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At least 415 records · Page 23

Microstructure and property characterization of sintered Si3N4, SiC, and SiAlON

Commercially-produced, pressureless sintered Si3N4, SiC, and SiAlON were characterized with respect to density, phases present, bend strength, and oxidation resistance. The room-temperature bend strengths of sintered Si3N4, SiC, and SiAlON are comparable. However, the room-temperature strengths are much lower (approximately 40 to 50%) than the room-temperature strength of hot-pressed Si3N4 (NC-132). The strength loss in Si3N4 and SiAlON materials at high temperature was attributed to a viscous grain-boundary phase, retained during cooling from the sintering temperature. The oxidation resistance of sintered alpha-SiC was the best of any materials tested.

Dutta, S.↗

In situ probing of interfacial roughness and transient phases during ceramic cold sintering process

The ceramic cold sintering process (CSP) offers an eco-friendly approach to producing fully dense ceramics at low temperatures. However, an incomplete mechanistic understanding hinders its optimization and widespread adoption. In this study, we analyze the microstructural and structural changes in ZnO, a model CSP system, using in situ synchrotron-based high-energy small-angle X-ray scattering and X-ray diffraction techniques. Our results reveal the time evolution of ZnO particles' surface area and roughness, reflecting the dissolution and re precipitation processes that enable densification. The in situ measurements supply valuable kinetic data for these stages of CSP. Alongside microstructural changes and densification, we observed the evolution of secondary phases representing reaction products between ZnO and acetic acid, the solvent used. The initial ZnO/solvent mixture's dominant secondary phase is attributed to zinc acetate, which is gradually replaced by a zinc soap-type structure during CSP. This structure has a large (≈ 21 Å) lattice parameter and is assumed to have a layered nature. The formation of this soap phase, which is retained in the sintered product as an intergranular component, appears to be a signature of successful cold sintering as it facilitates mass transport, leading to densification. Here, our study underscores the potential of in situ synchrotron characterization for revealing microstructural and phase-evolution details during CSP. These findings, which would be challenging to obtain through ex situ measurements, provide crucial data to guide and validate theoretical models, ultimately enhancing CSP's effectiveness and adoption.

36 MATERIALS SCIENCE↗

Developing Robust Ceria-Supported Catalysts for Catalytic NO Reduction and CO/Hydrocarbon Oxidation

Synthesis of robust and hydrothermally stable PGM/ceria materials for NO, CO, and hydrocarbon abatement remains a formidable challenge, as ceria and PGMs are known to sinter severely >800 °C under hydrothermal conditions, leading to irreversible activity loss. In this work, we tackle this challenge by synthesizing well-defined catalysts with atomically dispersed rhodium supported on ceria with varying abundance of (100), (101), and (111) facets. Evaluation of these catalysts for NO reduction by CO as well as CO and propylene oxidation under model and industrially relevant conditions reveals pronounced reactivity and stability differences. Different modes of interaction of Rh ions with the ceria facets and their facile reducibility were shown to be the crucial parameters controlling reactivity, resulting in pronounced activity and stability variations. Facet-dependent poisoning of surfaces by nitrites was identified as the main reason for deactivation of the catalysts at low temperature, which is mitigated for (111) ceria facets. (111)-enriched ceria nanoparticles survive very harsh hydrothermal aging at 950 °C by maintaining and preserving (111) facets, unlike other ceria nanoparticles which sinter into poorly defined shapes. Thus, putting atomically dispersed PGM sites on (111) ceria facets lead to the catalytic material with the highest activity and stability for all studied reactions, providing the pathway to catalysts that can endure extremely harsh hydrothermal aging conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Laboratory studies on cometary crust formation: The importance of sintering

It is demonstrated by experiments and theoretical considerations that sintering processes, so far used to describe the densification of metal and ceramic powders, are relevant for icy materials and therefore probably also for comets. A theoretical model is presented which describes the evolution of so called sinter necks, the contact zone between ice particles. With this model the strength increase of a porous, loosley packed icy body is calculated in which the sinter necks grow by evaporation and condensation of water vapor at a constant temperature. Experiments with ice powders validate the model qualitatively. An increase in strength up to a factor of four is observed during isothermal sintering. In order to check the relevance of the experimental results and the basic theoretical ideas with respect to real comets, more exact theories and improved experiments taking into account additional mass transport mechanisms are needed.

