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At least 253 records · Page 14

Microstructure refinement of hot deformed Dy-free NdFeB magnets through a novel cold sintering approach by pressure-assisted spark plasma sintering

Anisotropic fine-grained Dy-free NdFeB high-performance magnets were produced using a novel cold sintering approach by pressure-assisted spark plasma sintering (SPS). The NdFeB nanocrystalline ribbon powders were subjected to cold sintering below 450 °C using pressure-assisted SPS, followed by hot deformation at 710 °C and 810 °C via SPS. Results indicate that cold sintering below 450 °C effectively restricts grain growth in the NdFeB magnets, yielding sub-100 nm scale grains across both fine-grained regions and most coarse-grained regions. The refined grain structure achieved through cold sintering allows for a lower hot deformation temperature as compared with the magnet by conventional sintering, as finer grains allow easier deformation and grain sliding/rotation. This process produces a highly fine-grained and anisotropic microstructure to achieve high magnetic performance (i.e., high intrinsic coercivity, remanence, and maximum energy product) in the magnets. The cold sintering (at 350 °C) and lower hot deformation temperatures required (e.g., 710 °C) help control grain coarsening and limit grain size that is commensurate with the size of a single magnetic domain of the Nd 2 Fe 14 B magnetic matrix phase, resulting in high intrinsic coercivity (H ci =11.4 kOe). Furthermore, the reduced hot deformation temperature mitigates the formation of coarse grain bands, leading to improved magnetic properties, specifically an increased remanence (B r = 14.3 kGs) and a high maximum energy product ((BH) max = 48 MGOe). In conclusion, cold sintered hot deformed NdFeB magnet also shows good thermal stability with reversible temperature coefficient α(B r )= -0.097 %/K and α(H ci )= -0.616 %/K at elevated temperatures up to 400 K.

Cold Sintering↗

Solar cell having improved back surface reflector

The operating temperature is reduced and the output of a solar cell is increased by using a solar cell which carries electrodes in a grid finger pattern on its back surface. These electrodes are sintered at the proper temperature to provide good ohmic contact. After sintering, a reflective material is deposited on the back surface by vacuum evaporation. Thus, the application of the back surface reflector is separate from the back contact formation. Back surface reflectors formed in conjunction with separate grid finger configuration back contacts are more effective than those formed by full back metallization of the reflector material.

Chai, A. T.↗

Enhancing CMC Temperature Performance in High Hydrogen Environments using Field Assisted Sintering Technology

This final report summarizes the developments in field assisted sintering technology (FAST) for rapid fabrication of ceramic matrix composite (CMC) materials with integrated environmental barrier coatings (EBCs), as well as their performance in a representative gas turbine combustor environment including stagnant flame zones, and high velocity product zones. CMCs are a possible high temperature tolerant material system for gas turbine engines, which are currently the dominant source of electric power production and the primary source of aircraft propulsion. However, CMCs are costly and time-consuming (on the order of weeks to months) to fabricate, and CMCs based on silicon carbide (SiC) ceramics are susceptible to water vapor degradation requiring the use of specialized EBCs. The manufacturing technique known as FAST can create consolidated parts in as little as a few hours using high pressure and temperature, and may be useful to integrate EBCs into CMCs directly during consolidation.

08 HYDROGEN↗

UO 2 + 5 vol% ZrB 2 nano composite nuclear fuels with full boron retention and enhanced oxidation resistance

