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At least 289 records · Page 16

Effects of processing conditions on flash sintering of commercial ZrN

Flash sintering (FS) is a potentially rapid and low-cost manufacturing technique for advanced ceramics. There are still many unknowns about ceramic FS, especially for highly conductive high-temperature ceramics (HTC), which often display decreased bulk conductivity with increasing temperature. This study qualitatively characterizes the flash behavior of highly conductive HTC materials using zirconium nitride (ZrN) as an example. The effects of processing parameters (e.g., DC voltage/electrical field strength, voltage ramp rate, post-flash holding time, mechanical pressure, sample milling, and choice of electrode materials) on ZrN flash behavior are also qualitatively studied and linked to samples microstructure and hardness. It is observed that best densification was achieved using 5 min Spex-milled ZrN powder under 25 MPa of applied pressure and constant 8 V DC. The potential mechanism for ZrN FS and the similarity and difference from FS of conventional oxides like YSZ have been proposed based on experimental observations, and the directions for future research are also pointed out.

Flash Sintering↗

Using in situ UO 2 bicrystal sintering to understand grain boundary dislocation nucleation kinetics and creep

Capillary evolution at bicrystal UO 2 grain boundaries is characterized using in situ transmission electron microscopy. The discontinuous nature of the densification process, both particle rotation and axial strain, along with the large activation stress for densification support a hypothesis that grain boundary strain in UO 2 follows nucleation rate limited kinetics at low to intermediate stresses, that is, less than ≈ 10 8 PA. Further, the temperature dependence of the average activation stress for sintering agrees well with analysis of bulk sintering data and creep data reported within the literature when analyzed in the context of a grain boundary dislocation nucleation rate limited kinetic model.

36 MATERIALS SCIENCE↗

Novel strategy for low-temperature, high-rate growth of dense, hard, and stress-free refractory ceramic thin films

Growth of fully dense refractory thin films by means of physical vapor deposition (PVD) requires elevated temperatures T{sub s} to ensure sufficient adatom mobilities. Films grown with no external heating are underdense, as demonstrated by the open voids visible in cross-sectional transmission electron microscopy images and by x-ray reflectivity results; thus, the layers exhibit low nanoindentation hardness and elastic modulus values. Ion bombardment of the growing film surface is often used to enhance densification; however, the required ion energies typically extract a steep price in the form of residual rare-gas-ion-induced compressive stress. Here, the authors propose a PVD strategy for the growth of dense, hard, and stress-free refractory thin films at low temperatures; that is, with no external heating. The authors use TiN as a model ceramic materials system and employ hybrid high-power pulsed and dc magnetron co-sputtering (HIPIMS and DCMS) in Ar/N{sub 2} mixtures to grow dilute Ti{sub 1−x}Ta{sub x}N alloys on Si(001) substrates. The Ta target driven by HIPIMS serves as a pulsed source of energetic Ta{sup +}/Ta{sup 2+} metal–ions, characterized by in-situ mass and energy spectroscopy, while the Ti target operates in DCMS mode (Ta-HIPIMS/Ti-DCMS) providing a continuous flux of metal atoms to sustain a high deposition rate. Substrate bias V{sub s} is applied in synchronous with the Ta-ion portion of each HIPIMS pulse in order to provide film densification by heavy-ion irradiation (m{sub Ta} = 180.95 amu versus m{sub Ti} = 47.88 amu) while minimizing Ar{sup +} bombardment and subsequent trapping in interstitial sites. Since Ta is a film constituent, primarily residing on cation sublattice sites, film stress remains low. Dense Ti{sub 0.92}Ta{sub 0.08}N alloy films, 1.8 μm thick, grown with T{sub s} ≤ 120 °C (due to plasma heating) and synchronized bias, V{sub s} = 160 V, exhibit nanoindentation hardness H = 25.9 GPa and elastic modulus E = 497 GPa compared to 13.8 and 318 GPa for underdense Ti-HIPIMS/Ti-DCMS TiN reference layers (T{sub s} < 120 °C) grown with the same V{sub s}, and 7.8 and 248 GPa for DCMS TiN films grown with no applied bias (T{sub s} < 120 °C). Ti{sub 0.92}Ta{sub 0.08}N residual stress is low, σ = −0.7 GPa, and essentially equal to that of Ti-HIPIMS/Ti-DCMS TiN films grown with the same substrate bias.

