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At least 793 records · Page 44
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

The thermodynamic stability of intermediate solid solutions in LiFePO 4 nanoparticles

Theoretical predictions from first principles and recent advances in in situ electrochemical characterization techniques have confirmed the presence of solid-solution states during electrochemical (de)lithiation of LiFePO 4 nanoparticles. Surprisingly, however, such thermodynamically unfavorable solid solution states have been observed at rates as low as 0.1C. Given the high diffusivity of Li in LiFePO 4 and the thermodynamic instability of homogeneous solid solution states, spinodal decomposition to a thermodynamically favorable two-phase state is expected to occur on time scales as rapid as 1–100 ms. Here, we resolve this apparent paradox by demonstrating that, given the symmetry of the low-energy solid-solution Li/Va orderings and the 1D character of Li diffusion, spinodal decomposition from a solid solution preferentially leads to the formation of a diffuse ac interface with a large intermediate solid-solution region, as opposed to the commonly assumed bc interface. Our first principles predictions not only rationalize the persistence of solid-solution states at low-to-moderate C-rates in high-rate LiFePO 4 electrodes, but also explain the observations of large intermediate solid-solution regions at an ac interface in single Li x FePO 4 particles quenched from a high-temperature solid solution.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Bench-scale Development of an Advanced Solid Sorbent-based CO 2 Capture Process for Coal-fired Power Plants

It is increasingly clear that CO 2 capture and sequestration (CCS) must play a critical role in curbing worldwide CO 2 emissions to the atmosphere. Development of these technologies to cost-effectively remove CO 2 from coal-fired power plants is very important to mitigating the impact these power plants have within the world’s power generation portfolio. Currently, conventional CO 2 capture technologies, such as aqueous-monoethanolamine based solvent systems, are prohibitively expensive and if implemented could result in a 75 to 100% increase in the cost of electricity for consumers worldwide. Solid sorbent CO 2 capture processes – such as RTI’s Advanced Solid Sorbent CO 2 , Capture Process – are promising alternatives to conventional, liquid solvents. Supported amine sorbents – of the nature RTI has developed – are particularly attractive due to their high CO 2 loadings, low heat capacities, reduced corrosivity/volatility and the potential to reduce the regeneration energy needed to carry out CO 2 capture. Previous work in this area has failed to adequately address various technology challenges such as sorbent stability and regenerability, sorbent scale-up, improved physical strength and attrition-resistance, proper heat management and temperature control, proper solids handling and circulation control, as well as the proper coupling of process engineering advancements that are tailored for a promising sorbent technology. The remaining challenges for these sorbent processes have provided the framework for the project team’s research and development and target for advancing the technology beyond lab- and bench-scale testing. Under a cooperative agreement with the US Department of Energy, and part of NETL’s CO 2 Capture Program, RTI has led an effort to address and mitigate the challenges associated with solid sorbent CO 2 capture. The overall objective of this project was to mitigate the technical and economic risks associated with the scale-up of solid sorbent-based CO 2 capture processes, enabling subsequent larger pilot demonstrations and ultimately commercial deployment. An integrated development approach has been a key focus of this project in which process development, sorbent development, and economic analyses have informed each of the other development processes. Development efforts have focused on improving the performance stability of sorbent candidates, refining process engineering and design, and evaluating the viability of the technology through detailed economic analyses. Sorbent advancements have led to a next generation, commercially-viable CO 2 capture sorbent exhibiting performance stability in various gas environments and a physically strong fluidizable form. The team has reduced sorbent production costs and optimized the production process and scale-up of PEI-impregnated, fluidizable sorbents. Refinement of the process engineering and design, as well as the construction and operation of a bench-scale research unit has demonstrated promising CO 2 capture performance under simulated coal-fired flue gas conditions. Parametric testing has shown how CO 2 capture performance is impacted by changing process variables, such as Adsorber temperature, Regenerator temperature, superficial flue gas velocity, solids circulation rate, CO 2 partial pressure in the Regenerator, and many others. Long-term testing has generated data for the project team to set the process conditions needed to operate a solids-based system for optimal performance, with continuous 90% CO 2 capture, and no operational interruptions. Data collected from all phases of testing has been used to develop a detailed techno-economic assessment of RTI’s technology. These detailed analyses show that RTI’s technology has significant economic advantages over current amine scrubbing and potential to achieve the DOE’s Carbon Capture Program’s goal of >90% CO 2 capture rate at a cost of < $40/T-CO 2 captured by 2025. Through this integrated technology development approach, the project team has advanced RTI’s CO 2 capture technology to TRL-4 (nearly TRL-5, with the missing variable being testing on actual, coal-fired flue gas), according to the DOE/FE definitions for Technology Readiness Levels. At a broader level, this project has advanced the whole of the solid sorbent CO 2 capture field, with advancements in process engineering and design, technical risk mitigation, sorbent scale-up optimization, and an understanding of the commercial viability and applicability of solid sorbent CO 2 capture technologies for the U.S. existing fleet of coal-fired power plants.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2020