The boron isotope ( 10 B) can be used as a neutron absorber in UO 2 to control the reactivity of nuclear fuel pellets, however, the boron source can react with oxygen source in UO 2 to form B 2 O 3 that vaporize readily at temperatures above 1200 °C. Unfortunately, the sintering of UO 2 fuel requires hours holding at high temperature (>1700 °C), resulting in an inevitable B loss during sintering and unpredictable B concentration in final product. It is challenging to incorporate boron through a conventional sintering method. In this work, we demonstrated that spark plasma sintering (SPS), a field assisted sintering technology, can effectively densify UO 2 + 5 vol% ZrB 2 composite fuel pellets by rapid consolidation at 1600 °C for a short duration of 5 min under an applied pressure of 40 MPa. Further, thermogravimetric analysis (TGA) measurements confirm that ZrB 2 is fully retained inside the composite fuel pellets. Inside the composite fuel pellets, nano sized ZrB 2 particles are uniformly distributed along the grain boundaries of the UO 2 matrix. The ZrB 2 particle transforms to a glassy B 2 O 3 phase covering the sample surface and grain boundaries of UO 2 matrix after a simple post-sintering annealing at 1000 °C in flowing Argon gas for 4 h. The formed glassy B 2 O 3 slows down the diffusion of oxygen ions and postpones the onset temperature for oxidation of UO 2 from 400 °C to 550 °C. This study demonstrates the capability of SPS, an advanced fuel manufacturing technique, to achieve a full retention of ZrB 2 in UO 2 oxide fuel and increase oxidation resistance through a simple post-sintering annealing. The reported work holds great engineering potential for development of advanced oxide fuel for nuclear application.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Implementation Challenges for Sintered Silicon Carbide Fiber Bonded Ceramic Materials for High Temperature Applications

During the last decades, a number of fiber reinforced ceramic composites have been developed and tested for various aerospace and ground based applications. However, a number of challenges still remain slowing the wide scale implementation of these materials. In addition to continuous fiber reinforced composites, other innovative materials have been developed including the fibrous monoliths and sintered fiber bonded ceramics. The sintered silicon carbide fiber bonded ceramics have been fabricated by the hot pressing and sintering of silicon carbide fibers. However, in this system reliable property database as well as various issues related to thermomechanical performance, integration, and fabrication of large and complex shape components has yet to be addressed. In this presentation, thermomechanical properties of sintered silicon carbide fiber bonded ceramics (as fabricated and joined) will be presented. In addition, critical need for manufacturing and integration technologies in successful implementation of these materials will be discussed.

Singh, M.↗

Pressureless sintered beta prime-Si3N4 solid solution: Fabrication, microstructure, and strength

Si3N4, AlN, and Al2O3 were used as basic constituents in a study of the pressureless sintering of beta prime-Si3N4 solid solution as a function of temperature. Y2O3-SiO2 additions were used to promote liquid-phase sintering. The sintered specimens were characterized with respect to density, microstructure, strength, oxidation, and thermal shock resistance. Density greater than 98 percent of theoretical was achieved by pressureless sintering at 1750 C. The microstructure consisted essentially of fine-grained beta prime-Si3N4 solid solution as the major phase. Modulus of rupture strengths up to 483 MPa were achieved at moderate temperature (1000 C), but decreased to 228 MPa at 1380 C. This substantial strength loss was attributed to a glassy grain boundary phase formed during cooling from the sintering temperature. The best oxidation resistance was exhibited by a composition containing 3 mol % Y2O3-SiO2 additives. Water quench thermal shock resistance was equivalent to that of reaction sintered silicon nitride but lower than hot-pressed silicon nitride.

Dutta, S.↗

Fabrication Of Metal Chloride Cathodes By Sintering

Transition-metal chloride cathodes for use in high-temperature rechargeable sodium batteries prepared by sintering transition-metal powders mixed with sodium chloride. Need for difficult and dangerous chlorination process eliminated. Proportions of transition metal and sodium chloride in mixture adjusted to suit specific requirements. Cathodes integral to sodium/metal-chloride batteries, which have advantages over sodium/sulfur batteries including energy densities, increased safety, reduced material and thermal-management problems, and ease of operation and assembly. Being evaluated for supplying electrical power during peak demand and electric vehicles.

