase-specific hardness and modulus values for the constituent TiB 2 , TiC, and B 4 C phases.

36 MATERIALS SCIENCE↗

Unravelling the sintering temperature-induced phase transformations in Ba(Fe 0.7 Ta 0.3 )O 3-δ ceramics

This work reports on the fundamental details of the crystal structure and phase transformations in Ba(Fe 0.7 Ta 0.3 )O 3-δ , the best known temperature-independent oxygen-sensing ceramic material for applications in extreme environments. Ba(Fe 0.7 Ta 0.3 )O 3-δ ceramics were synthesized using conventional solid-state ceramic reaction under variable sintering temperatures (T s = 1200–1350 °C). Combined X-ray diffraction (XRD) and high-resolution transmission electron microscopy (TEM) measurements revealed the T s -induced phase transformations and their origin in Ba(Fe 0.7 Ta 0.3 )O 3-δ . Associated with phase transformations, pseudo-cubic (PC) reflections, such as {200} PC , {211} PC , and {220} PC , exhibited distinct anomalies with increasing T s . At T s = 1200 °C, Ba(Fe 0.7 Ta 0.3 )O 3-δ stabilized in mixed orthorhombic + rhombohedral phases (Amm2 + R3m). With increasing T s (≥1250 °C), Ba(Fe 0.7 Ta 0.3 )O 3-δ ceramics stabilized in tetragonal/rhombohedral [P4mm + R3m] mixed phases, while variations in the quantity of the respective phases were observed. Because both structure and crystal chemistry play key roles in achieving enhanced performance in chemical sensing and catalytic converters, detailed understanding of the phase transformations and crystal structure of Ba(Fe 0.7 Ta 0.3 )O 3-δ ceramics, as derived in this work, will be useful to develop chemical sensors with optimum performance for high-temperature and corrosive environments.

36 MATERIALS SCIENCE↗

Semiconductor structural damage attendant to contact formation in III-V solar cells

In order to keep the resistive losses in solar cells to a minimum, it is often necessary for the ohmic contacts to be heat treated to lower the metal-semiconductor contact resistivity to acceptable values. Sintering of the contacts, however can result in extensive mechanical damage of the semiconductor surface under the metallization. An investigation of the detailed mechanisms involved in the process of contact formation during heat treatment may control the structural damage incurred by the semiconductor surface to acceptable levels, while achieving the desired values of contact resistivity for the ohmic contacts. The reaction kinetics of sintered gold contacts to InP were determined. It was found that the Au-InP interaction involves three consecutive stages marked by distinct color changes observed on the surface of the Au, and that each stage is governed by a different mechanism. A detailed description of these mechanisms and options to control them are presented.

Fatemi, Navid S.↗

Joint Theoretical and Experimental Study of the Electronic, Magnetic, and Lattice Phonon Dynamics Properties of Ca x Fe y O z Compounds Applied to CO 2 Capture

Unleashing energy innovation ensures a resilient and reliable energy supply. There is a critical need for the development of new carbon dioxide (CO 2 ) captors that have improved energy efficiency accompanied by lower capital and operational costs to ensure abundant, affordable, and secure energy. Among solid materials, CaO is a good CO 2 sorbent for capture technology due to its wide availability and low cost. However, CaO also suffers from some disadvantages, such as high calcination temperature, decreasing capability due to sintering, attrition, and reaction with SO x and NO x . In this study, we employed an ab initio thermodynamic approach and experimental measurements to improve its CO 2 capture performance during the cycles. To do so, we explored the electronic, magnetic, and lattice dynamic properties of a series of calcium ferrites (Ca x Fe y O z ) and applied them for CO 2 capture. Our results showed that all of them can thermodynamically react with CO 2 to form CaCO 3 and iron oxides. Compared to pure CaO capturing CO 2 , CaFe 3 O 4 , CaFe 2 O 4 , and Ca 2 Fe 2 O 5 could shift the CO 2 regeneration temperature to a lower range. The experimental measurements showed that CaFeO 2 is a good CO 2 captor with or without the presence of an O 2 presence. The calculated thermodynamic properties of Ca x Fe y O z capturing the CO 2 reactions can be used to find their operational temperature ranges for different CO 2 capture technologies.

