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At least 91 records · Page 5

Properties of Semiconducting Ru_2Ge_3

Transport properties of large single crystalline samples of Ru_2Ge_3 grown from the melt have been investigated in a 25-1000 C temperature range. A diffusionless transition between 500 and 550C from a high temperature tetragonal structure to a low temperature orthorhombic structure was clearly observed. Results showed that both the low temperature orthorhombic and the high temperature structural tetragonal phase are semiconductors. Some anisotropy of the transport coefficients was determined by measuring the samples in orientations parallel and perpendicular to the preferential direction of crystal growth. Large Seebeck coefficient (up to 400 microVK^(-1)) and low thermal conductivity (as low as 20x10^(-3) Wcm^(-1)K^(-1)) were achieved for the low temperature orthorhombic phase. Difficulties in preparing heavily doped samples and low Hall mobilities have limited values for the maximum figure of merit to 0.5 x 10^(-3) K^(-1) at 500 C.

Fleurial, Jean-Pierre↗

High performance thermoelectric materials and methods of preparation

Transition metals (T) of Group VIII (Co, Rh and Ir) have been prepared as semiconductor alloys with Sb having the general formula TSb.sub.3. The skutterudite-type crystal lattice structure of these semiconductor alloys and their enhanced thermoelectric properties results in semiconductor materials which may be used in the fabrication of thermoelectric elements to substantially improve the efficiency of the resulting thermoelectric device. Semiconductor alloys having the desired skutterudite-type crystal lattice structure may be prepared in accordance with the present invention by using vertical gradient freeze techniques, liquid-solid phase sintering techniques, low temperature powder sintering and/or hot-pressing. Measurements of electrical and thermal transport properties of selected semiconductor materials prepared in accordance with the present invention, demonstrated high Hall mobilities (up to 8000 cm.sup.2.V.sup.-1.s.sup.-1), good Seebeck coefficients (up to 400 .mu.VK.sup.-1 between 300.degree. C. and 700.degree. C.), and low thermal conductivities (as low as 15 mW/cmK). Optimizing the transport properties of semiconductor materials prepared from elemental mixtures Co, Rh, Ir and Sb resulted in a two fold increase in the thermoelectric figure of merit (ZT) at temperatures as high as 400.degree. C. for thermoelectric elements fabricated from such semiconductor materials.

Fleurial, Jean-Pierre↗

Polyimide Aerogel Thin Films

Polyimide aerogels have been crosslinked through multifunctional amines. This invention builds on "Polyimide Aerogels With Three-Dimensional Cross-Linked Structure," and may be considered as a continuation of that invention, which results in a polyimide aerogel with a flexible, formable form. Gels formed from polyamic acid solutions, end-capped with anhydrides, and cross-linked with the multifunctional amines, are chemically imidized and dried using supercritical CO2 extraction to give aerogels having density around 0.1 to 0.3 g/cubic cm. The aerogels are 80 to 95% porous, and have high surface areas (200 to 600 sq m/g) and low thermal conductivity (as low as 14 mW/m-K at room temperature). Notably, the cross-linked polyimide aerogels have higher modulus than polymer-reinforced silica aerogels of similar density, and can be fabricated as both monoliths and thin films.

Meador, Mary Ann↗

Insulation Reformulation Development

The current Space Launch System (SLS) internal solid rocket motor insulation, polybenzimidazole acrylonitrile butadiene rubber (PBI-NBR), is a new insulation that replaced asbestos-based insulations found in Space Shuttle heritage solid rocket boosters. PBI-NBR has some outstanding characteristics such as an excellent thermal erosion resistance, low thermal conductivity, and low density. PBI-NBR also has some significant challenges associated with its use: Air entrainment/entrapment during manufacture and lay-up/cure and low mechanical properties such as tensile strength, modulus, and fracture toughness. This technology development attempted to overcome these challenges by testing various reformulated versions of booster insulation. The results suggest the SLS program should continue to investigate material alternatives for potential block upgrades or use an entirely new, more advanced booster. The experimental design was composed of a logic path that performs iterative formulation and testing in order to maximize the effort. A lab mixing baseline was developed and documented for the Rubber Laboratory in Bldg. 4602/Room 1178.