Bugga, Ratnakumar V.↗

Sintering Behaviors of ZrC, NbC, and TaC Mono-and Binary Carbides

Nuclear Thermal Propulsion (NTP) has undergone development as an alternate in-space propulsion system to traditional chemical propulsion methods since the 1950s. In an NTP system, the energy released from fission in the core is utilized as the heat source to directly heat a propellant for propulsion, rather than chemical combustion in a traditional rocket. NTP has many desirable capabilities including flexible mission launch dates and reduced transit times due to it’s capability for high specific impulse. One of the main challenges with NTP systems is the structural integrity of the fuel. The fuel form required in the reactor core must withstand temperatures above 2700 Kelvin. Ceramic-metallic matrix fuel, ceramic-ceramic matrix fuel, and solid solution carbide fuels are the three strongest candidates for the extreme environments. Solid solution carbides have the potential to exhibit promising behavior as a fuel form in an NTP system. Of the multiple refractory metal carbides of interest, here we focus on zirconium carbide (ZrC), niobium carbide (NbC), and tantalum carbide (TaC). ZrC, NbC, and TaC powders were consolidated in monocarbide (ZrC, NbC, and TaC) and bi-carbide (ZrC-NbC, ZrC-TaC, NbC-TaC) forms using spark plasma sintering (SPS). In addition to the pure endpoint carbides, the examined compositions of the various bi-carbides ranged from 25-75 mol%. The sintering temperatures, pressures, and hold times were varied to determine the ideal sintering conditions. Grain size analysis, Archimedes’ density, scanning electron microscopy (SEM), X-ray diffraction (XRD), and energy dispersion spectroscopy (EDS) were used to determine and characterize the grain size, ideal density, porosity, phase stability, and chemical composition of each sample. The data from each sample was then used to generate a Master Sintering Curve (MSC) unique to each monocarbide or bi-carbide.

nuclear thermal propulsion↗

High temperature reflectance of hyperpure slip cast silica

An experimental program to optically characterize hyperpure slip cast silica at elevated temperatures is described. This sintered ceramic material is being used in the development of a reflective heat shield for the Outer Planet Entry Probe. A unique high temperature integrating sphere reflectometer is described and reflectance data in the spectral range 0.23-2.3 micron are presented at temperatures up to 1427 C in air and helium environments. Kubelka-Munk (K-M) scattering and absorptance coefficients (K and S), using the Reichman extension of the K-M theory, are presented as is a unique method of obtaining K and S from the Reichman equations using only reflectance data. The hyperpure slip cast silica material was found to retain its high diffuse reflectance at temperatures up to 1204 C, with slight degradation occurring at higher temperatures.

Dillow, C. F.↗

Densification, microstructure, and mechanical properties of Mo–30W alloys fabricated from conditioned powders

Refractory alloys, such as molybdenum-based systems, are attracting growing interest for applications in extreme environments, such as in the nuclear and aerospace industries. Recent advances in sintering technologies, coupled with mechanical alloying, have enabled the tailored design of these alloys by leveraging powder characteristics to control final microstructures and mechanical properties. In this study, Mo-30W alloys were fabricated using electric field-assisted sintering (EFAS) from ball-milled powders with and without hydrogen treatment to investigate the influence of surface oxides on material properties and sintering behavior. The results revealed that samples processed from as-ball-milled powder contained a high density of oxides within the microstructure, whereas oxide presence was significantly reduced in samples fabricated from hydrogen-treated powders. Interestingly, the two powder types led to opposite trends in grain size distribution: samples from untreated powders exhibited grain refinement from sample periphery to the center, while samples from hydrogen-treated powders showed grain coarsening toward the center. This behavior is attributed to temperature gradients present during sintering due to electrical percolation pathway differences during Joule heating. The powder surface oxides may have influenced the temperature distribution and grain evolution. Microhardness profiles measured along both axial and thickness directions were consistent with the grain size distribution. Furthermore, oxide films on powder surfaces have delayed densification by hindering particle necking and atomic diffusion during sintering.