CO2 capture↗

Effect of alkali metal addition on catalytic performance of Ag/ZrO 2 /SBA-16 catalyst for single-step conversion of ethanol to butadiene

Here, we describe how adding Na and K to a 4Ag/4ZrO 2 /SBA-16 catalyst enhances catalytic performance for single-bed conversion of ethanol to butadiene. While adding Na and K leads to a slight decrease in conversion (i.e., ~10% loss), the production of desired butadiene is significantly increased with up to 50% improvement in productivity for the 4Ag/4ZrO 2 /SBA-16 catalyst promoted with 0.5% Na. The reasons for this improvement are a beneficial decrease in Lewis acid site concentration and higher Ag dispersion when Na or K are added, which results in decreased activity involving ethanol dehydration to ethylene and diethyl ether. A remarkable butadiene selectivity of 75% was achieved while maintaining high conversion (i.e., 90%) with 0.5Na/4Ag/4ZrO 2 /SBA-16 catalyst. A 72-hour catalyst lifetime study shows that because of higher coke formation from polymerization of desired butadiene, catalyst deactivation occurs more rapidly with the 0.5Na/4Ag/4ZrO 2 /SBA-16 (55% loss in conversion) than with 4Ag/4ZrO 2 /SBA-16 (45% loss in conversion). However, this does not alter the advantageous effect of Na addition because the butadiene yield remained higher throughout the study period for 0.5Na/4Ag/4ZrO 2 /SBA-16. A key finding is that during the reaction, Na limits sintering of Ag particles and promotes selective coking of the acid sites responsible for ethylene and diethyl ether formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fabrication of ceramic components for advanced gas turbine engines

The AGT101 ceramic gas turbine engine feasibility study has made use of the slip casting of silicon or silicon nitride powders to produce either reaction-bonded or sintered components such as turbine rotors, turbine shrouds, and inner and outer diffusers. Attention is given to the effects of processing parameters on the microstructure and properties of the finished components; the parameters encompass powder particle size distribution, casting slip viscosity, pH, and solid content fraction. The green slip cast components were consolidated by nitriding, sintering, or sinter/HIPping.

Liu, F.↗

Bend strengths of reaction bonded silicon nitride prepared from dry attrition milled silicon powder

Dry attrition milled silicon powder was compacted, sintered in helium, and reaction bonded in nitrogen-4 volume percent hydrogen. Bend strengths of bars with as-nitrided surfaces averaged as high as 210 MPa at room temperature and 220 MPa at 1400 C. Bars prepared from the milled powder were stronger than those prepared from as-received powder at both room temperature and at 1400 C. Room temperature strength decreased with increased milling time and 1400 C strength increased with increased milling time.

Herbell, T. P.↗

Dynamic Copper Site Redispersion through Atom Trapping in Zeolite Defects

Single-site copper-based catalysts have shown remarkable activity and selectivity for a variety of reactions. However, deactivation by sintering in high-temperature reducing environments remains a challenge and often limits their use due to irreversible structural changes to the catalyst. Here, we report zeolite-based copper catalysts in which copper oxide agglomerates formed after reaction can be repeatedly redispersed back to single sites using an oxidative treatment in air at 550 °C. Under different environments, single-site copper in Cu–Zn–Y/deAlBeta undergoes dynamic changes in structure and oxidation state that can be tuned to promote the formation of key active sites while minimizing deactivation through Cu sintering. For example, single-site Cu 2+ reduces to Cu 1+ after catalyst pretreatment (270 °C, 101 kPa H 2 ) and further to Cu0 nanoparticles under reaction conditions (270–350 °C, 7 kPa EtOH, 94 kPa H 2 ) or accelerated aging (400–450 °C, 101 kPa H 2 ). After regeneration at 550 °C in air, agglomerated CuO was dispersed back to single sites in the presence and absence of Zn and Y, which was verified by imaging, in situ spectroscopy, and catalytic rate measurements. Ab initio molecular dynamics simulations show that solvation of CuO monomers by water facilitates their transport through the zeolite pore, and condensation of the CuO monomer with a fully protonated silanol nest entraps copper and reforms the single-site structure. Importantly, the capability of silanol nests to trap and stabilize copper single sites under oxidizing conditions could extend the use of single-site copper catalysts to a wider variety of reactions and allows for a simple regeneration strategy for copper single-site catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mullite fiber reinforced reaction bonded Si3N4 composites