Chapman, Cynthia↗

Recent development and manufacturing of coal-derived building materials

Coal has been challenged because coal combustion generates large quantities of carbon dioxide (CO2), which contributes to global warming. Pyrolysis char (PC), a valuable byproduct of coal that does not liberate CO2 when produced in an inert environment, can be used as a high carbon content fuel in combustion and gasification. However, using PC as a fuel is not an eco-friendly and cost-efficient way to make energy. Contrastingly using PC to make engineered products does offer an eco-friendly, attractive and value-added use. This paper introduces a novel integrated coal pyrolysis and solvent extraction process invented by the University of Wyoming (UW) to convert as-mined coal from the Powder River Basin Coal Field, Wyoming, to functional carbon products, which together liberates very little CO2. PC and coal deposit, extract and residual (CDER) are two functional carbon products that can be used in the development and manufacture of high value coal-derived building materials. The novel development of three building products known as coal-derived char bricks (CCB), carbon structural unit (CSU), and char-based insulation foam (CIF) are introduced. The approaches to manufacture them are investigated, including consideration of the eco-friendly approaches, optimization of engineering performance, and cost effectiveness relative to traditional products. CCBs show advantages in terms of their light weight (< 1 g/cm3) and good compressive strength (> 14 MPa). CSUs possess high compressive strength (> 30 MPa) and low thermal conductivity (< 0.3 W/mK), while CIFs can achieve a low thermal conductivity of 0.06 W/mK. Two demonstration houses have been built on UW campus, one using CCBs and another using commercial clay bricks. The performances of these houses are being monitored for temperature control, humidity uptake, noise reduction, inside air volatile organic content, indoor air quality and weatherability. The performance of the CCBs in terms of these criteria is discussed.

Ng, Kam↗

Temperature-Following Thermal Barrier Coatings for High Efficiency Engines (Final Report)

HRL Laboratories and General Motors (GM), pursued this effort to increase the efficiency of internal combustion engines (ICEs) by developing and implementing temperature-following thermal barrier coatings (TBCs) to decrease heat loss from the combustion chamber. HRL developed microsphere TBCs based on hollow high-temperature alloy spheres with average diameter of 50 μm and wall thickness ~1 μm (microspheres) that achieve unprecedented low thermal conductivity and heat capacity (10X lower than the state of the art) while offering exceptional environmental and mechanical resistance.> In current ICEs, approximately 29% of the fuel’s energy is lost to the cooling system and about 22% goes into moving the car. By limiting heat losses from the combustion chamber with insulating coatings, fuel energy can be redirected into additional piston work and into the exhaust stream. The additional energy that goes into the exhaust stream can be turned into useful work through the use of an exhaust energy recovery device, such as turbocompounding and/or through driving a turbocharger to increase the power density of the engine allowing downsizing. Insulating coatings for piston crowns have been pursued in the past, but previous materials—typically ceramics—exhibited low thermal conductivity but retained high heat capacity. Such materials reduce heat losses but stabilize at a high surface temperature. The high surface temperature heats the incoming gases, which lowers volumetric efficiency and increases propensity for knock, resulting in degraded engine performance. This program developed an innovative new material that combines low thermal conductivity with low heat capacity. These unique properties allow it to follow rapid changes in gas temperature during each combustion cycle. A metallic microsphere TBC has been demonstrated that exhibits increased surface temperature during the combustion period, resulting in reduced heat transfer losses, while still returning to a low surface temperature during the gas exchange period. A 10X lower thermal conductivity and heat capacity than state-of-the-art thermal barrier coatings has been demonstrated. These unprecedented thermal properties are achieved through the coating architecture, which consists of closed pores on the microscale and exhibits a total porosity of 90% to 95%. By selecting a high-temperature nickel alloy as the coating material, the ductility and strength of metals can be harnessed to achieve much better durability and damage tolerance than brittle ceramic coatings can achieve.

33 ADVANCED PROPULSION SYSTEMS↗

Accelerated discovery of a large family of quaternary chalcogenides with very low lattice thermal conductivity

The development of efficient thermal energy management devices such as thermoelectrics and barrier coatings often relies on compounds having low lattice thermal conductivity (κ l ). Here, we present the computational discovery of a large family of 628 thermodynamically stable quaternary chalcogenides, AMM'Q 3 (A = alkali/alkaline earth/post-transition metals; M/M' = transition metals, lanthanides; Q = chalcogens) using high-throughput density functional theory (DFT) calculations. We validate the presence of low κ l in these materials by calculating κ l of several predicted stable compounds using the Peierls–Boltzmann transport equation. Our analysis reveals that the low κ l originates from the presence of either a strong lattice anharmonicity that enhances the phonon-scatterings or rattler cations that lead to multiple scattering channels in their crystal structures. Our thermoelectric calculations indicate that some of the predicted semiconductors may possess high energy conversion efficiency with their figure-of-merits exceeding 1 near 600 K. Our predictions suggest experimental research opportunities in the synthesis and characterization of these stable, low κ l compounds.