36 - MATERIALS SCIENCE↗

Pt Particles on a Dynamic TiO 2 Support in Near-Ambient Conditions−Disentangling Size, Pressure, and Support Effects

Platinum particles on reducible oxides are known to form complex and highly dynamic catalyst systems at elevated pressures and temperatures, often adopting active structures that differ from those found at room temperature and under ultrahigh vacuum (UHV). Here, we study the oxidation and structural evolution of subnanometer Pt clusters and nanoparticles supported on rutile TiO 2 (110) across an oxygen pressure range from UHV to 0.1 mbar, using near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS), scanning tunneling microscopy (STM) under UHV and NAP conditions, and low-energy ion scattering (LEIS). Our results reveal distinct differences in oxidation behavior and thermal stability between Pt nanoparticles and clusters, which are further modulated by the support stoichiometry and oxygen pressure. Small Pt clusters become oxidized even at room temperature but are susceptible to accelerated sintering in 0.1 mbar O 2 at elevated temperatures. In contrast, well-crystallized Pt nanoparticles on near-stoichiometric TiO 2 show weaker oxidation. On a reduced, defective TiO 2 support, Pt instead quickly becomes deeply buried by new titania layers, which are formed during support reoxidation. This process appears to result primarily from interactions of the support with the gas phase, unlike the classical, selflimited encapsulation that is induced by the strong metal−support interaction (SMSI). Finally, we address the full complexity of real catalysts in a direct side-by-side comparison of the single-crystalline model system with a Pt-loaded TiO 2 powder catalyst (P25). We conclude that the stoichiometry of the model supports must be carefully chosen and controlled to accurately reproduce the expected state of powder supports during redox reactions.

metal nanoparticles↗

Sintering Characteristics of Multilayered Thermal Barrier Coatings Under Thermal Gradient and Isothermal High Temperature Annealing Conditions

Pyrochlore oxides have most of the relevant attributes for use as next generation thermal barrier coatings such as phase stability, low sintering kinetics and low thermal conductivity. One of the issues with the pyrochlore oxides is their lower toughness and therefore higher erosion rate compared to the current state-of-the-art TBC material, yttria (6 to 8 wt%) stabilized zirconia (YSZ). In this work, sintering characteristics were investigated for novel multilayered coating consisted of alternating layers of pyrochlore oxide viz Gd2Zr2O7 and t' low k (rare earth oxide doped YSZ). Thermal gradient and isothermal high temperature (1316 C) annealing conditions were used to investigate sintering and cracking in these coatings. The results are then compared with that of relevant monolayered coatings and a baseline YSZ coating.

Thermal Barrier Coatings↗

Characteristics of Si3N4-SiO2-Ce2O3 compositions sintered in high-pressure nitrogen

Full-density Si3N4-SiO2-Ce2O3 compositions were prepared by sintering with 2.5 MPa nitrogen pressure at temperatures of 1900 and 2090 C. Room-temperature flexural strengths near 700 MPa for sintered material compared favorably with the strength of hot-pressed material. At 1370 C, where flexural strengths as high as 363 MPa were obtained, it was observed that the coarsest structure was the strongest and the finest structure was the weakest. One of the compositions tested, Si3N4-8.7 wt pct SiO2-8.3 wt pct-Ce2O3, was found to have excellent 200-h oxidation resistance at 700, 1000, and 1370 C, without incidence of 700 to 1000 C phase instability and cracking.

Sanders, W. A.↗

Cubic and hexagonal boron nitride phases and phase boundaries

We used temperature-dependent spark plasma sintering to induce phase transformations of metastable 3D c-BN to mixed-phase 3D/2D c-BN/h-BN and ultimately to the stable 2D h-BN phase at high temperature, useful for extreme-temperature technology.

