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At least 325 records · Page 18

Role of Si2N2O in the passive oxidation of chemically-vapor-deposited Si3N4

The results of two-step oxidation experiments on chemically-vapor-deposited Si3N4 and SiC at 1350 C show that a correlation exists between the presence of a Si2N2O interphase and the strong oxidation resistance of Si3N4. During normal oxidation, k sub p for SiC was 15 times higher than that for Si3N4, and the oxide scale on Si3N4 was found by SEM and TEM to contain a prominent Si2N2O inner layer. However, when oxidized samples are annealed in Ar for 1.5 h at 1500 C and reoxidized at 1350 C as before, three things happen: the oxidation k sub p increases over 55-fold for Si3N4, and 3.5-fold for SiC; the Si3N4 and SiC oxidize with nearly equal k sub p's; and, most significantly, the oxide scale on Si3N4 is found to be lacking an inner Si2N2O layer. The implications of this correlation for the competing models of Si3N4 oxidation are discussed.

Ogbuji, Linus U. J. T.↗

MoSi2-Base Composite for Engine Applications

The intermetallic compound MoSi2 has long been known as a high temperature material that has excellent oxidation resistance and electrical/thermal conductivity. Also its low cost, high melting point (2023 C), relatively low density (6.2 g/cm versus 8 g/cm for current engine materials), and ease of machining make it an attractive structural material. However, the use of MoSi2 has been hindered because of the brittle nature of the material at low temperatures, inadequate creep resistance at high temperatures, accelerated oxidation (also known as 'pest' oxidation) at temperatures between approximately 400 and 500 C, and a coefficient of thermal expansion (CTE) that is relatively high in comparison to potential reinforcing fibers such as SiC. This CTE mismatch between the fiber and the matrix resulted in severe matrix cracking during thermal cycling.

Hebsur, Mohan G.↗

A New Approach of Designing Superalloys for Low Density

New low-density single-crystal (LDS) alloy, have bee. developed for turbine blade applications, which have the potential for significant improvements in the thrust-to-weight ratio over current production superalloys. An innovative alloying strategy was wed to achieve alloy density reductions, high-temperature creep resistance, microstructural stability, and cyclic oxidation resistance. The alloy design relies on molybdenum as a potent. lower-density solid-solution strengthener in the nickel-based superalloy. Low alloy density was also achieved with modest rhenium levels tmd the absence of tungsten. Microstructural, physical mechanical, and environmental testing demonstrated the feasibility of this new LDS superalloy design.

MacKay, Rebecca A.↗

In-Situ TEM Molten Salt Corrosion

Molten salt reactors (MSRs) offer a compelling pathway for next-generation nuclear energy, with advantages in thermal efficiency, inherent safety, and flexible fuel management. Yet, halide-based molten salts introduce significant materials challenges, particularly alloy corrosion. Alloy performance in these environments ultimately depends on understanding how corrosion initiates and progresses at the nanoscale, however most existing models rely on post-exposure characterization, leaving degradation mechanisms largely inferred rather than directly observed. NiCr alloys have garnered interest in MSRs applications as the Ni-based matrix provides strength and creep resistance, while Cr content offers oxidation resistance in air. However, NiCr corrosion resistance in chloride salts has proven poor due to preferential chromium dissolution, the formation of Cr-depleted pathways, and grain-boundary attack. This work aims to directly visualize corrosion of Ni-20Cr exposed to LiCl-KCl using in-situ Transmission Electron Microscopy (TEM) to capture real-time microstructural evolution during corrosion. Experiments will be performed at ~800 °C under controlled pressure conditions while utilizing Energy-Dispersive X-ray Spectroscopy (EDS) to analyze elemental redistribution. Observation of chromium depletion fronts, associated surface restructuring, and localized chloride enrichment are expected. Ultimately, this study is expected to provide a link between microscale processes and the macroscopic degradation behaviors relevant to MSR operation in advanced reactor environments. Simultaneously, this approach enables future in-situ investigations regarding alloy composition, salt chemistry, and their influence on corrosion pathways and long-term stability.?

36 - MATERIALS SCIENCE↗

Heat resistant polymers of oxidized styrylphosphine

A flame resistant, nontoxic polymer which may be used safely in confined locations where there is inadequate ventilation is prepared either by polymerizing compounds having the formula R-N=P(C6H5)2(C6H4)CH=CH2 where R is an organic moeity selected from the group of (C6H5)2P(O)-, (C6H5O)2P(O)-, (C6H5)2 C3N3-, or their mixtures, or by reacting a polymer with an organic azide such as diphenylphosphinylazide, diphenyl-phosphorylazide, 2-azido-4,6-diphenly-5-triazine, 2,4-diazido-6-phenyl-s-triazine, trimethylsilyoazide, triphenylsilylazine, and phenylazine. The reaction of the styrylphosphine with the organozaide results in the oxidation of the trivalent phosphorus atom to the pentavalent state in the form of an unsaturated P=N linkage known as a phosphazene group.

