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At least 937 records · Page 52

Alkali metal pool boiler life tests for a 25 kWe advanced Stirling conversion system

The overall operating temperature and efficiency of solar-powered Stirling engines can be improved by adding an alkali metal pool boiler heat transport system to supply heat more uniformly to the heater head tubes. One issue with liquid metal pool boilers is unstable boiling. Stable boiling is obtained with an enhanced boiling surface containing nucleation sites that promote continuous boiling. Over longer time periods, it is possible that the boiling behavior of the system will change. An 800-h life test was conducted to verify that pool boiling with the chosen fluid/surface combination remains stable as the system ages. The apparatus uses NaK boiling on a - 100 + 140 stainless steel sintered porous layer, with the addition of a small amount of xenon. Pool boiling remained stable to the end of life test. The pool boiler life test included a total of 82 cold starts, to simulate startup each morning, and 60 warm restarts, to simulate cloud cover transients. The behavior of the cold and warm starts showed no significant changes during the life test. In the experiments, the fluid/surface combination provided stable, high-performance boiling at the operating temperature of 700 C. Based on these experiments, a pool boiler was designed for a full-scale 25-kWe Stirling system.

Anderson, W. G.↗

Review—Electrospun Inorganic Solid-State Electrolyte Fibers for Battery Applications

Inorganic solid-state electrolytes (SSEs), especially Li 7 La 3 Zr 2 O 12 (LLZO), are promising candidates for all solid-state batteries. Generally, SSEs are synthesized by solid-state reactions at high temperatures. The high temperature required to synthesize useful polymorphs (e.g., cubic phase, in the case of LLZO) increases their production cost. To lower the synthesis temperature, several approaches, including doping and crystallite size control via sol-gel processes, have been explored. Recently, electrospinning was used to synthesize the inorganic SSE fibers to control the crystallite size and lower the calcination temperature. Several publications followed that investigated the properties of fibers and demonstrated the use of these fibers in inorganic-polymer composite SSEs. This paper presents a concise discussion of electrospinning, the parameters that control fiber morphology, the synthesis of inorganic SSE fibers, the effect of sintering conditions on the fiber morphology and composition, and the recent use of these fibers in making composite SSEs and other battery applications. Additionally, most of the discussion focuses on LLZO, but this paper also discusses applications of other types of electrospun inorganic electrolyte fibers, the challenges of using these fibers, and possible future directions in this research field.

25 ENERGY STORAGE↗

High-strength silicon carbides by hot isostatic pressing

Silicon carbide has strong potential for heat engine hardware and other high-temperature applications because of its low density, good strength, high oxidation resistance, and good high-temperature creep resistance. Hot isostatic pressing (HIP) was used for producing alpha and beta silicon carbide (SiC) bodies with near-theoretical density, ultrafine grain size, and high strength at processing temperatures of 1900 to 2000 C. The HIPed materials exhibited ultrafine grain size. Furthermore, no phase transformation from beta to alpha was observed in HIPed beta-SiC. Both materials exhibited very high average flexural strength. It was also shown that alpha-SiC bodies without any sintering aids, when HIPed to high final density, can exhibit very high strength. Fracture toughness K (sub C) values were determined to be 3.6 to 4.0 MPa m (sup 1/2) for HIPed alpha-SiC and 3.7 to 4.1 MPa m (sup 1/2) for HIPed beta-SiC. In the HIPed specimens strength-controlling flaws were typically surface related. In spite of improvements in material properties such as strength and fracture toughness by elimination of the larger strength-limiting flaws and by grain size refinement, HIPing has no effect on the Weibull modulus.

