Material descriptors for thermoelectric performance of narrow-gap semiconductors and semimetals
Simple descriptors to search for low-temperature thermoelectric materials.
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Simple descriptors to search for low-temperature thermoelectric materials.
Direct synthesis of thin-film carbon nanomaterials on oxide-coated silicon substrates provides a viable pathway for building a dense array of miniaturized (micron-scale) electrochemical sensors with high performance. However, material synthesis generally involves many parameters, making material engineering based on trial and error highly inefficient. Here, we report a two-pronged strategy for producing engineered thin-film carbon nanomaterials that have a nano-graphitic structure. First, we introduce a variant of the metal-induced graphitization technique that generates micron-scale islands of nano-graphitic carbon materials directly on oxide-coated silicon substrates. A novel feature of our material synthesis is that, through substrate engineering, the orientation of graphitic planes within the film aligns preferentially with the silicon substrate. This feature allows us to use the Raman spectroscopy for quantifying structural properties of the sensor surface, where the electrochemical processes occur. Second, we find phenomenological models for predicting the amplitudes of the redox current and the sensor capacitance from the material structure, quantified by Raman. Our results indicate that the key to achieving high-performance micro-sensors from nano-graphitic carbon is to increase both the density of point defects and the size of the graphitic crystallites. Our study offers a viable strategy for building planar electrochemical micro-sensors with high-performance.
Proton exchange membrane water electrolyzers (PEMWEs) are expected to play a crucial role in the global green energy transition during the 21st century. They provide a versatile and sustainable solution for generating hydrogen with very high purity in combination with renewable energies, such as solar and wind. Despite their promise, PEMWEs face several critical problems, including high costs, performance limitations, and durability challenges, particularly at low iridium (Ir) loading on the anode. Advancing next-generation PEMWEs requires extensive work on materials engineering of all cell components, including the catalyst layer (CL), membrane, porous transport layer (PTL), bipolar plate (BPP), and gasket. This task must be performed with the complementary contribution of different modeling and characterization techniques. This review presents a critical perspective from academia, research centers, and industry, mapping main developments, remaining gaps, and strategic pathways to advance PEMWE technology. A focus is devoted to key aspects, such as operation at low Ir loading, membrane durability, multiscale transport layers, porous and non-porous flow fields, multiphysics modeling, and multipurpose characterization techniques, which are thoroughly discussed. By unifying these topics, this review provides readers with the essential knowledge to grasp current developments and tackle tomorrow's challenges in PEMWE engineering.
An ablative material composed of silica-filled elastomeric silicone was tested to evaluate its thermal and structural performance as an external insulator, or heat shield, for a hypersonic research aircraft. The material was also tested to determine whether it would form a durable char layer when initially heated and thereafter function primarily as an insulator with little further pyrolysis or char removal. Aerothermal tests were representative of nominal Mach 6 cruise conditions of the aircraft, and additional tests were representative of Mach 8 cruise and interference heating conditions. Radiant heating tests were used to simulate the complete nominal Mach 6 surface-temperature history. The silica char that formed during aerothermal tests was not durable. The char experienced a general and preferential surface recession, with the primary mechanism for char removal being erosion. Tests revealed that radiant heating is not a valid technique for simulating aerodynamic heating of the material.
This review describes the advancements in the field of Ni-rich NCM cathodes in terms of manufacturing processes, material challenges, modification techniques, and future research directions, and discusses the correlation between the synthesis and electrochemical performance.
Abstract Following the 2nd release of the “Emerging PV reports,” the best achievements in the performance of emerging photovoltaic devices in diverse emerging photovoltaic research subjects are summarized, as reported in peer‐reviewed articles in academic journals since August 2021. Updated graphs, tables, and analyses are provided with several performance parameters, e.g., power conversion efficiency, open‐circuit voltage, short‐circuit current density, fill factor, light utilization efficiency, and stability test energy yield. These parameters are presented as a function of the photovoltaic bandgap energy and the average visible transmittance for each technology and application, and are put into perspective using, e.g., the detailed balance efficiency limit. The 3rd installment of the “Emerging PV reports” extends the scope toward triple junction solar cells.