36 MATERIALS SCIENCE↗

New insights on carbon black suspension rheology—Anisotropic thixotropy and antithixotropy

We report a detailed experimental study of peculiar thixotropic dynamics of carbon black (CB, Vulcan XC-72) suspensions in mineral oil, specifically the observation of sequential stress increase then decrease at a fixed shear rate in a step-down test. We verify that such dynamics, though peculiar, come from a true material response rather than experimental artifacts. We also reveal how this long-time stress decay is associated with antithixotropic structural change rather than viscoelastic stress relaxation by using orthogonal superposition (OSP) rheometry to probe viscoelastic moduli during the step-down tests. The orthogonal storage and loss moduli are present, showing this two-timescale recovery then decay response, which demonstrates that this response is antithixotropic, and it involves shear-induced structuring. We further show a mechanical anisotropy in the CB suspension under shear using OSP. Based on the rheological results, a microstructural schematic is proposed, considering qualitatively thixotropic structure build-up, antithixotropic densification, and anisotropic structure evolution. Our observation for these CB suspensions is outside the standard paradigm of thixotropic structure-parameter models, and the elastic response provides us with new insight into the transient dynamics of CB suspensions.

Mechanics↗

Anode-supported tubular SOFC at low temperature using Ni, Fe, GDC, and YSZ based anode support

NiO-GDC, NiO-YSZ, NiO-Fe2O3-GDC, NiO-Fe2O3-YSZ anode tube supported tubular fuel cells was fabricated at the co-sintering temperature from 1250 C to 1400 C to investigate how the co-sintering temperature affect the open-circuit voltage. To focus on the changing of anode tube, all the tubular fuel cells support a ScSZ electrolyte layer and a LSCF cathode layer. The microstructure of the electrolyte layer sintered under 1300 C included pores inside it, and the densification of the electrolyte completed at the sintering temperatures above 1300 C. Furthermore, the shrinkage both in length and in diameter of a tubular fuel cell reaches as much as 20% at co-sintering temperature of 1400 C. The densification of ScSZ electrolyte layer and shrinkage of anode tube will result in the changing of open-circuit voltage of fuel cell from 1.0 V to 1.1 V.

30 DIRECT ENERGY CONVERSION↗

Demonstration of a Pilot-Scale Plant for Biomass Torrefaction and Briquetting

Abstract. A semi-mobile torrefaction and densification pilot plant was constructed in order to determine ideal operating conditions and evaluate briquette quality and throughput rate using forest residuals as the input feedstock. Experiments were conducted at various conditions with feedstock moisture content ranging from 4% to 25% (wet basis), reactor residence times of 10 and 20 min, and final product temperatures between 214°C and 324°C. Optimal operating conditions, evaluated based on throughput rate, specific electricity demand, torrefied briquette grindability, briquette volumetric energy density, and briquette durability, were identified to occur with a short residence time (10 min), low feedstock moisture content (<11% wet basis), and high final product temperature between 267°C and 275°C. These conditions were able to process 510 to 680 kg h -1 (wet basis) feedstock with a dry mass yield of 79% to 84% to produce torrefied biomass with a higher heating value of 21.2 to 23.0 MJ kg -1 (dry basis) compared to 19.6 MJ kg -1 for the original biomass. Torrefied briquettes produced at these conditions had a neatly stacked packing density of 990 kg m -3 and a volumetric energy density of 21,800 MJ m -3 . Their specific grinding energy was an average 37% of the energy required to grind a raw biomass briquette. These torrefied briquettes were more durable (94% DU) than raw briquettes (85% DU) directly following production, but were less durable after undergoing temperature and humidity fluctuations associated with long distance transportation (74% DU for torrefied and 84% DU for raw biomass briquettes). Results from this pilot plant are promising for commercial scale production of high quality torrefied briquettes and should lead to additional research and development of a torrefaction system optimized for a higher throughput rate at these conditions. Keywords: Biomass, Biomass conversion technology, Bioenergy, Briquetting, Densification, Forest residuals, Pyrolysis, Torrefaction.