Technical Gaps in Hanford High-Level Waste Solids Settling Behavior and Settling Time Evaluation for Direct Feed High-Level Waste (DFHLW) Operations

Settling of high-level waste (HLW) solids in process vessels is a key conceptual process step in providing HLW feed directly to the Hanford Waste Treatment and Immobilization Plant (WTP) HLW Vitrification Facility. Direct Feed High-Level Waste (DFHLW) is a potential approach to initiating HLW vitrification prior to completing of the WTP Pretreatment Facility. Settling would be used with subsequent supernatant decant to concentrate HLW feed. To support planning for DFHLW, Washington River Protection Solutions (WRPS) requested support from the Pacific Northwest National Laboratory to evaluate the current data set available to predict the time needed for HLW solids to settle, to identify gaps in the understanding and predictive capability of HLW solids waste settling times, and to provide scoping estimates of the potential settling time. Eight technical gaps were identified for predicting settling times and characteristics of the formed sediment layers including: Gap 1: In-Tank Settling Rates Faster than Settling of Laboratory Samples, Gap 2: Effect of Sludge Leaching/Washing on Predicted Settling Times, Gap 3: Predicting Waste Settling from Waste Chemistry (Waste Type), Gap 4: Predicting Waste Settling from Particle Size and Density Distributions (PSDDs), Gap 5: Insufficient Laboratory and In-Tank Settling Data to Represent Hanford Waste, Gap 6: Methods for Real-Time, In-Tank Tracking of Settling, Gap 7: Prediction of Sediment Erosion Resistance as a Function of Settling Time, and Gap 8: Prediction of Sediment Solids Content as a Function of Settling Time. In addition to the data gaps, an overarching observation of the settling rate and settled layer data is the significant variation in behavior. At similar solids concentrations, settling rates can vary by as much as 3 orders of magnitude depending on the source waste tank, and significantly different settling rates are noted between laboratory and in situ tests for the same waste tank. The range of average solids concentration in existing HLW sediment, which may have been quiescent for decades, can vary from less than 7 wt% to greater than 74 wt% solids. The shear strengths (or yield stresses) measured on laboratory samples range from less than 27 Pa to greater than 6400 Pa. These variations can challenge process planning for the application of a settle/decant process for DFHLW. This report describes the significance of the gaps to the settle/decant process and presents uncertainties by way of examples. Potential technical approaches for resolving these gaps are described and the estimated difficulty in resolving these gaps is evaluated. Based on the significance of the gap and the difficulty of resolution, recommendations are made to address specific gaps. Scoping estimates of the potential settling times for DFHLW solids have been made based on the existing data set with its associated gaps. Depending on the process vessel depth and final sediment concentration, substantial fractions of the scoping estimate results for settling times for characterized HLW exceed the 2-week period that has been previously assumed for process planning. There is also significant disparity, potentially greater than a factor of 5000 difference, in the estimated settling times depending on process vessel depth and final sediment solid concentration. This variation in results underscores the significance of the identified gaps and uncertainties with respect to process planning for utilizing settle/decant operations for DFHLW.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Targeted Rare Earth Element Extraction from Mine Drainage Treatment Solids Informed by Advanced Characterization