A performance prediction was adapted to evaluate the use of ceramic materials in solar receivers for point focusing distributed applications. System requirements were determined including the receiver operating environment and system operating parameters for various engine types. Preliminary receiver designs were evolved from these system requirements. Specific receiver designs were then evaluated to determine material functional requirements.
The Hanford site stores more than 200 million liters of radioactive and chemically hazardous wastes from the production of weapons materials. The wastes are stored in 177 underground carbon-steel storage tanks, separated between 149 single shell tanks (SSTs) and 28 double shell tanks (DSTs). The DSTs provide critical retrieval and interim storage before the waste is vitrified in the Waste Treatment and Isolation Plant (WTP). The tanks will need to remain in-service far beyond the initial 40-year design life, and effective corrosion control practices must remain in force to extend the tanks’ lifespans. This effort includes direct measurements of corrosion rate (e.g., ultrasonic measurements and corrosion coupons) and electrochemical processes (e.g., linear polarization measurements and open circuit potential measurements). The Hanford site began monitoring the corrosion potential in select DSTs in 2008. Of the 45 reference electrodes that have been installed, 29 have failed and 6 others provided unreliable results. DOE-EM is supporting a 3-year program to develop a chemical and radiation resistant reference electrode for application in the Hanford tanks. The first year of the program focused on understanding the failure mechanism for the reference electrodes and identification of candidate construction materials that would mitigate degradation of the electrodes in the waste environment. During the second year of the program, the objectives were to: 1) test candidate materials under simulated waste conditions, 2) design components that will extend the service life of the electrode, 3) fabricate materials for prototype reference electrodes, and 4) assemble prototype reference electrodes for accelerated testing. The reference electrode is constructed of four principal parts: 1) junction, 2) casing, 3) inner chamber backfill materials, and 4) the sensing wire. Principally, improvements of the junction, casing, and inner chamber backfill materials are being pursued. The junction material at the interface between the waste and the inner chamber of the reference electrode was identified as a critical component in the failure of the reference electrodes. Nine candidate replacement junction materials were tested under simulated waste conditions to evaluate permeation rate. These materials included a variety of polymeric and ceramic materials, some of which were 3-D printed. Thus far, porous polyvinylidene fluoride materials have performed satisfactorily and are being considered for prototype development. The commercial electrode casing materials in general have performed well. Additionally, 3-D printing of chemically and mechanically stable materials is being investigated as a means for further improvement in fabrication consistency. SRNL has also investigated altering the reference electrode design to extend the service life. The new design of the interior of the reference electrode casing creates a longer, more tortuous path between the junction material and the electrode sensing wire. A finite element model was used to optimize the design without adversely impacting the circuit resistance of the electrode during the measurements, thus preserving the measurement accuracy while enhancing the service life. The inner chamber back fill materials are also critical to the performance of the reference electrode. Materials that are resistant to intruding tank waste and provide a conductive path to the sensing wire were investigated. Gel and powder materials that are interspersed with a conductive chloride bearing material were tested for their influence on diffusion and electrode resistance. All the investigated materials and components will be assembled, with collaboration from commercial vendors, to fabricate the initial prototypes. Accelerated testing of the prototypes will be initiated in Year 2 of the program and will be completed in Year 3. A recommendation on the materials of construction and the design of the new robust reference electrode will be presented to the Hanford tank farm facility.
Lightning tests were performed on composite materials as a part of an investigation of electromagnetic effects on the materials. Samples were subjected to direct and remote simulated lightning strikes. Samples included various thicknesses of graphite filament reinforced plastic (GFRP), material enhanced by expanded aluminum foil layers, and material with an aluminum honeycomb core. Shielding properties of the material and damage to the sample surfaces and joints were investigated. Adding expanded aluminum foil layers and increasing the thickness of GFRP improves the shielding effectiveness against lightning induced fields and the ability to withstand lightning strikes. A report describing the lightning strike tests performed by the U.S. Army Redstone Technical Test Center, Redstone Arsenal, AL, STERT-TE-E-EM, is included as an appendix.