Ratke, L.↗

Low-Thermal-Conductivity Pyrochlore Oxide Materials Developed for Advanced Thermal Barrier Coatings

When turbine engines operate at higher temperatures, they consume less fuel, have higher efficiencies, and have lower emissions. The upper-use temperatures of the base materials (superalloys, silicon-based ceramics, etc.) used for the hot-section components of turbine engines are limited by the physical, mechanical, and corrosion characteristics of these materials. Thermal barrier coatings (TBCs) are applied as thin layers on the surfaces of these materials to further increase the operating temperatures. The current state-of-the-art TBC material in commercial use is partially yttria-stabilized zirconia (YSZ), which is applied on engine components by plasma spraying or by electron-beam physical vapor deposition. At temperatures higher than 1000 C, YSZ layers are prone to sintering, which increases thermal conductivity and makes them less effective. The sintered and densified coatings can also reduce thermal stress and strain tolerance, which can reduce the coating s durability significantly. Alternate TBC materials with lower thermal conductivity and better sintering resistance are needed to further increase the operating temperature of turbine engines.

Bansal, Narottam P.↗

Predicting Sintering Window of Binder Jet Additively Manufactured Parts Using a Coupled Data Analytics and CALPHAD Approach

Batch-to-batch variation in powder compositions for binder jet additive manufacturing (BJAM) can significantly deter defining an “ideal” sintering window for a given alloy. One way to overcome the problem is by running sintering experiments at various temperatures for each batch of the powder. However, such an approach increases the time required to achieve large-scale production of parts. The predictive capabilities of computational thermodynamic tools like CALPHAD can be leveraged to overcome the challenge, especially for binder jet additive manufacturing, since the process occurs under near-equilibrium conditions. However, calculating the sintering window using CALPHAD can be computationally expensive, considering many possible feedstock compositions within “specification”. Here, we generate high throughput CALPHAD data for nickel-based superalloys to develop machine learning models to predict the sintering window rapidly. The predictive capability of the models has been validated using published results on BJAM of Inconel 718 and 625. Further, validated models are lightweight and can be deployed in an industrial setting to get sintering window in an accelerated manner.

36 MATERIALS SCIENCE↗

Comparison of the contact stress and friction behavior of SiC and ZrO2 materials

Studies were performed to further elucidate the friction and contact-stress characteristics of structural ceramic materials. New data for fully stabilized and partially stabilized zirconia ceramics are compared with prior test results for sintered SiC. The comparison provides further evidence that the high temperature friction characteristics of sintered SiC are strongly influenced by the presence of a viscous surface layer. The results also show that a ceramic material with lower coefficient of friction and higher fracture toughness has increased resistance to strength-reducing surface damage due to contact stress.

Lindberg, L. J.↗

Tribological properties of PM212: A high-temperature, self-lubricating, powder metallurgy composite

This paper describes a research program to develop and evaluate a new high temperature, self-lubricating powder metallurgy composite, PM212. PM212 has the same composition as the plasma-sprayed coating, PS212, which contains 70 wt percent metal-bonded chromium carbide, 15 wt percent silver and 15 wt percent barium fluoride/calcium fluoride eutectic. The carbide acts as a wear resistant matrix and the silver and fluorides act as low and high temperature lubricants, respectively. The material is prepared by sequential cold press, cold isostatic pressing and sintering techniques. In this study, hemispherically tipped wear pins of PM212 were prepared and slid against superalloy disks at temperatures from 25 to 850 C in air in a pin-on-disk tribometer. Friction coefficients range from 0.29 to 0.38 and the wear of both the composite pins and superalloy disks was moderate to low in the 10(exp -5) to 10(exp -6) cubic mm/N-m range. Preliminary tests indicate that the material has a compressive strength of at least 130 MPa over the entire temperature range of 25 to 900 C. This material has promise for use as seal inserts, bushings, small inside diameter parts and other applications where plasma-sprayed coatings are impractical or too costly.

Dellacorte, Christopher↗

Tribological properties of PM212 - A high temperature, self-lubricating, powder metallurgy composite

This paper describes a research program to develop and evaluate a new high temperature, self-lubricating powder metallurgy composite, PM212. PM212 has the same composition as the plasma-sprayed coating, PS212, which contains 70 wt percent metal-bonded chromium carbide, 15 wt percent silver and 15 wt percent barium fluoride/calcium fluoride eutectic. The carbide acts as a wear resistant matrix and the silver and fluorides act as low and high temperature lubricants, respectively. The material is prepared by sequential cold press, cold isostatic pressing and sintering techniques. In this study, hemispherically tipped wear pins of PM212 were prepared and slid against superalloy disks at temperatures from 25 to 850 C in air in a pin-on-disk tribometer. Friction coefficients range from 0.29 to 0.38 and the wear of both the composite pins and superalloy disks was moderate to low in the 10(exp -5) to 10(exp -6) cubic mm/N-m range. Preliminary tests indicate that the material has a compressive strength of at least 130 MPa over the entire temperature range of 25 to 900 C. This material has promise for use as seal inserts, bushings, small inside diameter parts and other applications where plasma-sprayed coatings are impractical or too costly.

