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At least 163 records · Page 9

Compositional control of radionuclide retention in hollandite-based ceramic waste forms for Cs-immobilization

Hollandite materials, as a class of crystalline nuclear waste forms, are promising candidates for the immobilization of radioactive elements, such as Cs, Ba, as well as a variety of lanthanide and transition-metal fission products. In this study, three Ga-doped titanate hollandite-type phases, Ba 1.33 Ga 2.67 Ti 5.33 O 16 , Ba 0.667 Cs 0.667 Ga 2 Ti 6 O 16 , and Cs 1.33 Ga 1.33 Ti 6.67 O 16 , were synthesized using a solid-state reaction route. All synthesized phases adopted a single phase tetragonal structure, as determined by powder X-ray diffraction (XRD), and elemental analysis confirmed the measured stoichiometries were close to targeted compositions. Extended X-ray absorption fine structure spectroscopy (EXAFS) was used to determine the local structural features for the framework of octahedrally coordinated cations. EXAFS data indicated that Cs 1.33 Ga 1.33 Ti 6.67 O 16 possessed the most disordered local structure centered around the Ga dopant. The enthalpies of formation of all three hollandite phases measured using high-temperature oxide melt solution calorimetry were found to be negative, indicating enthalpies of formation of these hollandites from oxides are thermodynamically stable with respect to their constituent oxides. Furthermore, the formation enthalpies were more negative and hence more favorable with increased Cs content. Finally, aqueous leaching tests revealed that high Cs content hollandite phases exhibited greater Cs retention as compared to low Cs content hollandite. While preliminary in nature, this work draws attention to the links between the capacity for radionuclide retention, atomistic level structural features and bulk thermodynamic properties of materials.

nuclear (including radiation effects), materials a↗

Toward All-Solid-State Lithium Batteries: Three-Dimensional Visualization of Lithium Migration in β-Li 3 PS 4 Ceramic Electrolyte

All-solid lithium batteries are an attractive next-generation technology that use ion-conducting solids such as ..beta..-Li3PS4 (LPS) to enable use of a lithium metal anode, which increases theoretical capacity and widens the stable voltage window over traditional lithium-ion systems. These ion-conductive solids also provide increased safety by replacing flammable liquid electrolytes. Although solid-state electrolytes are significantly more stable and dendrite-resistant than traditional liquid electrolytes, lithium anodes in all-solid systems may nevertheless grow dendrites under high stress or repeated cycling, leading to short circuits and premature battery breakdown. For this reason, we study the formation and propagation of Li metal features within solid electrolytes using synchrotron-based X-ray tomography with in-situ current-voltage cycling supported by our custom sample platform. Our results demonstrate the ability of this technique to delineate different layers of the Li/LPS/Li structure with spatial resolution approaching 1 um. At this resolution, we are able to detect expansion of voids, especially in early stages of cycling. This expansion of voids is observed throughout the volume of the symmetric cells and visually resembles propagation of cracks resulting from interactions between the Li metal and pre-existing voids in the LPS electrolyte.

25 ENERGY STORAGE↗

A thermodynamics-based damage model for the non-linear mechanical behavior of SiC/SiC ceramic matrix composites in irradiation and thermal environments

A damage model is developed and validated with experimental data for the non-linear mechanical behavior of SiC/SiC composite materials in nuclear applications. Cyclic thermal and mechanical loading associated with neutron irradiation effects of these composites leads to wide-spread and progressive micro-cracking that leads to loss of thermal conductivity and further enhancement of thermo-mechanical damage. A physics-based model of wide-spread micro-cracking is developed within the thermodynamic framework of continuum damage mechanics. Evolution equations for damage parameters that describe the growth of continuum damage are developed, where the material variables are obtained from experiments. The model novelty is in coupling mechanical, thermal, and irradiation damage through a consistent thermodynamic framework, including loss of thermal conductivity due to the evolution of mechanically induced micro-cracks. A number of thermo-mechanical experiments were conducted to confirm model assumptions. The model is shown to be validated with out-of-pile experiments, and then implemented using commercial finite element code COMSOL to the fuel cladding problem with normal and high radiation dose cases.

Materials Science↗

Diffraction Methods for Qualitative and Quantitative Texture Analysis of Ferroelectric Ceramics

Crystallographic textures are pervasive in ferroelectrics and underpin the functional properties of devices utilizing these materials because many macroscopic properties (e.g., piezoelectricity) require a non-random distribution of dipoles. Inducing a preferred grain texture has become a viable route to improve these functional properties. X-ray and neutron diffraction have become valuable tools to probe crystallographic textures. This paper presents an overview of qualitative and quantitative methods for assessing crystallographic textures in electroceramics (domain and grain textures) and discusses their strengths and weaknesses.

36 MATERIALS SCIENCE↗

High-temperature ceramic-to-ceramic seals

Noble-metal braze applied to appropriately prepared zirconia parts produces a gas-tight, durable seal that can withstand temperature of 825 C for over 2000 hours without deterioration.

