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At least 451 records · Page 25

Pt-Zn Clusters on Stoichiometric MgO(100) and TiO2(110): Dramatically Different Sintering Behavior

Zn was suggested to be a promising additive to Pt in the catalysis of dehydrogenation reactions. In this work, mixed Pt-Zn clusters deposited on two simple oxides, MgO(100) and TiO2(110), were investigated. The stability of these systems against cluster sintering, one of the major mechanisms of catalyst deactivation, is simulated using a Metropolis Monte Carlo scheme under the assumption of the Ostwald ripening mechanism. Particle migration, association to and dissociation from clusters, and evaporation and redeposition of monomers were all included in the simulations. Simulations are done at several high temperatures relevant to reactions of catalytic dehydrogenation. The effect of temperature is included via both the Metropolis algorithm and the Boltzmann-weighted populations of the global and thermally accessible local minima on the density functional theory potential energy surfaces of clusters of all sizes and compositions up to tetramers. On both surfaces, clusters are shown to sinter quite rapidly. However, the resultant compositions of the clusters most resistant to sintering are quite different on the two supports. On TiO2(110), Pt and Zn appear to phase separate, preferentially forming clusters rich in just one or the other metal. On MgO(100), Pt and Zn remain well-mixed and form a range of bimetallic clusters of various compositions that appear relatively stable. However, Zn is more easily lost from MgO through evaporation. These phenomena were rationalized by several means of chemical bonding analysis.

Environmental Molecular Sciences Laboratory↗

Crystallization Mechanism in Spark Plasma Sintered Bulk Metallic Glass Analyzed using Small Angle Neutron Scattering

Understanding the thermal stability of metallic glasses is critical to determining their safe temperatures of service. In this paper, the crystallization mechanism in spark plasma sintered Fe 48 Cr 15 Mo 14 Y 2 C15B6 metallic glass is established by analyzing the crystal size distribution using x-ray diffraction, transmission electron microscopy and in-situ small angle neutron scattering. Isothermal annealing at 700 °C and 725 °C for 100 min resulted in the formation of (Fe,Cr) 23 C 6 crystals, measured from transmission electron micrographs, to be from 10 to 30 nm. The small angle neutron scattering intensity measured in-situ, over a Q-range of 0.02 to 0.3 Å -1 , during isothermal annealing of the sintered samples, confirmed the presence of (Fe,Cr) 23 C 6 crystals. The measured scattering intensity, fitted by the maximum entropy model, over the Q-range of 0.02 to 0.06 Å -1 , revealed that the crystals had radii ranging from 3 to 18 nm. The total volume fraction of crystals were estimated to be 0.13 and 0.22 upon isothermal annealing at 700 °C and 725 °C for 100 min respectively. The mechanism of crystallization in this spark plasma sintered iron based metallic glass was established to be from pre-existing nuclei as confirmed by Avrami exponents of 0.25 ± 0.01 and 0.39 ± 0.01 at the aforesaid temperatures.

42 ENGINEERING↗

Rheology improvement for silicon nitride and resin slurries for vat photopolymerization printing and sintering

This work presents the formulation, rheological characterization, and sintering of silicon nitride (Si₃N₄) slurries for vat photopolymerization (VPP) using digital light processing (DLP). Bimodal Si₃N₄ powder was dispersed into commercial photopolymer resin using two different dispersants with opposing effects on surface charge, resulting in varied slurry stability and flow behavior. Slurries were engineered to exhibit shear-thinning behavior suitable for VPP, and their flow properties were quantified using a power-law fluid model. The formulations achieved cure depths of approximately 40 µm and enabled printing of green bodies. Post-processing included thermal debinding and liquid-phase sintering, yielding primarily β-Si₃N₄ with a minor Y-Si-Al-O-N glass phase. The sintered parts reached ~85% of theoretical density and demonstrated a flexural strength of ~330 MPa. Microstructural analysis revealed closed porosity along with some defects related to powder agglomeration and interlayer adhesion. These findings provide insights into slurry formulation strategies for additive manufacturing of high-performance non-oxide ceramics.