Fracture toughnesses of brittle ceramic materials have been improved by introducing reinforcements and carefully tailored interface layers. Silicon carbide and Si3N4 have been emphasized as matrices of structural composites intended for high temperature service because they combine excellent mechanical, chemical, thermal and physical properties. Both matrices have been successfully toughened with SiC fibers, whiskers and particles for ceramic matrix composite (CMC) parts made by sintering, hot pressing or reaction forming processes. These SiC reinforced CMCs have exhibited significantly improved toughnesses at low and intermediate temperature levels, as well as retention of properties at high temperatures for selected exposures; however, they are vulnerable to attack from elevated temperature dry and wet oxidizing atmospheres after the matrix has cracked. Property degradation results from oxidation of interface layers and/or reinforcements. The problem is particularly acute for small diameter (-20 tim) polymer derived SiC fibers used for weavable toes. This research explored opportunities for reinforcing Si3N4 matrices with fibers having improved environmental stability; the findings should also be applicable to SiC matrix CMCs.

Saleh, T.↗

Additive manufacturing of silicon carbide for nuclear applications

Additive manufacturing (AM) is a rapidly evolving technology being considered for nuclear applications. A special focus on AM to fabricate nuclear-grade silicon carbide (SiC) is explored in this paper. First, we present currently available AM processing options for SiC. AM methods commonly used for other ceramics, in which the feedstocks are forms of polymers, powders, and/or reactive chemical vapors, are also applicable to SiC. SiC phases are formed by pyrolysis of pre-ceramic polymer, direct reaction of powder precursors, sintering of SiC powders, or chemical vapor deposition/infiltration. Second, we discuss how the different microstructures of SiC materials fabricated by various processing methods affect their behavior in nuclear environments. Third, we discuss state-of-the-art AM technologies for the fabrication of relatively pure SiC, which show great potential to retain its strength under neutron irradiation: (1) binder jet printing followed by chemical vapor infiltration, (2) laser chemical vapor deposition, and (3) selective laser sintering of SiC powders.

36 MATERIALS SCIENCE↗

Fractographic and microstructural evaluation of 3500-hour durability specimens

Long term durability testing of candidate ceramic materials for advanced gas turbine applications was performed. Specimens of the materials were exposed to combustion atmospheres under temperature cyclic conditions for times up to 3500 hours and at peak temperatures of 1200 and 1370 C. The specimen strengths after exposure were measured at room temperature and at 1200 C. In addition, a number of physical measurements were taken; however, no microstructural examination of the specimens was performed. Materials examined include: sintered alpha silicon carbide, sintered silicon nitride, and reaction bonded silicon nitride. Sample preparation techniques were developed to provide high quality thin-section specimens which can be examined by transmitted light or thinned using an ion mill for subsequent transmission electron microscopic examination. Specimen preparation techniques and the results of optical and electron microscopic examination of the reaction interfaces of the selected specimens are presented.

