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At least 307 records · Page 17

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↗

Simultaneous Spark Plasma Sintering of Multiple Complex Shapes

This work addresses the two great challenges of the spark plasma sintering (SPS) process: The sintering of complex shapes and the simultaneous production of multiple parts. A new controllable interface method is employed to concurrently consolidate two nickel gear shapes by SPS. A graphite deformable sub-mold is specifically designed for the mutual densification of both complex parts in a unique 40 mm powder deformation space. An energy efficient SPS configuration is developed to allow the sintering of a large-scale powder assembly under electric current lower than 900 A. The stability of the developed process is studied by electro-thermal-mechanical (ETM) simulation. The ETM simulation reveals that homogeneous densification conditions can be attained by inserting an alumina powder at the sample/punches interfaces, enabling the energy efficient heating and the thermal confinement of the nickel powder. Finally, the feasibility of the fabrication of the two near net shape gears with a very homogeneous microstructure is demonstrated.

36 MATERIALS SCIENCE↗

A Comprehensive Characterization of Pyrolysis Oil from Softwood Barks

Pyrolysis of raw pine bark, pine, and Douglas-Fir bark was examined. The pyrolysis oil yields of raw pine bark, pine, and Douglas-Fir bark at 500 °C were 29.18%, 26.67%, and 26.65%, respectively. Both energy densification ratios (1.32–1.56) and energy yields (48.40–54.31%) of char are higher than pyrolysis oils (energy densification ratios: 1.13–1.19, energy yields: 30.16–34.42%). The pyrolysis oils have higher heating values (~25 MJ/kg) than bio-oils (~20 MJ/kg) from wood and agricultural residues, and the higher heating values of char (~31 MJ/kg) are comparable to that of many commercial coals. The elemental analysis indicated that the lower O/C value and higher H/C value represent a more valuable source of energy for pyrolysis oils than biomass. The nuclear magnetic resonance results demonstrated that the most abundant hydroxyl groups of pyrolysis oil are aliphatic OH groups, catechol, guaiacol, and p-hydroxy-phenyl OH groups. The aliphatic OH groups are mainly derived from the cleavage of cellulose glycosidic bonds, while the catechol, guaiacol, and p-hydroxy-phenyl OH groups are mostly attributed to the cleavage of the lignin β–O-4 bond. Significant amount of aromatic carbon (~40%) in pyrolysis oils is obtained from tannin and lignin components and the aromatic C–O bonds may be formed by a radical reaction between the aromatic and aliphatic hydroxyl groups. In this study, a comprehensive analytical method was developed to fully understand and evaluate the pyrolysis products produced from softwood barks, which could offer valuable information on the pyrolysis mechanism of biomass and promote better utilization of pyrolysis products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Infiltration of Nanoparticles into Porous Binder Jet Printed Parts

The densification of parts that are produced by binder jetting Additive Manufacturing (AM; a.k.a. “3D Printing”) is an essential step in making them mechanically useful. By increasing the packing factor of the powder bed by incorporating nanoparticles into the binder has potential to alleviate the amount of shrinkage needed for full densification of binder jet parts. We present preliminary data on the use of 316L Stainless Steel Nanoparticles (SSN) to densify 316L stainless steel binder jet parts. Aqueous solutions of Diethylene Glycol (DEG) or Ethylene Glycol (EG) were prepared at different DEG/water and EG/water molar ratios; pH of the solutions was adjusted by the use of 0.10 M sodium hydroxide. Nanoparticles were suspended in a resulted solution at a volume percentage of SSN/solution at 0.5%. The suspension was then sonicated for thirty minutes. One milliliter of the suspension was added stepwise to a sintered, printed disk with the dimensions: (d = 10 mm, h = 3 mm) in the presence of a small magnet. The 3D part was then sintered again. Moreover, the increase in the mass of the 3D part was used as indication of the amount of nanoparticles that diffused in the 3D part. This mass percent increase was studied as a function of pH of the suspension and as function DEG/water molar ratio. Unlike EG, data show that change in pH affects the mass percent when the suspension was made with DEG. Finally, optical analysis of the discs’ cross sections revealed trends metallic densities similar to trends in the data for mass increase with changing pH and water molar ratio.