In support of a clean energy transition in the U.S., National Energy Technology Laboratory (NETL) has collaborated with staff at Hedin Environmental and students at the University of Pittsburgh to characterize critical mineral content and recovery potential from acid mine drainage treatment solids (AMD solids). AMD solids in Appalachia are an unconventional feedstock of rare earth elements (REEs), with potential of suppling 1,102 tons REE/year. To inform recovery efforts, select AMD solids were examined using synchrotron microprobe analysis in conjunction with USGS-developed geochemical modeling to indicate likely phases hosting critical minerals (REE, Co, Ni, etc.) and associated metals . More than 100 AMD solids were collected from 94 passive AMD treatment systems in Pennsylvania, where limestone aggregates are used for acidity neutralization. As pH increases, dissolved metals and critical minerals in AMD are attenuated as surface coatings on limestone. The collected AMD solids contained up to 2000 mg/kg REE, up to 13,000 mg/kg transition metals (Co, Ni, Zn) and up to 440 mg/kg Li. Regardless of the diverse chemical compositions from AMD solids (Al-rich, Mn-rich, or Al,Fe,Mn-rich), REEs were mostly associated with Al and Mn (hydr)oxides, while select heavy REEs (e.g., Gd, Dy) were co-localized with Fe (hydr)oxides. Co and Ni have different distribution zones, while both co-localized with Mn (hydr)oxides. Based on this characterization, NETL developed a patent-pending innovative step-leaching protocol, “Targeted Rare Earth Extraction (TREE)” to effectively recover up to 90% REE and 60% Co in separate steps. In addition, select post-TREE solid residuals (purified Al oxides, or Mn oxides) can be further developed into functional materials (e.g., lithium and CO2 sorbents) needed for green energy transition and carbon management. This characterization-informed approach as well as TREE processing from AMD solids can be used for other legacy wastes (e.g., coal ash, oil and gas drill cutting, mine tailings), and offers an opportunity to transform waste streams into environmental and economic assets that meet U.S. Department of Energy and U.S. Environmental Protection Agency goals.

characterization and extraction of rare earth elem↗
DOE OSTI2017

Bench-Scale Evaluation of the Genifuel Hydrothermal Processing Technology for Wastewater Solids

Hydrothermal Liquefaction (HTL) and Catalytic Hydrothermal Gasification (CHG) proof-of-concept bench-scale tests were performed to assess the potential of the Genifuel hydrothermal process technology for handling municipal wastewater sludge. HTL tests were conducted at 300-350°C and 20 MPa on three different feeds: primary sludge (11.9 wt% solids), secondary sludge (9.7 wt% solids), and post-digester sludge (also referred to as digested solids) (16.0 wt% solids). Corresponding CHG tests were conducted at 350°C and 20 MPa on the HTL aqueous phase output using a ruthenium based catalyst. A comprehensive analysis of all feed and effluent phases was also performed. Total mass and carbon balances closed to within ± 15% in all but one case. Biocrude yields from HTL tests were 37%, 25%, and 34% for primary sludge, secondary sludge, and digested solids feeds, respectively. The biocrude yields accounted for 59%, 39%, and 49% of the carbon in the feed for primary sludge, secondary sludge, and digested solids feeds, respectively. Biocrude composition and quality were comparable to that seen with biocrudes generated from algae feeds. Subsequent hydrotreating (i.e., upgrading) of the biocrude produced from primary sludge and digested solids resulted in a product with comparable physical and chemical properties to petroleum crude oil. CHG product gas consisted primarily of methane, with methane yields (relative to CHG input) on a carbon basis of 47%, 61%, and 64% for aqueous feeds that were the output of HTL tests with primary sludge, secondary sludge, and digested solids, respectively. Siloxane concentrations in the CHG product gas were below the detection limit and well below fuel input composition limits set by several engine manufacturers. Relative to that of the sludge feeds, the HTL-CHG process resulted in a reduction in chemical oxygen demand (COD) of greater than 99.9% and a reduction in residual solids for disposal of 94-99%. The test results, as a whole, support further long term testing in a larger scale integrated system that is representative of what would be installed at a water resource recovery facility (WRRF) in order to fully assess the technical and economic viability of this technology for wastewater sludge treatment.