36 MATERIALS SCIENCE↗

Single crystal growth and thermoelectric properties of Nowotny chimney-ladder compound Fe 2 Ge 3

Fe 2 Ge 3 with an incommensurate Nowotny chimney-ladder (NCL) structure is a promising material for thermoelectric applications due to its low thermal conductivity. Previous experimental studies on Fe 2 Ge 3 have mainly focused on polycrystalline samples, resulting in a limited understanding of the material's intrinsic thermoelectric properties and the underlying causes of its low thermal conductivity. Here we report the synthesis and thermoelectric properties of single crystalline Fe 2 Ge 3 . Millimeter-sized Fe 2 Ge 3 single crystals grown by the chemical vapor transport method enable the study of the intrinsic thermoelectric properties. The Seebeck coefficient of Fe 2 Ge 3 is negative and its magnitude increases linearly with temperature, showing a degenerate n-type semiconductor behavior. Analysis of the electrical resistivity and specific heat data indicates the existence of an Einstein mode with a characteristic temperature of about 60 K, suggesting the presence of low-energy optical phonons. Further, the thermal conductivity of Fe 2 Ge 3 along the c axis is as low as 1.9Wm -1 K -1 at 300 K and exhibits a nearly temperature-independent characteristic, which is distinct from the previous theoretical calculations with a stronger temperature dependence. The low thermal conductivity may be attributed to the scattering of acoustic phonons by low-energy optical modes and the presence of non-extended diffuson modes, as reported in another NCL compound, MnSi 1.74 . This study provides valuable insights into the electrical and thermal properties of Fe 2 Ge 3 , which can open up possibilities for future advances in thermoelectric applications.

36 MATERIALS SCIENCE↗

Thermal and Electrical Properties of Isocyanate Derived Organic Aerogels for Cryogenic Insulation Applications

The use and storage of cryogens such as liquefied nitrogen, helium, hydrogen among others requires reliable and efficient thermal insulation systems. Passive insulation from high performance materials that are well-known for their inherent low thermal conductivity would reduce the overall costs involved in design, manufacture and maintenance of such systems. One such class of materials are referred to as aerogels. These materials are known for their low density, high mesoporosity, high surface areas, low thermal conductivity and high acoustic impedance. Aerogels were invented by S.S. Kistler in 1931 and the most common type are those made of silica. However, the inherent fragility of silica aerogels makes them hard to mass produce, and therefore applications have been limited. A major breakthrough was introduced by our team almost 20 years ago with the invention of polymer crosslinked silica aerogels. Those materials shifted attention to all-polymer aerogels that have overcome all fragility issues associated with their inorganic counterparts. This study focuses on such polymeric aerogels that can be mass produced as large monoliths while maintaining the low thermal conductivity of traditional silica aerogels over a wide temperature range. Manufacturing flexibility of polymeric aerogels allows fabrication of blocks and sheets that can be applied in various configurations to insulate cryogenic and superconducting devices. The thermal conductivity with 80 K and room temperature boundary are reported as well as other properties (electrical), that need to be considered when designing devices for cryogenic applications.

Churu, Gitogo↗

Thermal barrier coatings

High temperature stable thermal barrier coatings useful for substrates that form component parts of engines such as a component from a gas turbine engine exposed to high temperatures are provided. The thermal barrier coatings include a multiphase composite and/or a multilayer coating comprised of two or more phases with at least one phase providing a low thermal conductivity and at least one phase providing mechanical and erosion durability. Such low thermal conductivity phase can include a rare earth zirconate and such mechanical durability phase can include a rare earth a rare earth aluminate. The different phases are thermochemically compatible even at high temperatures above about 1200° C.