Miller, A. D.↗

Corrosion Issues for Ceramics in Gas Turbines

The requirements for hot-gas-path materials in gas turbine engines are demanding. These materials must maintain high strength and creep resistance in a particularly aggressive environment. A typical gas turbine environment involves high temperatures, rapid gas flow rates, high pressures, and a complex mixture of aggressive gases. Figure 26.1 illustrates the requirements for components of an aircraft engine and critical issues [1]. Currently, heat engines are constructed of metal alloys, which meet these requirements within strict temperature limits. In order to extend these temperature limits, ceramic materials have been considered as potential engine materials, due to their high melting points and stability at high temperatures. These materials include oxides, carbides, borides, and nitrides. Interest in using these materials in engines appears to have begun in the 1940s with BeO-based porcelains [2]. During the 1950s, the efforts shifted to cermets. These were carbide-based materials intended to exploit the best properties of metals and ceramics. During the 1960s and 1970s, the silicon-based ceramics silicon carbide (SiC) and silicon nitride (Si3N4) were extensively developed. Although the desirable high-temperature properties of SiC and Si3N4 had long been known, consolidation of powders into component-sized bodies required the development of a series of specialized processing routes [3]. For SiC, the major consolidation routes are reaction bonding, hot-pressing, and sintering. The use of boron and carbon as additives which enable sintering was a particularly noteworthy advance [4]. For Si3N4 the major consolidation routes are reaction bonding and hot pressing [5]. Reaction-bonding involves nitridation of silicon powder. Hot pressing involves addition of various refractory oxides, such as magnesia (MgO), alumina (Al2O3), and yttria (y2O3). Variations on these processes include a number of routes including Hot Isostatic Pressing (HIP), gas-pressure sintering, sinter-HIPing, and Encapsulation-HIPing. It is important to note that each process involves the addition of secondary elements, which later were shown to dramatically influence oxidation and corrosion behavior. As dense bodies of silicon-based ceramics became more readily available, their desirable high temperature properties were confirmed. These materials retained strength to very high temperatures (i.e. 1300-1400 C). Further, they were lightweight and made from abundant materials. SiC and Si3N4 therefore emerged as leading ceramic candidates for components in heat engines, designed to operate at higher temperatures for better performance and fuel efficiency. The first US programs for ceramics in heat engines have been reviewed [6]. Selected programs on ceramic engine parts are summarized here in regard to their contributions to understanding the corrosion behavior of a heat engine environment.

Jacobson, Nathan S.↗

Processing and microstructure of ZrB 2 –SiC composite prepared by reactive spark plasma sintering

In-situ formation of ZrB 2 –SiC composites was investigated by reactive spark plasma sintering of precursor powders according to the reaction B4C + 2ZrC + 3Si → 3SiC + 2ZrB 2 . The reaction and process presented here involves a diffusion reaction between B4C and ZrC which facilitates the formation of ZrB 2 , while liquid phase sintering of silicon facilitates atomic diffusion and combines with free C from the B4C and ZrC reaction to form SiC within minutes of heating and there were some residual unreacted precursor materials. An interpenetrating matrix of ZrB 2 –SiC was formed that shows increased fracture toughness (6.03 ± 0.45 MPa m 1/2 ) despite relatively low density (95 %).

36 MATERIALS SCIENCE↗

Electronic Structure, Chemical Bonding and Electrocatalytic Activity of Novel Ba(Fe0.7Ta0.3)O3-d Compounds