Agriculture↗

Shrub Expansion Simulations at Trail Valley Creek Tundra site using E3SM Land Model (ELM) Arctic-focused Version

The warming of the Arctic is causing substantial compositional, structural, and functional changes in tundra vegetation including shrub and densification in parts of the Arctic. Assessing the impact of these changes in vegetation composition on the Arctic’s carbon and energy budgets is important to constrain projected local and global surface-atmosphere exchanges. We conduct a sensitivity analysis of the projected surface energy fluxes, soil carbon pools, and carbon dioxide fluxes (net ecosystem exchange, gross primary production, and ecosystem respiration) between present day and 2100 to different shrub expansion rates and air temperature increases under future emission scenarios (intermediate – RCP4.5, and high – RCP8.5) using the Arctic-focused version of the Energy Exascale Earth System Model (E3SM) Land Model (ELM). We focus on Trail Valley Creek (TVC), a mineral upland tundra site located in the western Canadian Arctic, which is experiencing tall shrub densification and expansion. In this study, we run TVC under two different warming scenarios RCP4.5 and RCP 8.5 and simulate different shrubification rates projected until year 2100. In this repository, we include all the forcing, input, parameters, and output data corresponding to all the simulations performed. flmd.csv includes a detailed description of the datasets files.

54 ENVIRONMENTAL SCIENCES↗

Synthesis of high-strength W-Ta ultrafine-grain composites

Bulk samples of an ultrafine-grained tungsten–tantalum composite alloy have been synthesized by consolidating mechanically milled composite powders. The grain growth during densification is limited due to the submicron-scale layering of the individual metals in the composite particles and the relatively low sintering temperature (1300 °C). The ultrafine microstructure of the high-density (~99% theoretical density) samples leads to a high yield stress of ~3 GPa under quasi-static uniaxial compression. A tendency for Ta-rich solid-solution formation during densification was observed, and the high-temperature phase equilibria in the composite powders were examined further using high-energy x-ray diffraction at temperatures up to 1300 °C.

nanostructure↗

Oxidation Protection of Uranium Nitride Fuel using Liquid Phase Sintering

Two methods are proposed to increase the oxidation resistance of uranium nitride (UN) nuclear fuel. These paths are: (1) Addition of USi{sub x} (e.g. U3Si2) to UN nitride powder, followed by liquid phase sintering, and (2) 'alloying' UN nitride with various compounds (followed by densification via Spark Plasma Sintering or Liquid Phase Sintering) that will greatly increase oxidation resistance. The advantages (high thermal conductivity, very high melting point, and high density) of nitride fuel have long been recognized. The sodium cooled BR-10 reactor in Russia operated for 18 years on uranium nitride fuel (UN was used as the driver fuel for two core loads). However, the potential advantages (large power up-grade, increased cycle lengths, possible high burn-ups) as a Light Water Reactor (LWR) fuel are offset by uranium nitride's extremely low oxidation resistance (UN powders oxidize in air and UN pellets decompose in hot water). Innovative research is proposed to solve this problem and thereby provide an accident tolerant LWR fuel that would resist water leaks and high temperature steam oxidation/spalling during an accident. It is proposed that we investigate two methods to increase the oxidation resistance of UN: (1) Addition of USi{sub x} (e.g. U 3 Si 2 ) to UN nitride powder, followed by liquid phase sintering, and (2) 'alloying' UN nitride with compounds (followed by densification via Spark Plasma Sintering) that will greatly increase oxidation resistance.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Science of Ignition Workshop, Panel 3 Report: Implosion Hydrodynamics