Wolfe, Douglas E.↗

Extreme sensitivity of higher-order interatomic force constants and thermal conductivity to the energy surface roughness of exchange-correlation functionals

In this Letter, we report that the fourth-order interatomic force constants (4th-IFCs) are significantly sensitive to the energy surface roughness of exchange-correlation (XC) functionals in density functional theory calculations. This sensitivity, which is insignificant for the second- (2nd-) and third-order (3rd-) IFCs, varies for different functionals in different materials and can cause misprediction of thermal conductivity by several times of magnitude. As a result, when calculating the 4th-IFCs using the finite difference method, the atomic displacement needs to be taken large enough to overcome the energy surface roughness, in order to accurately predict phonon lifetime and thermal conductivity. We demonstrate this phenomenon on a benchmark material (Si), a high-thermal conductivity material (BAs), and a low thermal conductivity material (NaCl). For Si, we find that the LDA, PBE, and PBEsol XC functionals are all smooth to the 2nd- and 3rd-IFCs but all rough to the 4th-IFCs. This roughness can lead to a prediction of nearly one order of magnitude lower thermal conductivity. For BAs, all three functionals are smooth to the 2nd- and 3rd-IFCs, and only the PBEsol XC functional is rough for the 4th-IFCs, which leads to a 40% underestimation of thermal conductivity. For NaCl, all functionals are smooth to the 2nd- and 3rd-IFCs but rough to the 4th-IFCs, leading to a 70% underprediction of thermal conductivity at room temperature. In conclusion, with these observations, we provide general guidance on the calculation of 4th-IFCs for an accurate thermal conductivity prediction.

42 ENGINEERING↗

Optimizing Surfactant Templating of Yttria-Stabilized Zirconia Aerogels for High-Temperature Applications: Effect of Anionic and Nonionic Surfactant

Aerogels, mesoporous materials with extreme material properties including high specific surface area, low density, and low thermal conductivity, can be useful for applications including catalysis, sorption media, and drug delivery. The low thermal conductivity and high surface area of aerogels makes them advantageous as thermal management systems, specifically for aerospace or aeronautics applications. However, the pore collapse and subsequent surface area decrease of aerogels following exposure to high temperatures must be mitigated to allow aerogels to be effectively used in thermal management applications. This work investigates the anionic surfactant sodium dodecyl sulfate (SDS) and the nonionic surfactant Pluronic® P-123 as surfactant templates in yttria-stabilized zirconia (YSZ) aerogels. By utilizing surfactant templates, known to influence pore structure, it is anticipated that sintering and densification of the aerogels following high-temperature exposure will be mitigated. It was determined that the addition of SDS and P-123 increased the surface area and pore volume of as-dried aerogels and suppressed crystallite growth at high temperatures. However, the impact of surfactant templates on the surface area and pore volume of heat-treated aerogels was negligible, potentially due to low concentrations of surfactant and the removal of the surfactant following high-temperature exposure.

Yttria-stabilized zirconia aerogels↗

A modified thermal conductivity for low density plasma magnetic flux tubes

In response to inconsistencies which have arisen in results from a hydrodynamic model in simulation of high ion temperature (1-2 eV) observed in low density, outer plasmasphere flux tubes, we postulate a reduced thermal conductivity coefficient in which only particles in the loss cone of the quasi-collisionless plasma contribute to the thermal conduction. Other particles are assumed to magnetically mirror before they reach the topside ionosphere and therefore not to remove thermal energy from the plasmasphere. This concept is used to formulate a mathematically simple, but physically limiting model for a modified thermal conductivity coefficient. When this modified coefficient is employed in the hydrodynamic model in a case study, the inconsistencies between simulation results and observations are largely resolved. The high simulated ion temperatures are achieved with significantly lower ion temperatures in the topside ionosphere. We suggest that this mechanism may be operative under the limited low density, refilling conditions in which high ion temperatures are observed.

Comfort, R. H.↗

High-temperature thermal storage systems for advanced solar receivers materials selections

Advanced space power systems that use solar energy and Brayton or Stirling heat engines require thermal energy storage (TES) systems to operate continuously through periods of shade. The receiver storage units, key elements in both Brayton and Stirling systems, are designed to use the latent heat of fusion of phase-change materials (PCMs). The power systems under current consideration for near-future National Aeronautics and Space Administration space missions require working fluid temperatures in the 1100 to 1400 K range. The PCMs under current investigation that gave liquid temperatures within this range are the fluoride family of salts. However, these salts have low thermal conductivity, which causes large temperature gradients in the storage systems. Improvements can be obtained, however, with the use of thermal conductivity enhancements or metallic PCMs. In fact, if suitable containment materials can be found, the use of metallic PCMs would virtually eliminate the orbit associated temperature variations in TES systems. The high thermal conductivity and generally low volume change on melting of germanium and alloys based on silicon make them attractive for storage of thermal energy in space power systems. An approach to solving the containment problem, involving both chemical and physical compatibility, preparation of NiSi/NiSi2, and initial results for containment of germanium and NiSi/NiSi2, are presented.