biocrude↗
DOE OSTI2024

Planet Formation by Gas-assisted Accretion of Small Solids

We compute the accretion efficiency of small solids, with radii 1 cm ≤ R s ≤ 10 m, on planets embedded in gaseous disks. Planets have masses 3 ≤ M p ≤ 20 Earth masses (M ⊕ ) and orbit within 10 au of a solar mass star. Disk thermodynamics is modeled via 3D radiation-hydrodynamics calculations that typically resolve the planetary envelopes. Both icy and rocky solids are considered, explicitly modeling their thermodynamic evolution. The maximum efficiencies of 1 ≤ R s ≤ 100 cm particles are generally ≲10%, whereas 10 m solids tend to accrete efficiently or be segregated beyond the planet’s orbit. A simplified approach is applied to compute the accretion efficiency of small cores, with masses M p ≤ 1 M ⊕ and without envelopes, for which efficiencies are approximately proportional to $M^{2/3}_{p}$. The mass flux of solids, estimated from unperturbed drag-induced drift velocities, provides typical accretion rates dM p /dt ≲ 10 -5 M ⊕ yr -1 . In representative disk models with an initial gas-to-dust mass ratio of 70–100 and total mass of 0.05–0.06 M ⊙ , the solids’ accretion falls below 10 -6 M ⊕ yr -1 after 1–1.5 Myr. The derived accretion rates, as functions of time and planet mass, are applied to formation calculations that compute dust opacity self-consistently with the delivery of solids to the envelope. Assuming dust-to-solid coagulation times of ≈0.3 Myr and disk lifetimes of ≈3.5 Myr, heavy-element inventories in the range 3–7 M ⊕ require that ≈90–150 M ⊕ of solids cross the planet’s orbit. The formation calculations encompass a variety of outcomes, from planets a few times M ⊕ , predominantly composed of heavy elements, to giant planets. The peak luminosities during the epoch of the solids’ accretion range from ≈10 -7 to ≈10 -6 L ⊙ .

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1991

Experimental investigation of a solid rocket combustion simulator

The response of solid rocket motor materials to high-temperature corrosive gases is usually accomplished by testing the materials in a subscale solid rocket motor. While this imposes the proper thermal and chemical environment, a solid rocket motor does not provide practical features that would enhance systematic evaluations such as: the ability to throttle for margin testing, on/off capability, low test cost, and a low-hazards test article. Solid Rocket Combustion Simulators (SRCS) are being evaluated by NASA to test solid rocket nozzle materials and incorporate these essential practical features into the testing of rocket materials. The SRCS is designed to generate the thermochemical environment of a solid rocket. It uses hybrid rocket motor technology in which gaseous oxygen (Gox) is injected into a chamber containing a solid fuel grain. Specific chemicals are injected in the aft mixing chamber so that the gases entering the test section match the temperature and a non-dimensional erosion factor B' to insure similarity with a solid motor. Because the oxygen flow can be controlled, this approach allows margin testing, the ability to throttle, and an on/off capability. The fuel grains are inert which makes the test article very safe to handle. The objective of this work was to establish the baseline operating characteristics of a Labscale Solid Rocket Combustion Simulator (LSRCS). This included establishing the baseline burning rates of plexiglass fuels and the evaluation of a combustion instability for hydroxy-terminated polybutadyene (HTPB) propellants. The scope of the project included: (1) activation of MSFC Labscale Hybrid Combustion Simulator; (2) testing of plexiglass fuel at Gox ranges from 0.025 to 0.200 lb/s; (3) burning HTPB fuels at a Gox rate of 0.200 lb/s using four different mixing chamber configurations; and (4) evaluating the fuel regression and chamber pressure responses of each firing.