High performance polymeric materials are finding increased use in aerospace applications. Proposed high speed aircraft will require materials to withstand high temperatures in an oxidative atmosphere for long periods of time. It is essential that accurate estimates be made of the performance of these materials at the given conditions of temperature and time. Temperatures of 350 F (177 C) and times of 60,000 to 100,000 hours are anticipated. In order to survey a large number of high performance polymeric materials on a reasonable time scale, some form of accelerated testing must be performed. A knowledge of the rate of a process can be used to predict the lifetime of that process. Thermogravimetric analysis (TGA) has frequently been used to determine kinetic information for degradation reactions in polymeric materials. Flynn and Wall studied a number of methods for using TGA experiments to determine kinetic information in polymer reactions. Kinetic parameters, such as the apparent activation energy and the frequency factor, can be determined in such experiments. Recently, researchers at the McDonnell Douglas Research Laboratory suggested that a graph of the logarithm of the frequency factor against the apparent activation energy can be used to predict long-term thermo-oxidative stability for polymeric materials. Such a graph has been called a kinetic map. In this study, thermogravimetric analyses were performed in air to study the thermo-oxidative degradation of several high performance polymers and to plot their kinetic parameters on a kinetic map.
Evaluating the performance of materials on the exterior of spacecraft is of continuing interest, particularly in anticipation of those applications that will require a long duration in low Earth orbit. The Passive Optical Sample Assembly (POSA) experiment flown on the exterior of Mir as a risk mitigation experiment for the International Space Station was designed to better understand the interaction of materials with the low Earth orbit environment and to better understand the potential contamination threats that may be present in the vicinity of spacecraft. Deterioration in the optical performance of candidate space power materials due to the low Earth orbit environment, the contamination environment, or both, must be evaluated in order to propose measures to mitigate such deterioration. The thirty two samples of space power materials studied here include solar array blanket materials such as polyimide Kapton H and SiO(x) coated polyimide Kapton H, front surface aluminized sapphire, solar dynamic concentrator materials such as silver on spin coated polyimide and aluminum on spin coated polyimide, CV 1144 silicone, and the thermal control paint Z-93-P. The physical and optical properties that were evaluated prior to and after the POSA flight include mass, total, diffuse, and specular reflectance, solar absorptance, and infrared emittance. Additional post flight evaluation included scanning electron microscopy to observe surface features caused by the low Earth orbit environment and the contamination environment, and variable angle spectroscopic ellipsometry to identify contaminant type and thickness. This paper summarizes the results of pre- and post-flight measurements, identifies the mechanisms responsible for optical properties deterioration, and suggests improvements for the durability of materials in future missions.
Using a combination of in-situ high-resolution digital image correlation (HR-DIC), Heaviside-DIC method (H-DIC), and crystal plasticity finite element (CPFE), we investigate the evolution of intragranular lattice rotations and slip activity during monotonic and cyclic loading in a high performance, polycrystalline face centered cubic material. The CPFE employs a quasi-3D model microstructure, which is a highly resolved mirror representation of the experimental in-situ test sample. In agreement, the measurements and calculations reveal that most grains, regardless of their size and lattice orientation, develop intragranular lattice rotation gradients that span the grain. For a small cluster of grains on the deformed material, we perform HR-DIC analysis of slip lines to demonstrate agreement in the active slip systems and changes in this local slip activity across the individual grains. The combined analysis reveals that deforming grains are divided into sub-granular regions of uniform lattice rotation and these regions are most often associated with only one or two active slip systems. The gradient lines that divide them correspond to changes in the predominant slip system. The model is used to examine the evolution of intragranular lattice rotation in a single fully reversed tension-compression cycle. The calculations indicate that intragranular gradients intensify during the reverse loading path as nearest neighboring regions appear to shed lattice rotation, increasing the lattice rotation in some regions, while shutting down rotation in neighboring regions. So these findings provide insight into the irreversible changes that develop within deforming grains at the scale of the grain, particularly the heterogeneous development of intragranular lattice rotation in early stages of deformation, which could serve as precursors to localization.
Papers are presented dealing with the development of aircraft seats with the minimum fire risk. Criteria examined include: flame spread, heat release, and smoke and/or toxic fumes. Materials and performance specifications of all seat material options are provided.