Dutta, Sunil↗

High-strength silicon carbides by hot isostatic pressing

Silicon carbide has strong potential for heat engine hardware and other high-temperature applications because of its low density, good strength, high oxidation resistance, and good high-temperature creep resistance. Hot isostatic pressing (HIP) was used for producing alpha and beta silicon carbide (SiC) bodies with near-theoretical density, ultrafine grain size, and high strength at processing temperatures of 1900 to 2000 C. The HIPed materials exhibited ultrafine grain size. Furthermore, no phase transformation from beta to alpha was observed in HIPed beta-SiC. Both materials exhibited very high average flexural strength. It was also shown that alpha-SiC bodies without any sintering aids, when HIPed to high final density, can exhibit very high strength. Fracture toughness K (sub C) values were determined to be 3.6 to 4.0 MPa m (sup 1/2) for HIPed alpha-SiC and 3.7 to 4.1 MPa m (sup 1/2) for HIPed beta-SiC. In the HIPed specimens strength-controlling flaws were typically surface related. In spite of improvements in material properties such as strength and fracture toughness by elimination of the larger strength-limiting flaws and by grain size refinement, HIPing has no effect on the Weibull modulus.

Dutta, Sunil↗

Designing ultrastable Pt/CeO 2 -Al 2 O 3 nanosheet catalysts for three-way catalysts applications

Designing Rh-free, especially Pt-only, three-way catalysts with improved low-temperature activity/stability is highly desirable. Herein, we demonstrate that ultrastable Pt/CeO 2 -Al 2 O 3 nanosheet catalysts can be obtained based on a Sabatier principle of metal-support interaction. Tuning the surface coverage of penta-site rich γ-Al 2 O 3 nanosheets (AlNS, weak adhesion to Pt) by CeO 2 “nano-islands” (strong adhesion to Pt) can lead to the synthesis of Pt/60 wt.%CeO 2 -AlNS that have lower light-off temperatures for CO, hydrocarbons, and NO compared to conventional Pt/CeO 2 and Pt/Al 2 O 3 catalysts by 100–200°C and a similar performance with the state-of-the-art Rh-based catalyst. Further, incorporating CeO 2 on the surface of AlNS can retard the sintering of CeO 2 during harsh redox hydrothermal aging, associate with the strong interaction between CeO 2 “nano-island” and penta-site rich γ-Al 2 O 3 nanosheets. Moreover, the improved activity/stability of Pt/CeO 2 -AlNS catalysts can be attributed to tuning of the Pt detachment and migration from and back to the CeO 2 “nano-islands”, respectively, that keeps Pt as nanoclusters on CeO 2 , the most active species for three-way catalyst applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Glass-bonded ceramic waste forms for immobilization of radioiodine from caustic scrubber wastes

Glass-bonded sodalite composite waste forms have been developed for the immobilization of liquid radioactive wastes resulting from off-gas treatment during aqueous reprocessing of used nuclear fuel, with a particular focus on 129I. The proposed composite waste form is comprised of aluminosilicate ceramic phases containing volatile radionuclides bonded with a glassy matrix. In this work, a suite of ten candidate low-temperature glass binders (ZnO-Bi2O3-based glasses and a Na2O-B2O3-SiO2 glass) were examined. Six glasses were mixed with caustic scrubber waste simulant previously converted into a sodalite-rich material (to provide glass fractions of 10 and 20 wt.%), uniaxially pressed into pellets, and sintered at 350 °C or 550 °C for 8 h in air. Iodine retention after heat treatment was assessed by neutron activation analysis, showing retention of 67-100 % of expected iodine. The aqueous durabilities of the resulting materials were then determined, following the ASTM C1308 standard test, showing iodine releases of 1 to 23 g m-2 after 4 d. The cumulative iodine release for the best performing system (a zinc-bismuth-borate glass binder) was <1 g m-2, and its iodine retention from processing was 67 %. The iodine releases compared favorably with other waste forms. In parallel, this best-performing composition was also consolidated via hot isostatic pressing (HIP) in a stainless-steel canister at 550 °C for 2 h under 100 MPa pressure. The HIPed sample was produced at the ~20 g scale and showed improved densification and minimal reaction with the canister.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Improved silicon carbide for advanced heat engines