Ba(Fe0.7Ta0.3)O3-d (BFTO) compounds were synthesized using conventional, high-temperature solid-state ceramic reaction method by varying the sintering temperature (Ts=1200-1350 °C). The crystal structure, electronic structure and electrocatalytic activity of BFTO compounds were evaluated. Processing temperature induced phase transformations and structural quality influences the electronic structure and electrocatalytic activity of BFTO compounds. At Ts=1200 oC, Ba(Fe0.7Ta0.3)O3-d stabilizes in mixed phase of orthorhombic + rhombohedral phase (Amm2 + R3m). With increasing Ts (=1250 oC), Ba(Fe0.7Ta0.3)O3-d ceramics stabilize in tetragonal + rhombohedral [P4mm + R3m] mixed phase with a variation in the quantity of respective phases. High-resolution X-ray photoelectron spectroscopy of constituent elements, namely, Ba 3d, Fe2p, Ta 4f and O 1s reveal the electronic structure changes due to changes in chemical environment resulted from structural transformation. The electrocatalytic activity of BFTO was evaluated towards hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR). Though all the samples demonstrated appreciable electrocatalytic properties, the best electrochemical catalytic activity was shown by BFTO samples sintered at 1350 °C. BFTO-1350 oC showed an onset potential of -0.690 V vs. RHE for HER and an onset potential of 0.73 V vs. RHE for ORR indicating its significant electrocatalytic performance. A general increase in activity with sintering temperature is potentially due to the improved structural quality of the BFTO ceramics. In addition to offering the fundamental insights into solid state materials based on doped BaTiO3 for electrocatalysis, the present work may contribute to the design and development of materials for high-temperature electrocatalytic converters.

Ba(Fe0.7Ta0.3)O3-d, Phase Transformation↗

Rational synthesis of high-performance Ni-rich layered oxide cathode enabled via probing solid-state lithiation evolution

Lithium (Li)-ion batteries using nickel (Ni)-rich layered oxide cathode have been pursued with interest due to high practical energy density. A fundamental understanding of the reaction pathways and structural evolution of the solid-phase synthesis of these materials is crucial for their rational design and process development for mass production. In this work, structural evolution during solid-state synthesis was traced via in situ technique, with a particular emphasis on the lithiation reaction and migration of transition metal (TM) ions. The sintering process is governed by the competitive relationship of decomposition and lithiation reactions, which can be regulated through temperature windows. Controlling the melting point of the Li sources, as well as their affinity to cathode precursors, is highly desired to maintain the layered ordering of TM ions throughout the whole synthesis process, which simplifies the manufacturing process and improves the quality of the manufactured cathode material.

25 ENERGY STORAGE↗

Investigation of Solid Particle Reactors for Nonoxidative Dehydrogenation of Ethane: Toward Solar Thermal Ethylene Production

Concentrating solar power plants can generate renewable heat at temperatures well above those of most industrial processes. Ceramic particles irradiated with concentrated sunlight can store high-quality sensible heat and transfer this to power generation systems. These concepts and materials hold great potential to also enable thermal processes in the chemical industry, but effective strategies for transferring heat from thermal energy storage media into chemical reactors are still under development. This present work evaluated the thermal and chemical compatibility of various solid particle media (including quartz, bauxite, and alumina particles) integrated directly into tube reactors and the subsequent effects on reactor performance for the nonoxidative dehydrogenation of ethane reaction. Empty tube reactors without loaded particles (representing conventional ethane cracking coils) showed significant heat transfer limitations as the tube diameter was scaled. The incorporation of media into the reactor significantly aided heat transfer to the gaseous ethane reactant and increased its conversion by as much as 10% at similar space velocities. Despite direct contact with hydrocarbon gases, alumina and quartz media showed negligible coke formation. Even during reaction in 100% ethane feed gas at 825 °C, the average selectivity of the coke product was only 0.57% when using the quartz media. These materials further demonstrated excellent thermal stability during subsequent reoxidation in air at 800 °C, which simulated the reheating of particles in a circulating particle solar receiver. Conversely, high rates of coke formation, with a product selectivity of 27.5%, were observed on sintered bauxite particles during the reaction, likely promoted by transition metal constituents. These particles fractured upon reoxidation due to exotherms generated from coke combustion. In conclusion, while the use of cofed steam could mitigate attrition of redox-active particles, the ability of inert metal oxide particles to efficiently transfer heat to concentrated ethane reactant gas while suppressing side reactions or degradation suggests that these media could effectively couple solar thermal plants to reactors for next-generation production of ethylene and other critical chemicals.

Hydrocarbons↗