Paciorek, K. J. L.↗

Effects of silicon additions on oxidation and mechanical behavior of the nickel-base superalloy B-1900

Test specimens with nominal additions of Si were tested in oxidation, thermal fatigue, sulfidation, tension, and stress rupture, and were also extensively studied metallographically. Alloy B-1900 modified with 0.6- or 1.2-wt% Si exhibited oxidation resistance equivalent to that of aluminide-coated B-1900 during cyclic, high-gas-velocity oxidation tests. Resistances to thermal fatigue and sulfidation were improved by the Si additions, but were not superior to aluminide-coated B-1900. Stress-rupture tests at 1000 C of specimens given the standard heat treatment to simulate an aluminide coating cycle showed Si to be detrimental. However, application of another heat treatment increased the rupture life of the alloy with 0.6-wt% Si to that of the unmodified B-1900 given the standard heat treatment.

Miner, R. V., Jr.↗

Reactive flash sintering and characterization of bulk high entropy nitrides

Over the past decade, numerous high-entropy ceramics have been synthesized, often displaying attractive properties. However, the study on facile preparation of bulk high entropy nitrides (HEN) are limited, despite its broad potential applications. This research demonstrates for the first time rapid fabrication (within ∼6 min) of bulk high-entropy nitrides, especially (Al 0.17 Nb 0.17 Ta 0.17 Ti 0.32 Zr 0.17 )N, from binary nitride powder mixtures using a highly efficient reactive flash sintering (RFS) technique. X-ray diffraction (XRD) shows the HENs from RFS are near single-phase solid solutions with a rock salt crystal structure, while in situ synchrotron study carried out during RFS captured in real time the formation of HEN, which was preserved upon cooling, suggesting thermodynamic stability of the HEN phase, even up to extreme pressure (∼35.6 GPa). Microscopic analyses using SEM, STEM, and EDS reveal decent uniformity for HEN with no obvious segregation of elements, even to submicron scale. Some properties of the obtained bulk HENs are consistent with expectations. For example, their hardness and bulk modulus are close to estimates based on rule-of-mixture (ROM) values from the constituent binary nitrides. Meanwhile, some other measured properties seem to show surprises. For example, the fracture toughness for the HENs (e.g., 7.81 ± 1.40 MPa•m 1/2 or higher) turns out to be more than double of the expected ROM estimates. The significantly improved fracture toughness is attributed to the observed nano-layered structure of the HENs, despite the HEN’s cubic crystal structure and high hardness. In addition, the oxidation resistance shows improvement up till ∼800°C, possibly due to Ta doping that suppress oxygen vacancy formation in the oxide shell, while the 5-metal HEN of (Al 0.17 Nb 0.17 Ta 0.17 Ti 0.32 Zr 0.17 )N displays superconductivity (T c of ∼5–7 K from magnetism and resistivity measurements, slightly lower than ROM estimate), despite insulating property of starting AlN. Furthermore, future study combining experimental investigation using larger samples to confirm the observed increase in fracture toughness and oxidation resistance, theoretical modeling at different length scale, and more detailed structural/chemical characterization, especially at the atomic scale, are all needed to fully understand the inter-relationships between composition, processing, structure, and novel properties for these HENs and the development of related new materials for different applications.

Flash sintering↗

Synergistic Coating-Alloy Development for Harsh Environments

The primary objective of the work was to demonstrate model alloy-coating combinations with: A. Improved oxidation resistance with a barrier coating by at least 2x vs. uncoated alloy; B. Uniform coating on a greater than 100:1 aspect ratio structure; and C. Expected reduction of lifecycle cost of a component of >25% based on customer inputs. All three objectives have been achieved.

36 MATERIALS SCIENCE↗

UHTC Composites for Leading Edges

Ultrahigh temperature ceramics (UHTC) have performed unreliably due to material flaws and attachment design. These deficiencies are brought tot he fore by the low fracture tougness and thermal shock resistance of UHTC. In addition, poor oxidation resistance is a limitation on UHTC applicability to reusable launch vehicles. We have been addressing these deficiencies for the past two years via a small task at GRC that is in the Airframe part of the Next Generation Launch Technology Program. Our focus is on UHTC composite (UHTCC) constructions and functional grading to address the mechanical issues and on composition modification to address the oxidation issue. Processing, mechanical property, and oxidation resutls will be reported.