Wilson, D. F.↗

Polymer Aerogels for Lunar Survivability (PALS)

As the Space Community endeavors to reach new heights of exploration, materials for extreme environment are on the forefront of research. One such material would include polymer aerogels; lightweight solids with nano-scale pore size (10-20 nm), high internal surface area (500-850 m2/g), low thermal conductivity (~20 mW/K), low density ( 0.15-0.05 g/cm3) and extremely high porosities (>95%). Due to these interesting properties, aerogels are ideal as thermal insulators and are by no means limited to this application. The high porosity combined with high surface area, make aerogels an ideal host system for particle incorporation for applications such as IR filtration, sensor platforms, as well as vibro-acoustic, dust, and radiation mitigation materials.

Stephanie Vivod↗

High-Entropy Ceramic Coatings: Transformative New Materials for Environmentally-Compatible Thin-Film Insulators against High-T Molten Salts

An emerging new class of promising materials, High-Entropy Ceramics (HECs) or Compositionally-Complex Ceramics (CCCs), have been successfully fabricated in the last three years. This project evaluates HECs/CCCs in the concentrated solar power (CSP) context. In this project, we have identified a couple of simple, and key descriptors governing thermal conductivity in HECs. Size disorder among the cations was found to have a strong influence on the thermal conductivity across multiple systems and throughout a vast compositional space. Since identifying this, we have optimized previous compositions to achieve low thermal conductivities of $k$~$1-1.4Wm{-1}K{-1}$. We have further reduced our selection of promising compositions based on project guidelines and applied a theory that can potentially predict reactivity with molten salts to identify a small set of HECs that are suitable for further molten salt heat transfer media (HTM) stability testing. Many compositions reveal poor resistance to molten chloride salt after being exposed for 24 h compared to the reference structural alloy, Haynes 230. However, after 100 h, a few HECs/CCCs show strong parabolic rate constant effects and provide greater resistance to chloride salt compared to Haynes 230 alloy, which shows more linear kinetics. Postmortem characterization of the microstructure reveals the parabolic rate constant originates from a dense reaction layer form at the interface. This feature is absent in Haynes 230, which only shows grain boundary infiltration. The HECs/CCCs were also put in contact with the metal alloy under Ar for 800 h at 800°C and show negligible interaction. Lastly, parabolic rate constant HECs/CCCs also have low thermal conductivity $(<2 Wm^{-1} K^{-1})$ at 800°C. These specimens satisfy all project requirements and demonstrate their promising application in next-generation CSP.

14 SOLAR ENERGY↗

A Low-Temperature Structural Transition in Canfieldite, Ag 8 SnS 6 , Single Crystals

Canfieldite, Ag 8 SnS 6 , is a semiconducting mineral notable for its high ionic conductivity, photosensitivity, and low thermal conductivity. In this paper, we report the solution growth of large single crystals of Ag 8 SnS 6 of mass up to 1 g from a ternary Ag–Sn–S melt. On cooling from high temperature, Ag 8 SnS 6 undergoes a known cubic ($F\bar{4}3m$) to orthorhombic ($Pna2_1$) phase transition at ≈460 K. By studying the magnetization and thermal expansion between 5–300 K, we discover a second structural transition at ≈120 K. Single crystal X-ray diffraction reveals the low-temperature phase adopts a different orthorhombic structure with space group $Pmn2_1$ ($\textit{a}$ = 7.662 9(5) Å, $\textit{b}$ = 7.539 6(5) Å, $\textit{c}$ = 10.630 0(5) Å, Z = 2 at 90 K) that is isostructural to the room-temperature forms of the related Se-based compounds Ag 8 SnSe 6 and Ag 8 GeSe 6 . The 120 K transition is first-order and has a large thermal hysteresis. On the basis of the magnetization and thermal expansion data, the room-temperature polymorph can be kinetically arrested into a metastable state by rapidly cooling to temperatures below 40 K. We last compare the room- and low-temperature forms of Ag8SnS6 with its argyrodite analogues, Ag 8 TQ 6 ($\textit{T}$ = Si, Ge, Sn; $\textit{Q}$ = S, Se), and identify a trend relating the preferred structures to the unit cell volume, suggesting smaller phase volume favors the $Pna2_1$ arrangement. We support this picture by showing that the transition to the $Pmn2_1$ phase is avoided in Ge alloyed Ag 8 Sn 1–x Ge x S 6 samples as well as in pure Ag 8 GeS 6 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