Using an ablation pressure of ~100 Mbars over a period of ~10 ns, the implosion hydrodynamics of an ICF capsule have always been a balance between obtaining high implosion velocities (> 370 km/s), necessary to create sufficient fuel densification (ρR >1g/cm 2 ) and stagnation pressure (> 400 Gbars), while simultaneously attempting to avoid hydrodynamic instabilities and avoid raising the DT fuel entropy much -- either of which frustrates fuel densification and hot spot creation. Ideally, an ICF implosion should have yield within about 50% of 1D, but present evidence from NIC suggests that is not the case and it is presently difficult to estimate the degree to which irradiation asymmetries or high-mode mix, respectively, are contributing to this behavior. If the NIC implosion can resolve any low-mode implosion hydrodynamics issues, there remains the significant challenge of achieving the needed convergence ratios in excess of 30+ without generating unacceptable mid to high-mode instability growth. Indeed, in the handful of NIC shots where the implosion speed was pushed up above ~300 km/s, and which had less than 8% ablator mass remaining, hot spot ion temperature and yield both dropped significantly, with an increase in x-ray brightness, which is consistent with excessive perturbation growth due to hydrodynamic instabilities.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Assessment of Methods to Consolidate Iodine-Loaded Silver-Functionalized Silica Aerogel

The U.S. Department of Energy is currently investigating alternative sorbents for the removal and immobilization of radioiodine from the gas streams in a nuclear fuel reprocessing plant. One of these new sorbents, Ag 0 -functionalized silica aerogels, shows great promise as a potential replacement for Ag-bearing mordenites because of its high selectivity and sorption capacity for iodine. Moreover, a feasible consolidation of iodine-loaded Ag0-functionalized silica aerogels to a durable SiO 2 -based waste form makes this aerogel an attractive choice for sequestering radioiodine. This report provides a preliminary assessment of the methods that can be used to consolidate iodine-loaded Ag 0 -functionalized silica aerogels into a final waste form. In particular, it focuses on experimental investigation of densification of as prepared Ag 0 - functionalized silica aerogels powders, with or without organic moiety and with or without sintering additive (colloidal silica), with three commercially available techniques: 1) hot uniaxial pressing (HUP), 2) hot isostatic pressing (HIP), and 3) spark plasma sintering (SPS). The densified products were evaluated with helium gas pycnometer for apparent density, with the Archimedes method for apparent density and open porosity, and with high-resolution scanning electron microscopy and energy dispersive spectroscopy (SEM-EDS) for the extent of densification and distribution of individual elements. The preliminary investigation of HUP, HIP, and SPS showed that these sintering methods can effectively consolidate powders of Ag 0 -functionalized silica aerogel into products of near-theoretical density. Also, removal of organic moiety and adding 5.6 mass% of colloidal silica to Ag0-functionalized silica aerogel powders before processing provided denser products. Furthermore, the ram travel data for SPS indicated that rapid consolidation of powders can be performed at temperatures below 950°C.

Ag-Functionalized Silica Aerogel↗

Life-Cycle Analysis of Greenhouse Gas Emissions and Water Consumption – Effects of Coal and Biomass Conversion to Liquid Fuels as Analyzed with the GREET Model