Dellacorte, Christopher↗

3D-printed electrically conductive silicon carbide

The development of electrically conductive ceramics could achieve robust mechanical strength as well as practically high conductivity, offering applications in structural electrodes, conductors, catalyst supports, etc. However, its operating temperature is limited due to the intrinsic dense structures inevitably hindering the thermal management capability, thus resulting in a temperature-dependent electrical behavior in high-temperature environments. In this work, we report an additive manufacturing protocol through vat photopolymerization 3D printing to fabricate the architectured conductive silicon carbide (SiC) ceramics that simultaneously possess high electrical conductivity as well as low thermal conductivity, and demonstrate electric reliability under high-temperature environments above 600°C. The percolation of graphene into the ceramic scaffold establishes a uniform conductive network, exhibiting its electrical conductivity up to 1000 S m –1 . The bulk density of the 3D-printed ceramic is measured from 0.366 g cm –3 to 0.897 g cm –3 , with thermal conductivity ranging from 62 mW m –1 K –1 to 88 mW m –1 K –1 . Furthermore, the mechanical performance of conductive ceramic can be effectively reinforced by densifying the microstructures via spark plasma sintering treatment. The proposed additive manufacturing strategy widens the potential of ceramics as a structural and functional material, offering a promising pathway toward high-temperature electronics applications.

36 MATERIALS SCIENCE↗

Fabrication of sinterable silicon nitride by injection molding

Transformation of structural ceramics from the laboratory to production requires development of near net shape fabrication techniques which minimize finish grinding. One potential technique for producing large quantities of complex-shaped parts at a low cost, and microstructure of sintered silicon nitride fabricated by injection molding is discussed and compared to data generated from isostatically dry-pressed material. Binder selection methodology, compounding of ceramic and binder components, injection molding techniques, and problems in binder removal are discussed. Strength, oxidation resistance, and microstructure of sintered silicon nitride fabricated by injection molding is discussed and compared to data generated from isostatically dry-pressed material.

Quackenbush, C. L.↗

Chemically Inert Hydrocarbon-Based Slurries for Rapid Laser Sintering of Thin Proton-Conducting Ceramics

The process of rapid laser sintering of thin BaZrO 3 –BaCeO 3 -based proton-conducting electrolytes is being developed for easy fabrication of ceramic fuel cells and electrolyzers. However, cracks on the electrolytes caused by volume change due to chemical reactions between the basic ceramic constituents and the polar solvents during wet processing has been problematic. In order to address this issue, the use of chemically inert saturated-hydrocarbon-based slurries comprised of hexadecane, polybutene, and a long-chain saturated fatty acid were investigated in this work. By optimizing slurry composition and laser sintering conditions, a 20 mm long, 4 mm wide, 13.5-μm-thick and 97%-dense BaCe 0.7 Zr 0.1 Y 0.07 Sm 0.13 O 3-d membrane showing proton conductivity on the order of 10 –4 S•cm –1 at 600 °C was successfully prepared in just three seconds by laser sintering. As a result, the use of saturated-hydrocarbon-based slurries will facilitate wet processing and rapid laser sintering of proton-conducting ceramic electrolytes.

36 MATERIALS SCIENCE↗

Development of Binder Jet Compatible Silicon Carbide Mixtures for Increased Sintered Density

Binder jet additive manufacturing can process a variety of ceramic powder feedstocks to manufacture near net shape green parts that are subsequently sintered to achieve densification. In particular, silicon carbide (SiC) is a promising ceramic material for heat exchangers in energy storage applications and binder jet is a well-suited process for manufacturing these heat exchangers due to the often geometrically complex designs. However, the need for good powder flowability in binder jet printing often limits the feedstock powder to be larger particles rather than that of ultra fine submicron powders used in conventional ceramic processing, which are more readily densified during sintering. The present work explores the use of various powder mixtures and sintering settings to identify strategies for achieving high density sintered parts in binder jet compatible systems without the use of infiltration. Liquid-phase sintering additives and bimodal powder mixtures are explored alongside different sintering temperatures, rates, atmospheres, and hold times. Two mixtures were found to be good candidates for further exploration: 1) 90 wt% 0.6 µm SiC + 6.25 wt% Al 2 O 3 + 3.75 wt% Y 2 O 3 mixture achieved the highest sintered relative density of 91.2%; and 2) a bimodal mixture comprised of 45 wt% 10 µm SiC + 45 wt% 0.6 µm SiC + 6.25 wt% Al 2 O 3 + 3.75 wt% Y 2 O 3 had the best powder flowability of the powders measured and a 75.1% sintered relative density.