Frederick, Robert A., Jr.↗
NASA NTRS1999

Coarsening in Solid-Liquid Mixtures Studied on the Space Shuttle

Ostwald ripening, or coarsening, is a process in which large particles in a two-phase mixture grow at the expense of small particles. It is a ubiquitous natural phenomena occurring in the late stages of virtually all phase separation processes. In addition, a large number of commercially important alloys undergo coarsening because they are composed of particles embedded in a matrix. Many of them, such as high-temperature superalloys used for turbine blade materials and low-temperature aluminum alloys, coarsen in the solid state. In addition, many alloys, such as the tungsten-heavy metal systems, coarsen in the solid-liquid state during liquid phase sintering. Numerous theories have been proposed that predict the rate at which the coarsening process occurs and the shape of the particle size distribution. Unfortunately, these theories have never been tested using a system that satisfies all the assumptions of the theory. In an effort to test these theories, NASA studied the coarsening process in a solid-liquid mixture composed of solid tin particles in a liquid lead-tin matrix. On Earth, the solid tin particles float to the surface of the sample, like ice in water. In contrast, in a microgravity environment this does not occur. The microstructures in the ground- and space-processed samples (see the photos) show clearly the effects of gravity on the coarsening process. The STS-83-processed sample (right image) shows nearly spherical uniformly dispersed solid tin particles. In contrast, the identically processed, ground-based sample (left image) shows significant density-driven, nonspherical particles, and because of the higher effective solid volume fraction, a larger particle size after the same coarsening time. The "Coarsening in Solid-Liquid Mixtures" (CSLM) experiment was conducted in the Middeck Glovebox facility (MGBX) flown aboard the shuttle in the Microgravity Science Laboratory (MSL-1/1R) on STS-83/94. The primary objective of CSLM is to measure the temporal evolution of the solid particles during coarsening.

Caruso, John J.↗
DOE OSTI2027

A multi-region approach for the analysis of porous materials and gas-solid reactions using USAXS-SAXS-WAXS: application to CaO carbonation

The reaction rate of gas-solid non-catalytic reactions is typically investigated using reactant conversion data over time and ex-situ measurements of the porous solid reactant textural properties; these data enable the experimental estimation of the initial intrinsic reaction rate, whereas the evolution of the textural properties and the reaction rate over time are evaluated theoretically using reaction models. In this work, a different methodology is presented, based on: a) in-situ time-resolved USAXS-SAXS-WAXS measurements of the solid sample, and b) a multi-region modeling approach; this methodology allows for the estimation of the textural properties and the intrinsic reaction rate at any time during the reaction. Referring to a reaction in which a solid product is obtained from a solid reactant and a gaseous reactant, the porous particle is described as consisting of several distinct regions with different microstructural properties, and both a gas-solid reaction model and a SAXS model are derived and applied to the carbonation of porous CaO. The proposed reaction model highlights the role of the inaccessible reactant and accurately predicts the solid reactant conversion versus time profile. The SAXS model accurately predicts the measured linear trends of the Porod invariant and of the pre-factor of the power law scattering profile versus CaO mass fraction; in the absence of chemical reactions, the proposed equations extend classical SAXS theory to porous materials containing macropores and nonporous solid phases in addition to standard nanoscale inhomogeneous regions.

CO2 solid sorbents↗
DOE OSTI2014

From Ag{sub 2}Sb{sub 2}O{sub 6} to Cd{sub 2}Sb{sub 2}O{sub 7}: Investigations on an anion-deficient to ideal pyrochlore solid solution

A complete solid solution between the anion-deficient pyrochlore Ag{sub 2}Sb{sub 2}O{sub 6} and the ideal pyrochlore Cd{sub 2}Sb{sub 2}O{sub 7} has been synthesized through the standard solid state ceramic method. Each composition has been characterized by various different techniques, including powder X-ray diffraction, optical spectroscopy, electron paramagnetic resonance and {sup 121}Sb Mössbauer spectroscopy. Computational methods based on density functional theory complement this investigation. Photocatalytic activity has been studied, and transport properties have been measured on pellets densified by spark plasma sintering. The analysis of the data collected from these various techniques enables a comprehensive characterization of the complete solid solution and revealed an anomalous behavior in the Cd-rich end of the solid solution, which has been proposed to arise from a possible radical O{sup −} species in small concentrations. - Graphical abstract: A complete solid solution between the anion-deficient pyrochlore Ag{sub 2}Sb{sub 2}O{sub 6} and the ideal pyrochlore Cd{sub 2}Sb{sub 2}O{sub 7} has been synthesized and investigated through various techniques including X-ray diffraction, electron paramagnetic spectroscopy, and {sup 121}Sb-Mössbauer spectroscopy. Optical and electrical measurements have been performed, and computational methods have been applied to determine the density of states. Photocatalytic activity was monitored by the degradation of Methylene Blue, and upon cadmium substitution, the degradation amount decreased, which is attributed primarily to the changing optical and electrical properties of the solid solution. Display Omitted - Highlights: • A complete solid solution between Ag{sub 2}Sb{sub 2}O{sub 6} and Cd{sub 2}Sb{sub 2}O{sub 7} has been synthesized. • XRD reveals a relatively constant lattice parameter as the series progresses. • Optical and electrical properties have been measured for the solid solution. • Computational methods have been used to determine the density of states. • Photocatalytic degradation of Methylene Blue decreased upon cadmium substitution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Aqueous Electrochemical Energy Storage with a Mediator-Ion Solid Electrolyte