The vast reserves of coal in the U.S. provide a significant incentive for the development of processes for coal conversion to liquid fuels (CTL). Also, CTL using domestic coal can help move the U.S. toward greater energy independence and security. However, current conversion technologies are less economically competitive and generate greater greenhouse gas (GHG) emissions than production of petroleum fuels. Altex Technologies Corporation (Altex, hereinafter) and Pennsylvania State University have developed a hybrid technology to produce jet fuel from a feedstock blend of coal and biomass. Collaborating with Altex, Argonne National Laboratory has expanded and used the Greenhouse gases, Regulated Emissions, and Energy use in Transportation (GREET®) model to assess the life-cycle GHG emissions and water consumption of this hybrid technology. Biomass feedstocks include corn stover, switchgrass, and wheat straw. The option of biomass densification (bales to pellets) is also evaluated in this study. The results show that the densification process generates additional GHG emissions as a result of additional biomass process energy demand. This process coproduces a large amount of char, and this study investigates two scenarios to treat char: landfill disposal (Char-LF) and combustion for combined heat and power (CHP). Since the CHP scenarios export excess heat and electricity as coproducts, two coproduct handling methods are used for well-to-wake (WTWa) analysis: displacement (Char-CHP-Disp) and energy allocation (Char-CHP-EnAllo). When the feedstock contains 15 wt% densified wheat straw and 85 wt% lignite coal, WTWa GHG emissions of the coal-and-biomass-to-liquid pathways are 116, 97, and 137 gCO2e per megajoule (MJ) under the Char-LF, Char-CHP-Disp, and Char-CHP-EnAllo scenarios, respectively, as compared to conventional jet fuel production at 84 gCO2e/MJ. WTWa water consumption values are 0.072, -0.046, and 0.044 gal/MJ for Char-LF, Char-CHP-Disp, and Char-CHP-EnAllo, respectively, as compared to conventional jet fuel production at 0.028 gal/MJ. To reach the break-even point of 84 gCO2e/MJ, under the assumptions of constant product yields and energy demands regardless of the share of biomass and coal feedstocks, 31 wt%, 23 wt%, and 53 wt% of the feedstock blend need to be biomass under the Char-LF, Char-CHP-Disp, and Char-CHP-EnAllo scenarios, respectively.

09 BIOMASS FUELS↗

Milestone Report: Grain growth and fission gas behaviour in doped UO 2 M2MS-18LA0201034

Here, the microstructure of UO 2 can be modified during nuclear fuel fabrication by using additives. Several dopants (e.g. Cr, Ti, V, Mg, Nb) are used to enhance grain growth and densification during sintering. In previous work, we used atomic scale simulation techniques to identify a common interstitial solution mechanism for a range of dopants that form positively charged defects at sintering temperatures. As a result, negatively/positively charged defect concentrations were enhanced/suppressed relative to undoped fuel under the same conditions (temperature and oxygen partial pressure). Importantly U and fission gas migration is vacancy mediated, such that the increase in the concentration uranium vacancies (which have negative charge), due to doping, causes an increase in U and fission gas diffusivity. This is important because U diffusivity is the rate limiting step in mass transport during sintering and bulk fission gas diffusivity is the underlying property that governs fission gas release. In this work, we implement analytical expressions for uranium vacancy concentrations in doped fuel (based on atomic scale results) into mesoscale and engineering scale simulations of sintering and fission gas release. It is shown that densification is dramatically enhanced at 1850 K and 1950 K due to dopant solution and that Mn-doping has a greater effect than the more widely used Cr-doping. The effect of both dopants is strongly temperature dependent and is negligible below approximately 1800 K. The effect of enlarged grain size and enhanced fission gas diffusivity has been included in BISON. Fuel temperatures under normal operating conditions are not sufficient to activate the enhanced fission gas diffusivity mechanism predicted by atomic scale calculations. Therefore, the benefits of enlarged grains for reduced fission gas release should not undermined by enhanced fission gas diffusivity for doped UO 2 .

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Report Summarizing the Mechanical Properties of a Large ODS Ferritic Alloy Ingot by Forging at High Temperatures for Future Mother Tube Production