The Heatshield for Extreme Entry Environment Technology (HEEET) projects objective is to mature a 3-D Woven Thermal Protection System (TPS) to Technical Readiness Level (TRL) 6 to support future NASA missions to destinations such as Venus and Saturn. The scope of the project, status of which will be discussed, encompasses development of manufacturing and integration processes, fabrication of a prototype 1m diameter engineering test unit (ETU) that will undergo a series of structural tests, characterizing material aerothermal performance including development of a material response model, and structural testing and analysis to develop tools to support design and establish system capability.
The Orion Multi-Purpose Crew Vehicle (MPCV) will transport four crew members to and from lunar-class orbital destinations. The first orbital Exploration Flight Test (EFT-1) is scheduled for December 2014 and will provide valuable data on several systems, including the heat shield. The heat shield material is AvcoatTM, a mid-density ablator. Specifically, the heat shield contains a fiberglass-phenolic honeycomb structure filled with an ablative epoxy novolac resin. Post-flight characterization of the EFT-1 thermal protection system will be conducted in order to study the material response and measure the char front of the material. Avcoat density profiling will be conducted to study three critical material zones: char, pyrolysis, and virgin states as a function of material depth. As part of a ground test campaign, Avcoat coupons are tested at the NASA Ames Research Center Arc Jet Complex. The test campaign is set forth to study material response based on environments, perform Avcoat material density characterization, and compare the char depths from the HEAT sensor and density profiling studies. These investigations will then be compared to flight data in order to improve upon TPS material response models.
Alloy 709 has been selected as the next candidate material for Section III, Division 5 qualification in the American Society of Mechanical Engineers (ASME) Boiler and Pressure Vessel Code (BPVC) for elevated-temperature nuclear construction. The qualification data package requires an assortment of information and material data including tensile, creep, and creep-fatigue performance at elevated temperatures from different material heats. The goal of the project is to generate a dataset to support qualification of Alloy 709 material for ASME BPVC design code. Working towards the project goal, Idaho National Laboratory needs to conduct a series of tests on three different heats to support the A709 code case development. At present, there is a gap in the data package for one of the heats: Heat number 58776 manufactured by G.O. Carlson. To address this data gap, Argonne National Laboratory transmitted five plates of A709 heat 58776 manufactured by G.O. Carlson to Idaho National Laboratory. These plates were solution annealed at 1150°C and heat treated at 775°C for 10 hours. The objective of this specification is to procure a series of creep-fatigue specimens to support the qualification data package. The creep-fatigue specimen design captures the cyclic material performance at elevated temperature. The material performance data generated from specimens machined herein will support the ASME BPVC code case development and establish design limits, and design life curves for Alloy 709 material.
A lithium or sodium battery includes a cathode containing manganese; an anode containing an active anode material; a separator; an electrolyte; and a transition metal ion sequestration agent; wherein the transition metal ion sequestration agent contains a micron or nano-sized inorganic compound and the transition metal ion sequestration agent is located on and/or within the separator; on and/or within the anode; in the electrolyte; or any combination thereof.
To address the high cost, cobalt dependency, and resource constraints typical of conventional high-entropy oxide (HEO) anodes, this study reports the successful synthesis of two Co-free, six-component spinel-type HEOs(FeNiCrMnZnAl) 3 O 4 (HEO-Al) and (FeNiCrMnZnMg) 3 O 4 (HEO-Mg), via a sol-gel method. The distinct effects of Al 3+ and Mg 2+ incorporation on the electrochemical performance and lithium storage kinetics were systematically investigated. XRD, Raman, and TEM characterizations confirm that both materials possess a pure spinel phase, uniform particle size, and homogeneous elemental distribution. Notably, electrochemical evaluations reveal that HEO-Al delivers a superior reversible capacity of 480.7 mAh g −1 after 100 cycles at 0.1 A g −1 , and maintains 354.5 mAh g −1 after 1000 long-term cycles at 1 A g −1 , significantly outperforming HEO-Mg. Kinetic analysis indicates that HEO-Al exhibits lower charge transfer resistance, a higher Li + diffusion coefficient, and a pseudocapacitive contribution of up to 82%. Furthermore, these findings demonstrate that Al substitution effectively optimizes the structural stability and lithium storage kinetics of Co-free HEOs, providing a viable strategy for designing low-cost, highly stable HEO anode systems.