This study presents a battery concept with a “mediator-ion” solid electrolyte for the development of next-generation electrochemical energy storage technologies. The active anode and cathode materials in a single cell can be in the solid, liquid, or gaseous form, which are separated by a sodium-ion solid-electrolyte separator. The uniqueness of this mediator-ion strategy is that the redox reactions at the anode and the cathode are sustained by a shuttling of a mediator sodium ion between the anolyte and the catholyte through the solid-state electrolyte. Use of the solid-electrolyte separator circumvents the chemical-crossover problem between the anode and the cathode, overcomes the dendrite-problem when employing metal-anodes, and offers the possibility of using different liquid electrolytes at the anode and the cathode in a single cell. The battery concept is demonstrated with two low-cost metal anodes (zinc and iron), two liquid cathodes (bromine and potassium ferricyanide), and one gaseous cathode (air/O2) with a sodium-ion solid electrolyte. This novel battery strategy with a mediator-ion solid electrolyte is applicable to a wide range of electrochemical energy storage systems with a variety of cathodes, anodes, and mediator-ion solid electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2015

A solid solution series of atacamite type Ni{sub 2x}Mg{sub 2−2x}Cl(OH){sub 3}

For the first time a complete solid solution series Ni{sub 2x}Mg{sub 2−2x}Cl(OH){sub 3} of an atacamite type alkaline main group metal chloride, Mg{sub 2}Cl(OH){sub 3}, and a transition group metal chloride, Ni{sub 2}Cl(OH){sub 3}, was prepared and characterized by chemical and thermal analysis as well as by Raman and IR spectroscopy, and high resolution laboratory X-ray powder diffraction. All members of the solid solution series crystallize in space group Pnam (62). The main building units of these crystal structures are distorted, edge-linked Ni/MgO{sub 4}Cl{sub 2} and Ni/MgO{sub 5}Cl octahedra. The distribution of Ni{sup 2+}- and Mg{sup 2+}-ions among these two metal-sites within the solid solution series is discussed in detail. The crystallization of the solid solution phases occurs via an intermediate solid solution series, (Ni/Mg)Cl{sub 2x}(OH){sub 2−2x}, with variable Cl: OH ratio up to the 1:3 ratio according to the formula Ni{sub 2x}Mg{sub 2−2x} Cl(OH){sub 3}. For one isolated intermediate solid solution member, Ni{sub 0.70}Mg{sub 0.30}Cl{sub 0.58}(OH){sub 1.42}, the formation and crystal structure is presented as well. - Graphical abstract: For the first time a complete solid solution series, Ni{sub 2x}Mg{sub 2−2x} Cl(OH){sub 3}, was synthesized and characterized. Structure solution by revealed that Ni{sup 2+} prefers to occupy the Jahn–Teller-like distorted hole, out of two available cation sites. Substitution of Ni{sup 2+} by Mg{sup 2+} in atacamite type Ni{sub 2}Cl(OH){sub 3} results in systematic band shifts in Raman and IR spectra as well as in systematic changes in thermal properties. The α-polymorphs M{sub 2}Cl(OH){sub 3} with M=Mg{sup 2+}, Ni{sup 2+} and other divalent transition metal ions, as described in literature, were identified as separate compounds. - Highlights: • First synthesis of solid solution series between main and transition metal chloride. • Ni{sup 2+} prefers to occupy Jahn–Teller-like distorted octahedral holes. • Substitution of Ni{sup 2+} by Mg{sup 2+} results in systematic Raman and IR band shifts. • α-Polymorphs M{sub 2}Cl(OH){sub 3} with M=Mg{sup 2+}, Ni{sup 2+}, … as described in literature do not exist.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Microstructure evolution of wrought nickel based superalloy GH4037 in the semi-solid state