25 ENERGY STORAGE↗

Method for Molding Planar Billet of Thermally Insulative Material Into Predetermined Non-Planar Shape

A method and apparatus is discussed for molding thermal protection system (TPS) tiles for spacecraft. The apparatus and method include a bottom mold member defining a mold surface shaped like a surface of the spacecraft, e.g., the nose cap of wing leading edge, sought to be thermally protected. A flat billet of TPS material is positioned over the periphery of the mold surface, and a hollow weight element that has a periphery configured like the periphery of the mold surface is positioned on the billet. The billet is then heated in accordance with a predetermined heating regime, and during the heating process the weight of the weight element causes the billet to deform to assume the shape of the mold surface. If desired, a TUFI coating is impregnated into the billet prior to heating, and the coating is sintered to the billet during heating. After heating, a composite matrix material, e.g., a graphite or fiberglass cloth which is impregnated with epoxy or polimide, is bonded to the now-shaped tile to support the tile. Silicone can then be impregnated into the now-formed tile to provide flexibility of the tile.

Kolodziej, Paul↗

Synthesis and Photonic Sintering of Proton Conducting Lanthanide Nickelates

Lanthanide nickelate perovskites are known proton conductors at intermediate temperatures (350-600°C). They are attractive targets for proton conducting fuel cells and electrolyzers due to their operational temperature range and their stability in the presence of CO 2 . These materials have the formula LNiO 3 , with the lanthanide L = La, Ce, Pr, Nd, or Sm. Sintering is challenging due to phase transformations that occur at lower temperatures than those required for sintering. In this project, a series of lanthanide nickelate perovskites was synthesized via both a precursor solid solution method and the glycine nitrate process. Powders derived from the precursor solid solution method for LaNiO 3 and NdNiO 3 were sintered at Utility Global Inc. at various temperatures utilizing fast photonic sintering. LaNiO 3 was successfully sintered while maintaining the perovskite phase. NdNiO 3 underwent a phase transformation at all the conditions tested. The stability of the perovskite phase decreases moving right across the lanthanides in the periodic table, while the expected proton conductivity increases. These results will inform further investigations into lanthanide nickelate perovskites toward the goal of producing a free-standing, sintered, proton-conducting membrane.

36 MATERIALS SCIENCE↗

High-Temperature Proton-Conducting Ceramics Developed

High-temperature protonic conductors (HTPC) are needed for hydrogen separation, hydrogen sensors, fuel cells, and hydrogen production from fossil fuels. The HTPC materials for hydrogen separation at high temperatures are foreseen to be metal oxides with the perovskite structure A(sup 2+)B(sup 4+)C(sup 2-, sub 3) and with the trivalent cation (M(sup 3+)) substitution at the B(sup 4+)-site to introduce oxygen vacancies. The high affinity for hydrogen ions (H(sup +)) is advantageous for protonic transport, but it increases the reactivity toward water (H2O) and carbon dioxide (CO2), which can lead to premature membrane failure. In addition, there are considerable technological challenges related to the processing of HTPC materials. The high melting point and multi-cation chemistry of HTPC materials creates difficulties in in achieving high-density, single-phase membranes by solid-state sintering. The presence of secondary phases and grain-boundary interfaces are detrimental to the protonic conduction and environmental stability of polycrystalline HTPC materials.

Sayir, Ali↗

Production of Readily Compressible Dies for the Enhanced Sintering of Solids (PRESS) Preliminary Investigations

Non-oxide ceramics, which consist of predominantly carbides, borides, and nitrides, are of great interest to modern engineering because of their resistance to extreme conditions. Properties of such materials include high temperature resistance, high hardness, chemical resistance, and high fracture toughness. However, the main method for manufacturing parts of these materials is by machining cylindrical billets to the desired geometry. Not only does this produce waste, but the cost of machining is high since the part materials are of such high hardness. This method is used because these non-oxide ceramics must be sintered to high density using simultaneous heat and pressure within a hot-pressing unit. These units are inherently restricted to cylindrical geometries. A proposed way to expand the capabilities of a hot-press is by using intermediate compressible dies. This method consists of surrounding a ceramic part green body with a material that will shrink at the same rate as the part and survive the hot-pressing conditions. At the end, the compressible die material would be removed leaving a nearly net shaped hot-pressed part. In this study, graphite powder was investigated as the compressible die material with its shrinkage rate being controlled by particle size mixing. Both ceramic materials and graphite were then cast into parts and compressible dies respectively to show the feasibility of the compressible die hot-pressing method.

36 MATERIALS SCIENCE↗