Oxide dispersion strengthened (ODS) ferritic alloys are considered the benchmark fuel cladding and core structural material in advanced nuclear energy reactors that require high-temperature strength and creep properties and resistance to radiation damage. The ODS ferritic alloys including 14YWT are produced by mechanical alloying (MA), which is time-consuming and is associated with high manufacturing costs that are not beneficial to being used in advanced nuclear energy reactors. This report summarizes the accomplishments in FY24 in the INM program for producing an ODS ferritic alloy by high-deformation, high-temperature processing of reactive and ferritic alloy powders for advanced reactor fuel cladding applications. Following four hot forging experiments, it was concluded that several significant challenges were encountered that were difficult to overcome. These challenges were related to using high annealing temperatures for pressure assisted sintering processes to produce dense microstructures, but the high annealing temperatures result in long range diffusion of Ti through the bcc Fe lattice and react with the YIG particles that are distributed on the prior surfaces of the ferritic alloy powders. In addition, it was determined that the high deformations induced by forging at high temperatures were not very effective for fracturing the reactive YIG particles into smaller particles and distributing them into the interior of the ferritic alloy powders. Spark plasma sintering was attempted for shortening the time at high temperatures, which led to full densification but the microstructure characterization results still showed that Ti atoms diffused over long distances in the bcc Fe lattice and reacted with the YIG particles. Finally, a short 30 minute high intensity ball milling experiment was conducted on blended 14WT and YIG powders for inducing severe deformations that caused the initially spherical powders of 14WT decorated with the YIG particles on the surfaces to transform to flakes and fracturing of YIG particles into smaller particles that were incorporated into the bcc Fe lattice. Two forgings were performed with the high intensity milled powders: first annealing for 20 minutes at 850ºC followed by forging and second annealing for 20 minutes at 1,100ºC followed by forging. At 850ºC, Ti atoms are effectively immobile, thus allowing for densification albeit incomplete. The deformation by forging after annealing for 20 minutes at 1,100ºC favored dynamic recrystallization processes that led to nano-size grains with very high stored energy due to high dislocation density. The corresponding VH data showed significant hardening that correlated with estimated strengthening of ~1650 MPa. This hybrid processing approach combining high intensity ball milling of powder with annealing and forging showed the most promise for producing an oxide dispersing strengthened ferritic alloy.

36 MATERIALS SCIENCE↗

High Capacity Step-Shaped Hydrogen Adsorption in Robust, Pore-Gating Zeolitic Imidazolate Frameworks (Final Technical Report)

The use of porous adsorbents for the densification of H 2 under relatively mild pressures and temperatures has been long pursued through various avenues of synthetic organic frameworks, namely metal–organic frameworks. However, the overwhelming majority of these materials are macroscopically rigid, exhibiting adsorption–desorption profiles that require appreciable energetic input for their full payload capacity to be stored and subsequently delivered. This reduced “deliverable” capacity is a core inefficiency in the use of porous adsorbents for H 2 densification. Our core mission is to determine a material-based strategy that fundamentally alters the adsorption¬–desorption profile in a manner that obviates these deleterious energetic requirements. Towards this, we have focused on metal–organic frameworks that exhibit “cooperative flexibility”, wherein the material undergoes reversible macroscopic phase changes in response to changes to external temperature and/or adsorbate pressure (i.e., concentration). Where these reversible switches occur between states of disparate enough accessible porosity, cooperatively flexible frameworks can exhibit “step-shaped” adsorption–desorption profiles that enable use of the delivery gaseous payload without the aforementioned additional energy requirements. However, before our work, such the observation of this phenomenon with very weakly adsorbing H 2 had not been observed with the necessary profile and P/T conditions desired for H 2 storage and delivery. During this project we have leveraged a deep understanding of the phase change in family of cooperatively flexible metal–organic frameworks to systematically alter their adsorption–desorption profiles to achieve step-shaped adsorption and desorption of H 2 in a precise P/T regime that enables a high deliverable capacity. Specifically, the thermodynamics of the adsorption/desorption induced phase changes in the baseline framework CdIF-13 (sod–Cd(benzimidazolate) 2 ) were tuned using the mixed-linker, or multivariate, approach to framework derivatization. Follow this, we have pursued a similar approach to tuning the adsorption–desorption profile of a second framework family, MIL-53(Al), which contains only Al(III) and theoretically exhibits a much higher deliverable capacity. In total, our work demonstrates that by first understanding the structural consequences of phase changes in these materials, their behavior can be systematically altered through ligand substitutions, tuning the pressure and temperature conditions at which H 2 is adsorbed and desorbed. Thus, enabling high deliverable capacities of H 2 with minimized energetic requirements.