Highlights: • Semi-solid isothermal treatment of wrought superalloy (SSITWS). • Near-globular microstructure. • Carbide precipitates. - Abstract: Study on semi-solid processing of superalloy is little reported due to the difficulties in fabricating semi-solid billets. In this manuscript, a novel method called semi-solid isothermal treatment of wrought superalloy (SSITWS) was firstly proposed in order to fabricate semi-solid billets of superalloy. The effects of isothermal temperature and soaking time on microstructure of Ni-based superalloy GH4037 in the semi-solid state were investigated. The results show that the near-globular microstructure of wrought GH4037 superalloy can be obtained by the semi-solid isothermal treatment. The average grain size increased and the roundness decreased with the prolonged soaking time at 1350 °C and 1360 °C. When the isothermal temperature was elevated to 1370 °C or 1380 °C, the microstructure evolution was complex due to the combination of breaking up mechanism and coarsening mechanism. At 1390 °C, the dendritic grains were obviously observed in the microstructure. With the increasing of isothermal temperature and soaking time, the liquid boundary film coarsening behavior occurred in the microstructure. With the increasing of soaking time, the size of intragranular liquid droplets increased, but the amount of them decreased. When the isothermal temperature was high, the intragranular liquid droplets disappeared. The coarsening rate constant at 1360 °C was lower compared to that at 1350 °C. However, when the isothermal temperature was higher than 1370 °C, the coarsening kinetics was not suitable for describing the microstructure evolution. The discrete carbide precipitates appeared in the grain boundaries. The distribution of Ti and Mo were higher in the grain boundaries than that in solid grains, and the distribution of other elements was homogenous in the grain boundaries and inside the grains.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Low Melting Temperature Gallium–Indium Liquid Metal Anode for Solid-State Li-Ion Batteries

Solid-state Li-ion batteries are attracting attention for their enhanced safety features, higher energy density, and broader operational temperature range compared to systems based on liquid electrolytes. However, current solid-state Li-ion batteries face performance challenges, such as suboptimal cycling and poor rate capabilities, often due to inadequate interfacial contact between the solid electrolyte and electrodes. To address this issue, we incorporated a gallium–indium (Ga–In) liquid metal as the anode in a solid-state Li-ion battery setup, employing Li 6 PS 5 Cl as the solid electrolyte. Operating at room temperature, this configuration achieved an initial capacity of 389 mAh g –1 and maintained 88% of this capacity after 30 cycles at a 0.05 C rate. It also demonstrated a capacity retention of 66% after 500 cycles at a 0.5 C rate. In comparison to solid anode materials, such as tin, the Ga–In liquid metal exhibited superior cycling stability and rate capacity, which is due to the self-healing and fluid properties of the alloy that ensure stable interfacial contact with solid electrolytes. In situ X-ray diffraction (XRD) and ex situ scanning electron microscope (SEM) analyses revealed that indium does not directly participate in the lithiation/delithiation process. Instead, it helps maintain the alloy’s low melting point, facilitating its return to a liquid state after delithiation. In a comparative analysis of stack pressure during cycling in cells utilizing Ga–In liquid metal and tin, the Ga–In liquid metal cell demonstrated an ability to buffer pressure increases associated with deformation. In conclusion, these findings suggest a promising approach for enhancing solid-state batteries by integrating liquid metal anodes, which improve interfacial contact and stability.

Alloys↗
DOE OSTI2017

Hydrophobic Solid Acids and Their Catalytic Applications in Green and Sustainable Chemistry

Acid catalysts are widely used in petrochemical reactions, the synthesis of fine chemicals, and biomass conversions in industry. To comply with the principles of green and sustainable chemistry, much attention is being paid to the replacement of traditional liquid acids with solid acid catalysts. Normally, solid acids exhibit hydrophilicity because of the unique hydrophilic nature of the acidic sites on their surfaces. Water, as a typical solvent, byproduct, or negative component in a variety of acid-catalyzed reactions, may be adsorbed on solid acids and then cause the deactivation of catalytic sites or hydrolysis of the frameworks. The development of solid acids with suitable hydrophobicity largely overcomes these issues and enhances their catalytic activities and reusability. This Review discusses some recent advances in the preparation of novel solid acids with controllable wettability and suitable hydrophobicity and highlights their application in catalyzing various reactions such as esterification, transesterification, acylation, condensation, hydration, and depolymerization of crystalline cellulose. In addition, this Review discusses how the hydrophobicity of solid acids is affected by their structures, surface characteristics, and acid centers, and determines the principles for designing solid acids with high catalytic activity and good reusability. It is instructive for researchers who are interested in designing new kinds of solid acids with improved efficiency and reusability for applications in green and sustainable chemistry.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Evidence for a Solid-Electrolyte Inductive Effect in the Superionic Conductor Li 10 Ge 1– x Sn x P 2 S 12