Aerospace engineering↗

Onset of selective laser flash sintering of AlN

Abstract Flash sintering uses a combination of heating and electric fields to rapidly densify ceramics. Previously, it has been shown that a scanning laser can be used to initiate flash sintering in localized regions on an yttria‐stabilized zirconia (YSZ) sample in a process known as selective laser flash sintering (SLFS). In this work, we show using a combination of measurements of electric current flowing through the sample and observations of necks formed between powder particles that aluminum nitride (AlN) can also undergo SLFS. Scan conditions required to initiate SLFS are characterized over a range of laser powers and laser scan speeds in a dry nitrogen environment. It is shown that initiation of SLFS in AlN is governed by both the local input energy density per scan and heat dissipation and a numerical model is developed to predict temperatures during SLFS. Assuming the minimum temperature along the conductive path determines the onset of SLFS, the minimum temperature and time required is 450–670 K in 2–0.25 s for the pressed AlN pellets used in this study for laser scan speeds of 33–300 m/s, laser powers of 10–30 W, and an applied electric field of 3000 V/cm.

Gouws, Andre↗

Radiation Stability of Spark‐Plasma‐Sintered Lead Vanadate Iodoapatite

Spark‐plasma‐sintered lead vanadate iodoapatite Pb 9.85 (VO 4 ) 6 I 1.7 , a promising nuclear waste form for the immobilization of I‐129, was irradiated with energetic ions, electrons, and gamma rays, to investigate its radiation stability. In situ TEM observation of the 1 MeV Kr 2+ irradiation shows that lead vanadate iodoapatite generally exhibits higher tolerance against ion irradiation‐induced amorphization than lead vanadate fluorapatite, and the spark plasma sintering can further enhance its radiation stability attributed to the enhanced crystallinity, reduced defect concentration, and denser microstructure. The critical amorphization dose and critical temperature for the SPS‐densified iodoapatite at 700°C are determined to be 0.25 dpa at room temperature and 230°C, respectively. No significant phase transformation or microstructural damage occurred under energetic electron and gamma irradiations. Raman spectra of gamma‐ray‐irradiated iodoapatite indicate improved V–O bond order at 500 kGy dose. Generally, the spark‐plasma‐sintered iodoapatite exhibits excellent radiation stability for nuclear waste form applications. The significantly enhanced radiation stability of the SPS‐densified iodoapatite suggests that SPS holds great promise for fabricating iodoapatite waste form with minimum iodine loss and optimized radiation tolerance for effective management of highly volatile I‐129.

Lu, Fengyuan↗

Superior Reliability Via Two‐Step Sintering: Barium Titanate Ceramics

Two‐step sintering ( TSS ) in a reducing atmosphere has been employed to obtain fine‐grain BaTiO 3 ceramics with a core‐shell microstructure, a more uniform grain‐size distribution, and superior reliability for multilayer ceramic capacitor applications. Compared to ceramics of the same composition conventionally sintered for about the same time, TSS ceramics feature a thinner shell thickness thus a stronger dopant localization, which leads to a lower concentration, higher internal resistance and more dopant‐ association. Improved reliability is manifest in a 50% higher breakdown strength at ambient temperature and a 400% longer endurance time to withstand DC stress at 185°C, in addition to a less field‐and‐temperature‐dependent capacitance. A scaling analysis of the redistribution and endurance dynamics identifies transmission across the shell‐grain‐boundary region as the critical element beneficially impacted by core‐shell structure and two‐step sintering.

Zhao, Qiancheng↗

The Change of X‐ray Diffraction Peak Width During in situ Conventional Sintering of Nanoscale Powders

Diffraction peaks of nanoscale particles of 3 mol% yttria‐stabilized zirconia become sharper as the powder sinters. The reduction in the peak width is correlated with the increase in density. The sharpening of the peak agrees reasonably well with the remaining free surface area as the sample sinters. Therefore, high curvature of the free surface of the pores is assumed to lead to peak broadening (the grain boundaries that grow at the expense of the free surfaces of the pores do not have this curvature). The change in the grain size during sintering does not make a significant contribution to peak width.

Lebrun, Jean‐Marie↗

Thermal Runaway in Mold‐Assisted Flash Sintering

Analyzing the temperature evolution in pressureless mold‐assisted flash sintering, we found the same onset condition as in standard flash sintering: When sample's DC or AC Joule heating replaces environment's radiation heating as the dominant power input term, thermal runaway ensues. Various serial and parallel components connected to the sample, including the mold, insulation, and punches, can affect Joule heating and conduction heat loss, thus play an important role in successful mold‐assisted flash sintering.