08 HYDROGEN↗

Consolidation of iodine-loaded Ag 0 -functionalized silica aerogel with HUP, HIP and SPS

The U.S. Department of Energy is currently investigating alternative sorbents for the removal and immobilization of radioiodine from the gas streams in a nuclear fuel reprocessing plant. One of these new sorbents, silver-functionalized silica aerogel (Ag 0 -aerogel), shows promise as a potential replacement for silver mordenite because of its high selectivity and sorption capacity for iodine. Moreover, a feasible consolidation of iodine-loaded Ag 0 -aerogel to a durable SiO 2 -based waste form makes this aerogel an attractive choice for sequestering radioiodine. The main purpose of the study reported here was to investigate consolidation of Ag 0 -aerogel powders with or without iodine and with or without sintering additives with hot uniaxial pressing (HUP), HIP, and SPS. The selected densified samples were analyzed with a helium gas pycnometer for apparent density, with the Archimedes method for open porosity and apparent density, with scanning electron microscopy and energy dispersive spectroscopy (SEM-EDS) for the extent of densification, macro- and microstructural changes, and distribution of individual elements, and with X-ray diffraction (XRD) for crystalline phases. To convert the iodine-loaded Ag 0 -silica aerogel to a waste form, rapid consolidation with HUP, HIP, and SPS at moderate temperatures and pressures yields a final waste form consisting of AgI particles encapsulated in fused silica. HUP-processing (1200°C for 30 min under 29 MPa pressure) of Ag 0 -aerogel loaded with 20.2 mass% of iodine provided a product with residual open porosity of 16.9%. However, ~93% of sorbed iodine was retained in the sintered material. Densification with HIP at 1200°C for 30 min under 207 MPa pressure resulted in a fully dense silica-based waste form of 3.3 $\times$ 10 3 kg/m 3 bulk density containing ~22 mass% of iodine. Iodine was retained in the form of nano- and micro-inclusions of AgI dispersed in the silica matrix. Additives were not needed to enhance sintering process as depicted from the lack of open porosity and 100% retention of iodine in the consolidated product. The future tests will tell whether additives such as raw silica aerogel or Ag 0 -aerogel are required for HIPing to produce a fully dense waste form from iodine-loaded Ag 0 -aerogel containing higher concentrations of captured iodine. SPS-processing of samples with or without iodine revealed a benefit of additive-enhanced sintering. The samples containing additives (raw silica aerogel, colloidal silica, and Ag 0 -aerogel) shrunk faster and at lower temperatures. In addition, additives significantly improved distribution of silver compounds in the fully densified products, considerably decreasing the number of micron-sized inclusions of AgI, Ag and Ag 2 S at the grain boundaries.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Unconventional Materials Processing Using Spark Plasma Sintering

Spark plasma sintering (SPS) has gained recognition in the last 20 years for its rapid densification of hard-to-sinter conventional and advanced materials, including metals, ceramics, polymers, and composites. Herein, we describe the unconventional usages of the SPS technique developed in the field. The potential of various new modifications in the SPS technique, from pressureless to the integration of a novel gas quenching system to extrusion, has led to SPS’ evolution into a completely new manufacturing tool. The SPS technique’s modifications have broadened its usability from merely a densification tool to the fabrication of complex-shaped components, advanced functional materials, functionally gradient materials, interconnected materials, and porous filter materials for real-life applications. The broader application achieved by modification of the SPS technique can provide an alternative to conventional powder metallurgy methods as a scalable manufacturing process. The future challenges and opportunities in this emerging research field have also been identified and presented.

36 MATERIALS SCIENCE↗

Fabrication of Titanium-Niobium-Zirconium-Tantalium Alloy (TNZT) Bioimplant Components with Controllable Porosity by Spark Plasma Sintering

Spark Plasma Sintering (SPS) is used to fabricate Titanium-Niobium-Zirconium-Tantalum alloy (TNZT) powder—based bioimplant components with controllable porosity. The developed densification maps show the effects of final SPS temperature, pressure, holding time, and initial particle size on final sample relative density. Correlations between the final sample density and mechanical properties of the fabricated TNZT components are also investigated and microstructural analysis of the processed material is conducted. A densification model is proposed and used to calculate the TNZT alloy creep activation energy. The obtained experimental data can be utilized for the optimized fabrication of TNZT components with specific microstructural and mechanical properties suitable for biomedical applications.

36 MATERIALS SCIENCE↗