This is the third annual technical report for the program entitled, Improved Silicon Carbide for Advanced Heat Engines, for the period February 16, 1987 to February 15, 1988. The objective of the original program was the development of high strength, high reliability silicon carbide parts with complex shapes suitable for use in advanced heat engines. Injection molding is the forming method selected for the program because it is capable of forming complex parts adaptable for mass production on an economically sound basis. The goals of the revised program are to reach a Weibull characteristic strength of 550 MPa (80 ksi) and a Weibull modulus of 16 for bars tested in 4-point loading. Two tasks are discussed: Task 1 which involves materials and process improvements, and Task 2 which is a MOR bar matrix to improve strength and reliability. Many statistically designed experiments were completed under task 1 which improved the composition of the batches, the mixing of the powders, the sinter and anneal cycles. The best results were obtained by an attritor mixing process which yielded strengths in excess of 550 MPa (80 ksi) and an individual Weibull modulus of 16.8 for a 9-sample group. Strengths measured at 1200 and 1400 C were equal to the room temperature strength. Annealing of machined test bars significantly improved the strength. Molding yields were measured and flaw distributions were observed to follow a Poisson process. The second iteration of the Task 2 matrix experiment is described.

Whalen, Thomas J.↗

SiC and Si3N4 Recession Due to SiO2 Scale Volatility Under Combustor Conditions

Silicon carbide (SiC) and Si3N4 materials were tested in various turbine engine combustion environments chosen to represent either conventional fuel-lean or fuel-rich mixtures proposed for high-speed aircraft. Representative chemical vapor-deposited (CVD), sintered, and composite materials were evaluated by furnace and high-pressure burner rig exposures. Although protective SiO2 scales formed in all cases, the evidence presented supports a model based on paralinear growth kinetics (i.e., parabolic growth moderated simultaneously by linear volatilization). The volatility rate is dependent on temperature, moisture content, system pressure, and gas velocity. The burner tests were thus used to map SiO2 volatility (and SiC recession) over a range of temperatures, pressures, and velocities. The functional dependency of material recession (volatility) that emerged followed the form A[exp(-Q / RT)](P(sup x)v(sup y). These empirical relations were compared with rates predicted from the thermodynamics of volatile SiO and SiOxHy reaction products and a kinetic model of diffusion through a moving boundary layer. For typical combustion conditions, recession of 0.2 to 2 micrometers/hr is predicted at 1200 to 1400 C, far in excess of acceptable long-term limits.

Smialek, James L.↗

Low temperature catalytic conversion of CH 4 , CO 2 , and C 2 H 4 to value-added C 3 oxygenates and olefins via C 1 -C 2 coupling on Pd-Au/CeO 2

The catalytic conversion of CH 4 and CO 2 in the presence of more reactive co-reactants C 2 H 4 and O 2 on Pd-Au/CeO 2 is achieved at 200 °C and elevated pressures. Propene and acetone were produced from the catalyzed reaction of CH 4 +C 2 H 4 +O 2 ; addition of CO 2 to the reactant stream produced methyl acetate (MAc) but it significantly reduced the C-selectivities of propene and acetone. DRIFTS experiments confirmed the formation of methoxy species from CH 4 +CO 2 at 200 °C, which is an intermediate in the formation of MAc. Here, control experiments with blanks, and with CeO 2 did not show any propene, acetone, or MAc products. The complete oxidation of C 2 H 4 was avoided; the catalyst is stable, and reactant conversions and product yields were sustained for the observed 1200 min time-on-stream, indicating that there is little or no carbon deposition and sintering. This direct coupling of CH 4 and C 2 H 4 intermediates to higher carbon-number products at 200 °C is significant.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Metal alloy microparticle tagging of UO 2 fuel pellets for nuclear forensics

A tagging strategy for UO 2 fuel pellets will be discussed which involves the creation of alloyed metal microparticles that can be tuned to create a unique identification (“barcode”) indicating provenance of the pellets. These specialized markers would contain high temperature resistant materials, such as Ti, Mo, and Cr, in small quantities such that they do not interfere with the performance of the pellets but are recoverable by standard analytical techniques. The Amazemet rePowder ultrasonic atomization system was used to manufacture the microparticles, and sample pellets were fabricated and sintered containing these dopants. Various techniques, such as Scanning Electron Microscopy (SEM) and Electron Probe Microanalysis (EPMA), were used to evaluate these sample pellets to determine if particles (and their alloy compositions) were recoverable. Details on how the particles were manufactured and characterized will be detailed, as well as results from their incorporation into test pellets. Next steps will involve the scale of this technique using more conventional mass production methods, as well as the implementation of other alloys.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Phase evolution during reactive flash sintering of Li 6.25 Al 0.25 La 3 Zr 2 O 12 starting from a chemically prepared powder