Dong, Yanhao↗

Microwave sintering of complex shapes: From multiphysics simulation to improvements of process scalability

The microwave sintering homogeneity of large and complex shape specimens is analyzed. A new approach enabling the fabrication of complex shapes ceramics via 3D printing and microwave sintering is presented. The use of a dental microwave cavity is shown to enable a substantial level of densification of complex shape components while restricting the grain growth. The homogeneity of the processed samples during microwave sintering is studied by an electromagnetic-thermal-mechanical simulation. The realistic densification behavior, that phenomenologically takes into account the microwave effect, is included in the modeling framework. We observe that the simulation indicates the sharp correlation between the microwave field distribution in the cavity, the temperature profile, and the specimen's shape distortion.

36 MATERIALS SCIENCE↗

Reactive flash sintering of powders of four constituents into a single phase of a complex oxide in a few seconds below 700°C

Abstract Recent work on reactive flash sintering of powders of two oxides, bismuth and of iron oxide, into pure single phase bismuth ferrite, which was accomplished in a few seconds at low furnace temperatures, is expanded to four constituents, alumina, lithia, zirconia, and lanthana, to produce reasonably dense polycrystals of a predominantly single phase, cubic LLZO(Al). Transformation and sintering occur concurrently at a furnace temperature near 700°C, in ambient atmosphere, in just a few seconds. The process may simplify the preparation of complex ceramics with new chemistries and dopants, which are predicted from ab intio calculations to have special attributes, not only because the powders sinter quickly at low temperatures, but also because the need for stoichiometric powders as starting materials is obviated.

Avila, Viviana↗

The Impact of Sintering Atmosphere and Temperature on the Phase Evolution of High Surface Area LSCF Prepared by In Situ Carbon Templating

The thermochemical stability of lanthanum strontium cobalt ferrite (LSCF) processed between 1000 °C–1200 °C via the in situ carbon templating method was studied. This method generates high surface area ceramics at traditional solid oxide fuel cell (SOFC) sintering temperatures by generating a carbon template in situ and subsequently removing the template by oxidation at 700 °C. Argon processed samples produced an amorphous carbon template, whereas nitrogen tended to form graphitic carbon. Prior to the oxidation step, nitrogen samples comprised larger La 2 O 3 crystallites (22–40 nm) compared to argon (9–17 nm). Upon oxidation, argon samples resulted in a pure LSCF phase with surface areas in the 21–29 m 2 ·g −1 range, whereas nitrogen samples contained significant impurities. This demonstrates that the size of La 2 O 3 crystallites formed during inert processing limited the ability to produce a pure LSCF phase. Symmetrical cells comprising nano-LSCF electrodes generated by the templating method were compared to cells sintered directly in air. Impedance results suggest that nano-LSCF cells and cells processed in air were dominated by interfacial charge transfer resistance and gas diffusion, respectively. The results map out conditions for preparing and integrating high surface area, nanostructured LSCF into SOFC electrodes at traditional sintering temperatures. Strategies for improving the interfacial resistance of nano-LSCF electrodes are discussed.

Muhoza, Sixbert P. (ORCID:0000000299864241)↗

Modeling Sintering Processes of Nanoparticle Inks

The In-Pile Instrumentation program conducts research on advanced manufacturing of sensors for use within nuclear reactor experiments. The process for making these sensors involves the sintering of nanoparticles within solvent. The nanoparticles must be sintered in a way that minimizes pores and maximizes continuity. It has also been observed that the nanoparticle films may fall off the substrate, so maximizing adhesion is also important. To model the sintering process, the phase field method was employed for one and two nanoparticle - substrate systems and the contact angle was measured and compared to existing experimental and theoretical studies.

36 MATERIALS SCIENCE↗

Embedding of Optical Fibers with Electric Field Assisted Sintering

The Electric Field Assisted Sintering (EFAS) technique was used for embedding the fibers, involving rapid heating via an electric current and pressure, reducing fiber exposure to high temperatures. Stainless steel guide tubes were inserted at the fiber-matrix junctions to prevent fiber breakage during the sintering process. The study varied key EFAS parameters—temperature (800°C to 980°C), pressure (40-50 MPa), and hold time (5-10 minutes)—to assess how they influenced fiber embedding. After embedding, the fibers were inspected using optical frequency domain reflectometry (OFDR) to evaluate optical losses and strain along the fiber length. The OFDR scans confirmed that the fibers remained intact, and subsequent transmission tests demonstrated no macroscopic fractures. The embedded samples were also analyzed using scanning electron microscopy (SEM) and X-ray computed tomography (CT) scans. These tests confirmed good bonding between the fiber and matrix with no cracking, though some porosity was present in samples fabricated at lower temperatures. At higher temperatures (980°C), the fiber-matrix bonding was continuous and defect-free, with metal coatings aiding in the bonding process. Elemental analysis showed interdiffusion between the fiber coatings and matrix materials, particularly between the gold coating and stainless steel. Helium leak tests revealed that lower sintering temperatures resulted in matrix porosity, causing leaks, but samples fabricated at 980°C were leak-tight.