Strategies to enhance ionic conductivities in solid electrolytes typically focus on the effects of modifying their crystal structures or of tuning mobile-ion stoichiometries. A less-explored approach is to modulate the chemical bonding interactions within a material to promote fast lithium-ion diffusion. Recently, the idea of a solid-electrolyte inductive effect has been proposed, whereby changes in bonding within the solid-electrolyte host framework modify the potential energy landscape for the mobile ions, resulting in an enhanced ionic conductivity. Direct evidence for a solid-electrolyte inductive effect, however, is lacking—in part because of the challenge of quantifying changes in local bonding interactions within a solid-electrolyte host framework. Here, we consider the evidence for a solid-electrolyte inductive effect in the archetypal superionic lithium-ion conductor Li 10 Ge 1–x Sn x P 2 S 12 . Substituting Ge for Sn weakens the {Ge,Sn}–S bonding interactions and increases the charge density associated with the S 2– ions. This charge redistribution modifies the Li + substructure causing Li + ions to bind more strongly to the host framework S 2– anions, which in turn modulates the Li + ion potential energy surface, increasing local barriers for Li + ion diffusion. Each of these effects is consistent with the predictions of the solid-electrolyte inductive effect model. Density functional theory calculations predict that this inductive effect occurs even in the absence of changes to the host framework geometry due to Ge → Sn substitution. These results provide direct evidence in support of a measurable solid–electrolyte inductive effect and demonstrate its application as a practical strategy for tuning ionic conductivities in superionic lithium-ion conductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Solid neon as a noise-resilient host for electron qubits above 100 mK

Solid neon can be used as a solid host for single-electron qubits. At temperatures of around 10 mK, electron-on-solid-neon charge qubits exhibit long coherence times and high operation fidelities. However, a systematic characterization of the noise features of such systems is needed for the development of scalable quantum information architectures. Here, in this work, we show that solid neon can be used as a noise-resilient host for electron qubits above 100 mK. We examine the resilience of solid neon against charge and thermal noise when electron-on-solid-neon charge qubits are operated away from the charge-insensitive sweet spot and at elevated temperatures. We show that the extracted high-frequency charge noise density of electron-on-solid-neon qubits, projected as voltage fluctuations on nearby electrodes, is between 10 −4 μV 2 Hz −1 and 10 −6 μV 2 Hz −1 at 0.01 MHz to 1 MHz, which is comparable to common semiconductor hosts. We also show that the electron-on-solid-neon charge qubits operating at frequencies of around 5 GHz can maintain echo coherence times of over 1 μs at temperatures up to 400 mK.

42 ENGINEERING↗
DOE OSTI2013

Observation of strongly forbidden solid effect dynamic nuclear polarization transitions via electron-electron double resonance detected NMR

We present electron paramagnetic resonance experiments for which solid effect dynamic nuclear polarization transitions were observed indirectly via polarization loss on the electron. This use of indirect observation allows characterization of the dynamic nuclear polarization (DNP) process close to the electron. Frequency profiles of the electron-detected solid effect obtained using trityl radical showed intense saturation of the electron at the usual solid effect condition, which involves a single electron and nucleus. However, higher order solid effect transitions involving two, three, or four nuclei were also observed with surprising intensity, although these transitions did not lead to bulk nuclear polarization—suggesting that higher order transitions are important primarily in the transfer of polarization to nuclei nearby the electron. Similar results were obtained for the SA-BDPA radical where strong electron-nuclear couplings produced splittings in the spectrum of the indirectly observed solid effect conditions. Observation of high order solid effect transitions supports recent studies of the solid effect, and suggests that a multi-spin solid effect mechanism may play a major role in polarization transfer via DNP.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