Here, reactive flash sintering (RFS) of a chemically prepared multiphase precursor powder was performed to fabricate Li 6.25 Al 0.25 La 3 Zr 2 O 12 (Al-LLZO) ceramics. This approach allowed for obtaining single-phase dense samples in a remarkably short processing time of 30 s, at a furnace temperature of 600 °C, with an electric field of 50 V cm -1 and a current limit of 150 mA mm -2 . The ceramics display high bulk conductivity of 0.18 mS cm -1 at room temperature. Furthermore, phase evolution is studied by in-situ X-ray diffraction during: i) conventional heating and ii) RFS under current rate mode. As expected, the intermediate phases progressively dissolved into the Al-LLZO matrix by conventional heating. On the other hand, RFS promoted the growth of the intermediate La 2 Zr 2 O 7 , an effect that was overcome by the thermally driven formation of Al-LLZO at higher temperatures. The observed different reaction pathway suggests that RFS can be used for stabilizing phases that are not thermodynamically favored upon conventional heating.

36 MATERIALS SCIENCE↗

Special Test Methods for Batteries

Various methods are described for measuring heat generation in primary and secondary batteries as well as the specific heat of batteries and cell thermal conductance. Problems associated with determining heat generation in large batteries are examined. Special attention is given to monitoring temperature gradients in nickel cadmium cells, the use of auxiliary electrodes for conducting tests on battery charge control, evaluating the linear sweep of current from charge to discharge, and determining zero current voltage. The fast transient behavior of batteries in the microsecond range, and the electrical conductance of nickel sinters in the thickness direction are also considered. Mechanical problems experienced in the vibration of Ni-Cd batteries and tests to simulate cyclic fatigue of the steel table connecting the plates to the comb are considered. Methods of defining the distribution of forces when cells are compressed during battery packaging are also explored.

Gross, S.↗

Fracture of flash oxidized, yttria-doped sintered reaction-bonded silicon nitride

The oxidation behavior of a slip cast, yttria-doped, sintered reaction-bonded silicon nitride after 'flash oxidation' was investigated. It was found that both the static oxidation resistance and flexural stress rupture life (creep deformation) were improved at 1000 C in air compared to those of the same material without flash oxidation. Stress rupture data at high temperatures (1000 to 1200 C) are presented to indicate applied stress levels for oxidation-dependent and independent failures.

Govila, R. K.↗

Preformed Superconductive Devices

Process forms high-temperature superconductors into electrical components as connectors, coils, and conductors. Brittleness no obstacle because material preformed before heated to turn it into ceramic. Substrates made of glass-fiber-reinforced circuit-board material, reduce leakage of heat into ceramic, unlike silver or copper substrates used in making sintered-in-place superconducting ceramics.

Haertling, Gene H.↗

Simultaneous Luminescence Pressure and Temperature Measurement System for Hypersonic Wind Tunnels

Surface pressures and temperatures are determined from visible emission brightness and green-to-red color ratioing of induced luminescence from a ceramic surface with an organic dye coating. A ceramic-dye matrix of porous silica ceramic with an adsorbed dye is developed for high-temperature pressure sensitivity and stability (up to 150 C). Induced luminescence may be excited using a broad range of incident radiation from visible blue light (488-nm wavelength) to the near ultraviolet (365 nm). Ceramic research models and test samples are fabricated using net-form slip-casting and sintering techniques. Methods of preparation and effects of adsorption film thickness on measurement sensitivity are discussed. With the present 8-bit imaging system a 10% pressure measurement uncertainty from 50 to 760 torr is estimated, with an improvement to 5% from 3 to 1500 torr with a 12-bit imaging system.