Materials Science↗

Microstructure characterization of electric field assisted sintering (EFAS) sintered metallic and ceramic materials using local thermal diffusivity measurement

Electric Field Assisted Sintering (EFAS, also referred to as spark plasma sintering) is a powerful technology for the consolidation of powder materials. The high heating rate during the sintering process is critical for minimizing energy consumption, but it can also cause microstructure heterogeneities in sintered parts, such as spatially varied porosity. The examination of localized porosity usually requires the use of a scanning electron microscope with a carefully prepared surface. In this paper, photothermal radiometry is used to measure local thermal diffusivity and extract localized porosity of EFAS-sintered parts by using a percolation-threshold model. Applying this approach, we identified the radial position-dependent porosity variation in EFAS parts, which is likely formed due to the large temperature gradient during the sintering process. This approach has a unique advantage because it can measure samples with minimal or no surface preparation, enabling the possibility of in situ characterization in EFAS with proper system modification. Necessary modifications on the measurement approach for EFAS deployment and in situ characterization are also discussed.

36 MATERIALS SCIENCE↗

Fabrication and thermophysical properties of UO 2 -UB 2 and UO 2 -UB 4 composites sintered via spark plasma sintering

Uranium dioxide (UO 2 ) composites with uranium diboride (UB 2 ) and uranium tetraboride (UB 4 ) have been proposed as advanced fuel candidates due to their high thermal conductivity, high melting point, high fissile density and their ability to incorporate a built-in burnable poison by tailoring the targeted 10 B/ 11 B ratio. As such, it is important to assess the fabrication, and thermal and micromechanical properties of such composites. In this work, UO 2 -UB 2 and UO 2 -UB 4 samples with boride phase fractions of 5, 15 and 30 wt% were fabricated to high densities (above 95 % theoretical density) via spark plasma sintering (SPS). This enabled sintering at relatively low temperatures and short timescales. SPS also aided in maintaining the target phase fractions of the samples as reactions between the constituent phases were suppressed due to the short timescales and reducing environment during sintering. Here, thermal diffusivity measurements from 299 to 1273 K were conducted through laser flash analysis (LFA). The diffusivity increased as a function of boride weight fraction, and UB 2 additions increased the thermal diffusivity of the composites more than UB 4 additions. Assessment of the LFA results indicated in-situ reactions between the UO 2 and boride phases that suppress the thermal diffusivity occur above 800 K for all samples. Oxidation of the boride phase was proposed as the underlying reaction. This was supported by thermodynamic assessments from the literature, as well as microstructural, crystallographic, and nanoindentation characterization performed on these samples.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Tape casting and characterizations of MgO ceramics

Herein we report a high density MgO ceramic substrate produced by the tape casting technology. The tape casting formulation and process produced a uniform tape free of cracking. Y 2 O 3 and SiO 2 were used as the sintering aid for the pressureless sintering of the green tape. X-ray diffraction phase identification indicates that MgO is the main phase, while both Y 2 O 3 and SiO 2 sintering aids react with MgO to form MgY 4 Si 3 O 13 as the second phase. Liquid phase sintering occurs in the temperature range from 1030°C to ~1500°C, which is confirmed by the simultaneous Thermal Gravitation Analysis/ Differential Scanning Calorimeter (TGA/DSC) and the percent linear shrinkage and densification. A 96.5% theoretical density was achieved by presureless sintering at 1650°C for 2 hours, which was further increased to a fully dense structure using hotisostatic- pressing(HIP) at 1650°C and 207 MPa in argon. Scanning electron microscopy (SEM) and energy dispersive(EDS) spectroscopic analysis on the HIP’ed sample show that MgY 4 Si 3 O 13 is located at the MgO grain boundary and the sample has a fully dense structure. The refractive indices and extinction coefficient were measured on the HIP’ed sample along with thermal properties and dielectric properties. Thermal diffusivity and heat capacity were measured to calculate the thermal conductivity.

36 MATERIALS SCIENCE↗