Levine, Stanley R.↗

Improved high pressure turbine shroud

A new high pressure turbine shroud material has been developed from the consolidation of prealloyed powders of Ni, Cr, Al and Y. The new material, a filler for cast turbine shroud body segments, is called Genaseal. The development followed the identification of oxidation resistance as the primary cause of prior shroud deterioration, since conversion to oxides reduces erosion resistance and increases spalling under thermal cycled engine conditions. The NICrAlY composition was selected in preference to NIAL and FeCRALY alloys, and was formulated to a prescribed density range that offers suitable erosion resistance, thermal conductivity and elastic modulus for improved behavior as a shroud.

Bessen, I. I.↗

GRCop-84: A High Temperature Copper-based Alloy For High Heat Flux Applications

While designed for rocket engine main combustion chamber liners, GRCop-84 (Cu-8 at.% Cr-4 at.% Nb) offers potential for high heat flux applications in industrial applications requiring a temperature capability up to approximately 700 C (1292 F). GRCop-84 is a copper-based alloy with excellent elevated temperature strength, good creep resistance, long LCF lives and enhanced oxidation resistance. It also has a lower thermal expansion than copper and many other low alloy copper-based alloys. GRCop-84 can be manufactured into a variety of shapes such as tubing, bar, plate and sheet using standard production techniques and requires no special production techniques. GRCop-84 forms well, so conventional fabrication methods including stamping and bending can be used. GRCop-84 has demonstrated an ability to be friction stir welded, brazed, inertia welded, diffusion bonded and electron beam welded for joining to itself and other materials. Potential applications include plastic injection molds, resistance welding electrodes and holders, permanent metal casting molds, vacuum plasma spray nozzles and high temperature heat exchanger applications.

Ellis, David L.↗

The Development of HfO2-Rare Earth Based Oxide Materials and Barrier Coatings for Thermal Protection Systems

Advanced hafnia-rare earth oxides, rare earth aluminates and silicates have been developed for thermal environmental barrier systems for aerospace propulsion engine and thermal protection applications. The high temperature stability, low thermal conductivity, excellent oxidation resistance and mechanical properties of these oxide material systems make them attractive and potentially viable for thermal protection systems. This paper will focus on the development of the high performance and high temperature capable ZrO2HfO2-rare earth based alloy and compound oxide materials, processed as protective coating systems using state-or-the-art processing techniques. The emphasis has been in particular placed on assessing their temperature capability, stability and suitability for advanced space vehicle entry thermal protection systems. Fundamental thermophysical and thermomechanical properties of the material systems have been investigated at high temperatures. Laser high-heat-flux testing has also been developed to validate the material systems, and demonstrating durability under space entry high heat flux conditions.

Ceramic Matrix Composites↗

Spark plasma sintering (SPS) densified U 3 Si 2 pellets: Microstructure control and enhanced mechanical and oxidation properties

Dense U 3 Si 2 pellets with controlled grain structure and enhanced thermal-mechanical and oxidation properties are synthesized with spark plasma sintering (SPS). Microstructure and phase composition of the SPS densified pellets are characterized systematically using SEM, EDS, and XRD. Thermal-mechanical properties and oxidation behavior of the sintered silicide fuel pellets are analyzed by laser flash, indentation, and dynamic thermogravimetric analysis. Dense U 3 Si 2 pellets are consolidated by combining high energy ball milling and rapid sintering by SPS, and the microstructure structures are controlled from micron-sized (~5.7 μm grain size) for conventional silicide to a nanocrystalline matrix with an average grain size of ~280 nm. A dominant phase of distorted U 3 Si 2 was identified with lattice expansion due to residual thermal stress upon SPS consolidation and rapid cooling processes. Both micron-sized and nano-sized pellets show exceptional thermal transport properties, consistent with monolithic silicides reported in literature. The SPS-densified pellets possess simultaneously high hardness and fracture toughness. The SPS-densified silicide pellets also demonstrate exceptional oxidation performance with extended onset oxidation temperature above 500 °C and reduced oxidation kinetics, particularly for nano-sized pellets. A strong strain effect was proposed in which compressive stress in nano-sized pellets enhances the oxidation resistance of silicide fuels, as evidenced by the degradation of oxidation performance upon strain relaxation by isothermal annealing. The correlation among the sintering process – microstructure control – physical properties and fuel behavior is established. A new concept of strain engineering is proposed further properties optimization, enabling the development of potential oxidation and corrosion-resistant silicides with extended performance, the key technological challenge of U 3 Si 2 as the leading concept of accident tolerant fuels.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Boron/Carbon/Silicon/Nitrogen Ceramics And Precursors

Ceramics containing various amounts of boron, carbon, silicon, and nitrogen made from variety of polymeric precursors. Synthesized in high yield from readily available and relatively inexpensive starting materials. Stable at room temperature; when polymerized, converted to ceramics in high yield. Ceramics resist oxidation and other forms of degradation at high temperatures; used in bulk to form objects or to infiltrate other ceramics to obtain composites having greater resistance to oxidation and high temperatures.

Riccitiello, Salvatore↗