Buck, Gregory M.↗

Machined Titanium Heat-Pipe Wick Structure

Wick structures fabricated by machining of titanium porous material are essential components of lightweight titanium/ water heat pipes of a type now being developed for operation at temperatures up to 530 K in high-radiation environments. In the fabrication of some prior heat pipes, wicks have been made by extruding axial grooves into aluminum unfortunately, titanium cannot be extruded. In the fabrication of some other prior heat pipes, wicks have been made by in-situ sintering of metal powders shaped by the use of forming mandrels that are subsequently removed, but in the specific application that gave rise to the present fabrication method, the required dimensions and shapes of the heat-pipe structures would make it very difficult if not impossible to remove the mandrels due to the length and the small diameter. In the present method, a wick is made from one or more sections that are fabricated separately and assembled outside the tube that constitutes the outer heat pipe wall. The starting wick material is a slab of porous titanium material. This material is machined in its original flat configuration to form axial grooves. In addition, interlocking features are machined at the mating ends of short wick sections that are to be assembled to make a full-length continuous wick structure. Once the sections have been thus assembled, the resulting full-length flat wick structure is rolled into a cylindrical shape and inserted in the heatpipe tube (see figure). This wick-structure fabrication method is not limited to titanium/water heat pipes: It could be extended to other heat pipe materials and working fluids in which the wicks could be made from materials that could be pre-formed into porous slabs.

Rosenfeld, John H.↗

Laser Sintering of Thermoset Polyimide Composites

Selective Laser Sintering (SLS) is an additive manufacturing technique that builds 3D models layer by layer using a laser to selectively melt cross sections in powdered polymeric materials, following sequential slices of the CAD model. SLS generally uses thermoplastic polymeric powders, such as polyamides (i.e. Nylon), and the resultant 3D objects are often weaker in their strength compared to traditionally processed materials, due to the lack of polymer inter-chain connection in the z-direction. Our previous effort showed the challenges of printing a melt-processable RTM370 imide resin powder terminated with reactive 4-phenylethynylphthalic anhydride by LS, due to its inherently low viscosity of these oligomers. This paper presented the first successful 3D printing of high temperature carbon fiber filled thermoset polyimide composites, followed by post cure cycles to promote additional crosslinking for achieving higher temperature (Tg = 370 °C) capability. The processes to build tensile specimens and a component by LS, and the characterization of RTM370 imide resin by DSC and rheology as well as evaluation of the LS printed polyimide composite specimens by SEM and mechanical tests will be discussed.

Polyimide Composites↗

Controlled Solidification of Liquids Within the SFC Primary Phase Field of the “Fe{sub 2}O{sub 3}”-CaO-SiO{sub 2} System in Air

To provide fundamental information on the phases and microstructures formed during sintering, a liquid with a bulk composition within the silico ferrite of calcium (SFC) primary phase field in the ternary “Fe{sub 2}O{sub 3}”-CaO-SiO{sub 2} system in air was solidified at a controlled rate. Samples of a bulk composition with a CaO/SiO{sub 2} ratio of 4.00 and 69.24 wt pct Fe{sub 2}O{sub 3}, were cooled from 1623 K (1350 °C) at 2 K/s, with samples quenched at temperatures between 1513 K (1240 °C) to 1453 K (1180 °C). The silico ferrite of calcium and aluminium I (SFCA-I) and Ca{sub 7.2}Fe{sub 0.8}{sup 2+}Fe{sub 30}{sup 3+}O{sub 53} phases were observed to form an intergrowth (‘SFC-I’) rather than the anticipated SFC phase. Solidification was found to occur in three stages, Liquid + ‘SFC-I’, Liquid + ‘SFC-I’ + C{sub 2}S + CF{sub 2}, and C{sub 2}S + CF{sub 2} + CF, where C{sub 2}S denotes dicalcium silicate, CF denotes calcium ferrite and CF{sub 2} denotes calcium diferrite. The phases formed and the solidification sequence differ from those predicted under equilibrium and Scheil–Gulliver Cooling. Although not directly applicable to industrial operations, this research clearly shows that the formation of both the SFCA and SFCA-I phase in iron ore sinters is controlled by kinetic processes rather than equilibrium conditions.

36 MATERIALS SCIENCE↗