46 - INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AN↗

Laser sintering of Al nanoparticles for Al-air batteries

With the growing price of lithium material and associated safety concerns, there is an urgent need for developing new efficient, cost-effective battery systems as a successor for lithium ion batteries. Metal-air batteries have drawn huge attention and interest as energy storage devices due to their high theoretical energy density when Al, Zn, Ni, and Fe are used. In particular, Al-air batteries have the potential to become a promising primary battery system with their relatively low prices and significantly high energy density. In this paper, the authors report a printed Al anode for Al-air battery combined with a laser sintering method. The anode was fabricated by Al nanoparticle ink using squeezing printing. Furthermore, a laser sintering method was applied to remove the organic solvent in the slurry and increase the conductivity of the printed anode. By application of infrared laser sintering, the authors significantly improved electrical conductivity of Al nanoparticles and electrochemical performance of Al-air cells. A Pt/C coated hydrophobicity carbon paper was used for the air cathode to provide a good electrical conductivity, an oxygen flow ability, and the water vapor sealing. Gel-style KOH was introduced as the electrolyte, and waterways were also utilized in the chemical reaction. The authors show a full battery cell with a printed Al anode on flexible substrates. This microbattery can provide a 227 mWh/g energy density and a 239 mAh/g capacity at an operation voltage of 0.95 V.

25 ENERGY STORAGE↗

Densification of Reaction Bonded Silicon Nitride with the Addition of Fine Si Powder Effects on the Sinterability and Mechanical Properties

The densification behavior and strength of sintered reaction bonded silicon nitrides (SRBSN) that contain Lu2O3-SiO2 additives were improved by the addition of fine Si powder. Dense specimens (relative density: 99.5%) were obtained by gas-pressure sintering (GPS) at 1850oC through the addition of fine Si. In contrast, the densification of conventional specimens did not complete at 1950oC. The fine Si decreased the onset temperature of shrinkage and increased the shrinkage rate because the additive helped the compaction of green bodies and induced the formation of fine Si3N4 particles after nitridation and sintering at and above 1600oC. The amount of residual SiO2 within the specimens was not strongly affected by adding fine Si powder because most of the SiO2 layer that had formed on the fine Si particles decomposed during nitridation. The maximum strength and fracture toughness of the specimens were 991 MPa and 8.0 MPa m1/2, respectively.

Lee, Sea-Hoon↗

Activated sintering of ThO2 and ThO2-Y2O3 with NiO.

Scanning electron microscopy and isothermal shrinkage measurements were used to study the effects of additives on the sintering of Thoria-Yttria compacts and loose powders. Small amounts of the oxides of Ni, Zn, Co, and Cu were found to reduce the sintering temperature (which is normally above 2000 C). In particular, NiO, at a concentration of 0.8 wt %, was found to yield high-density bodies at temperatures below 1500 C. Densification occurs very rapidly, and is followed by a much slower sintering process typical of volume diffusion.

Halbfinger, G. P.↗

Sintering and hot pressing of Fra Mauro composition glass and the lithification of lunar breccias.

It is proposed that Apollo 14 type breccias lithify by sintering of particles of matrix glass under stress-free conditions. Meteorite impacts generate the heat necessary for sintering. Compacted angular particles of glass with the composition of an Apollo 14 rock were sintered experimentally. Loose clods of sub 37 micron grains form in several days at 700 C. Synthetic rocks, which texturally resemble the breccias, were produced at 795 C and above in 7.5 hours. Glass devitrified with increasing temperature. At 850 C, devitrification prevents much further densification of the synthetic breccias after 2 hours. Experiments compressing glass at 500 bars at 600 C produced dense vitreous masses which did not resemble lunar breccias. Confining pressure does not play a major role in lithifying the breccias. It is concluded that Apollo 14 type lunar breccias form at shallow depths at 800 C+ in a period of minutes to days.

Simonds, C. H.↗