36 MATERIALS SCIENCE↗

Miniature lowpass filters in low loss 9k7 LTCC

DuPont 9k7 low temperature cofired ceramic (LTCC) is a low loss, or high quality factor Q, tape system targeting at radio frequency (RF) applications. This paper reports the effect of a critical process parameter, heating rate, on the densification and dielectric properties of the 9k7 LTCC. The role of competing densification and crystallization during the sintering of 9k7 is discussed. The high Q of DuPont 9K7 can be used to improve RF system performance, for example a better receiver noise figure, by designing embedded passive RF components such as inductors, capacitors and filters. As a result, miniaturized multilayer low pass filters (LPF) with a wide stopband were fabricated to showcase the technology.

36 MATERIALS SCIENCE↗

Chemical Preconversion: Application of Low-Severity Pretreatment Chemistries for Commoditization of Lignocellulosic Feedstock

Securing biofuels project financing is challenging, in part because of risks in feedstock supply. Commoditization of the feedstock and decoupling its supply from the biorefinery will promote greater economies of scale, reduce feedstock supply risk and reduce the need for overdesign of biorefinery pretreatment technologies. We present benefits and detractions of applying low-severity chemical treatments or ‘chemical preconversion treatments’ to enable this approach through feedstock modification and densification early in the supply chain. General structural modifications to biomass that support cost-effective densification and transportation are presented, followed by available chemistries to achieve these modifications with minimal yield loss and the potential for harvesting value in local economies. A brief review of existing biomass pretreatment technologies for cellulolytic hydrolysis at biorefineries is presented, followed by a discussion toward economically applying the underlying chemistries at reduced severity in light of capital and operational limitations of small-scale feedstock depots.

09 BIOMASS FUELS↗

Sintered-reaction Bonded Silicon Nitride Densified by a Gas Pressure Sintering Process Effects of Rare Earth Oxide Sintering Additives

Reaction-bonded silicon nitrides containing rare-earth oxide sintering additives were densified by gas pressure sintering. The sintering behavior, microstructure and mechanical properties of the resultant specimens were analyzed. For that purpose, Lu2O3-SiO2 (US), La2O3-MgO (AM) and Y2O3-Al2O3 (YA) additive systems were selected. Among the tested compositions, densification of silicon nitride occurred at the lowest temperature when using the La2O3-MgO system. Since the Lu2O3-SiO2 system has the highest melting temperature, full densification could not be achieved after sintering at 1950oC. However, the system had a reasonably high bending strength of 527 MPa at 1200oC in air and a high fracture toughness of 9.2 MPa m1/2. The Y2O3-Al2O3 system had the highest room temperature bending strength of 1.2 GPa

36 MATERIALS SCIENCE↗

Miniature low-pass filter in low-loss 9k7 LTCC

DuPont 9k7 low-temperature cofired ceramic (LTCC) is a low-loss, or high-quality-factor Q, tape system targeting at radio frequency (RF) applications. This paper reports on the effect of a critical process parameter, the heating rate, on the densification and dielectric properties of the 9k7 LTCC. The role of competing densification and crystallization during the sintering of 9k7 is discussed. The high Q of DuPont 9K7 can be used to improve RF system performance, for example a better receiver noise figure, by designing embedded passive RF components such as inductors, capacitors and filters. Furthermore, miniaturized multilayer low-pass filters (LPF) with a wide stopband were fabricated to showcase the technology.

36 MATERIALS SCIENCE↗

Changes in the firn structure of the western Greenland Ice Sheet caused by recent warming

Atmospheric warming over the Greenland Ice Sheet during the last 2 decades has increased the amount of surface meltwater production, resulting in the migration of melt and percolation regimes to higher altitudes and an increase in the amount of ice content from refrozen meltwater found in the firn above the superimposed ice zone. Here we present field and airborne radar observations of buried ice layers within the near-surface (0–20 m) firn in western Greenland, obtained from campaigns between 1998 and 2014. We find a sharp increase in firn-ice content in the form of thick widespread layers in the percolation zone, which decreases the capacity of the firn to store meltwater. The estimated total annual ice content retained in the near-surface firn in areas with positive surface mass balance west of the ice divide in Greenland reached a maximum of 74 ± 25 Gt in 2012, compared to the 1958–1999 average of 13 ± 2 Gt, while the percolation zone area more than doubled between 2003 and 2012. Increased melt and column densification resulted in surface lowering averaging –0.80 ± 0.39 m yr⁻¹ between 1800 and 2800 m in the accumulation zone of western Greenland. Since 2007, modeled annual melt and refreezing rates in the percolation zone at elevations below 2100 m surpass the annual snowfall from the previous year, implying that mass gain in the region is retained after melt in the form of refrozen meltwater. If current melt trends over high elevation regions continue, subsequent changes in firn structure will have implications for the hydrology of the ice sheet and related abrupt seasonal densification could become increasingly significant for altimetry-derived ice sheet mass balance estimates.

58 GEOSCIENCES↗

High temperature compounds for turbine vanes

Fabrication and microstructure control studies were conducted on SiC, Si3N and composites based on Si3N. Charpy mode impact testing to 2400 F established that Si3N4/Mo composites have excellent potential. Attempts to fabricate composites of Si3N4 with superalloys, both by hot pressing and infiltration were largely unsuccessful in comparison to using Mo, Re, and Ta which are less reactive. Modest improvements in impact strength were realized for monolithic Si3N4; however, SiC strengths increased by a factor of six and now equal values achieved for Si3N4. Correlations of impact strength with material properties are discussed. Reduced MgO densification aid additions to Si3N4 were found to decrease densification kinetics, increase final porosity, decrease room temperature bend strength, increase high temperature bend strength, and decrease bend stress rupture properties. The decrease in bend strength at high temperature for fine grain size SiC suggested that a slightly larger grain size material with a nearly constant strength-temperature relation may prove desirable in the creep and stress rupture mode.

Rhodes, W. H.↗

Effects of pressure and temperature on hot pressing a sialon

The combined effects of temperature and pressure on the resulting density of a sialon (i.e., a ceramic composed of Si, Al, O, and N) are evaluated. Pressures in the 3.5-27.5 MPa range and temperatures in the 1550-1750 C range are considered. It is found that: (1) fully dense sialon bodies may be produced at lower temperatures than those usually used in the field, (2) the phase equilibrium reaction is increased by increased pressure, (3) the iso-density contour may be used to help design the desired microstructure, (4) phase changes occurring in the sample during hot pressing influenced sialon densification to a large extent, and (5) microstructures exceeding 98% theoretical density suggest that plastic deformation has contributed to densification.

Yeh, H. C.↗

Microstructural characterization of the HRSI thermal protection system for space shuttle

Components of the space shuttle high temperature reusable surface insulation (HRSI) system were microscopically characterized, both separately and as a system, to obtain information needed for stress analysis models of the thermal protection system. A tension specimen of the HRSI system was loaded in steps and was microscopically observed at each load condition to demonstrate the tension failure mode associated with strain isolation pad (SIP) behavior. A local failure occurred which should be associated with transfer of load through transverse fibers in the SIP. Stress concentrations attributed to the SIP behavior necessitated strengthening of the HRSI by densification of the RSI at the bondline. An HRSI tile was microscopically characterized after the densification process. The densified surface layer blended into the RSI which caused a gradual change in density. The gradation in density does not appear to represent a sharp discontinuity in elastic modulus between the densified layer and the parent material.

Ransone, P. O.↗