Smart, W.↗

Fracture toughness of fiber-reinforced glass ceramic and ceramic matrix composites

A fracture mechanics investigation of 2D woven Nicalon SiC/SiC and Nicalon SiC/LAS has been undertaken. An energy approach has been adopted to characterize and quantify the fracture properties of these materials. Chevron-notched bend specimens were tested in an edgewise configuration in which the crack propagated perpendicular to the ply direction. R-curves were obtained from repeated loading and unloading of specimens using several methods of data reduction. Values correconding to the plateau regions of the R-curves were taken as steady-state crack-growth resistance. These ranged from 37 to 63 kJ/sq m for 2D-SiC/LAS and 2.6 to 2.8 kJ/sq m for 2D-SiC/SiC composites.

Stull, Kevin R.↗

Refractory Materials for Flame Deflector Protection System Corrosion Control: Refractory Ceramics Literature Survey

Ceramics can be defmed as a material consisting of hard brittle properties produced from inorganic and nonmetallic minerals made by firing at high temperatures. These materials are compounds between metallic and nonmetallic elements and are either totally ionic, or predominately ionic but having some covalent character. This definition allows for a large range of materials, not all applicable to refractory applications. As this report is focused on potential ceramic materials for high temperature, aggressive exposure applications, the ceramics reviewed as part of this report will focus on refractory ceramics specifically designed and used for these applications. Ceramic materials consist of a wide variety of products. Callister (2000) 1 characterized ceramic materials into six classifications: glasses, clay products, refractories, cements, abrasives, and advanced ceramics. Figure 1 shows this classification system. This review will focus mainly on refractory ceramics and cements as in general, the other classifications are neither applicable nor economical for use in large structures such as the flame trench. Although much work has been done in advanced ceramics over the past decade or so, these materials are likely cost prohibitive and would have to be fabricated off-site, transported to the NASA facilities, and installed, which make these even less feasible. Although the authors reviewed the literature on advanced ceramic refractories 2 center dot 3 center dot 4 center dot 5 center dot 6 center dot 7 center dot 8 center dot 9 center dot 10 center dot 11 center dot 12 after the review it was concluded that these materials should not be ' the focus of this report. A review is in progress on materials and systems for prefabricated refractory ceramic panels, but this review is focusing more on typical refractory materials for prefabricated systems, which could make the system more economically feasible. Refractory ceramics are used for a wide variety of applications. Figure 2 shows many ofthese applications, their life expectancy or requirement, and the exposure temperature for the refractory ceramic. Note that the exposure temperatures for refractory ceramics are very similar to the exposure conditions for specialty ceramics (rocket nozzles, space vehicle re-entry fields, etc.) and yet the life expectancy or requirement is relatively low. Currently NASA is repairing the refractory lining in the flame trench after every launch - although this is not a direct indication of low life expectancy, it does indicate that the current system may not be sufficiently durable to maximize economy. Better performing refractory ceramics are needed to improve the performance, economy, and safety during and after launches at the flame trenches at Kennedy Space Center (KSC). To achieve this goal a current study is underway to assess different refractory systems for possible use in the flame trenches at KSC. This report will target the potential applicability of refractory ceramics for use in the flame trenches. An overview of the different refractory ceramics will be provided (see Figure I). This will be followed with a brief description of the structure of refractory products, the properties and characteristics of different systems, the methodology for selecting refractories, and then a general design methodology. Based on these sections, future challenges and opportunities will be identified with the objective of improving the durability, performance, economy, and safety of the launch complex. Refractory ceramics are used for a wide variety of applications. Figure 2 shows many ofthese applications, their life expectancy or requirement, and the exposure temperature for the refractory ceramic. Note that the exposure temperatures for refractory ceramics are very similar to the exposure conditions for specialty ceramics (rocket nozzles, space vehicle re-entry fields, etc.) and yet the life expectancy or requirement is relatively low. Currently NASA is repairing the refractory lining in the flame trench after every launch - although this is not a direct indication of low life expectancy, it does indicate that the current system may not be sufficiently durable to maximize economy. Better performing refractory ceramics are needed to improve the performance, economy, and safety during and after launches at the flame trenches at Kennedy Space Center (KSC). To achieve this goal a current study is underway to assess different refractory systems for possible use in the flame trenches at KSC. This report will target the potential applicability of refractory ceramics for use in the flame trenches. An overview of the different refractory ceramics will be provided (see Figure I). This will be followed with a brief description of the structure of refractory products, the properties and characteristics of different systems, the methodology for selecting refractories, and then a general design methodology. Based on these sections, future challenges and opportunities will be identified with the objective of improving the durability, performance, economy, and safety of the launch complex.

Calle, Luz Marina↗

Influence of Carbides and Alloying Elements on Intercrystallite Corrosion in Cutting-Ceramic Inserts

It is established that intercrystallite corrosion of cutting-ceramic inserts arises when the chromium content in the peripheral zone of the grains is depleted by the deposition of chromium carbides at the grain boundaries, in the presence of stress due to the fast cooling of the inserts from high temperatures. This is especially apparent when 12Kh18N10Т, 40Kh13, 14Kh17N2, and other steels that are hard to machine are worked by a tool equipped with inserts of VOK-60M modified cutting ceramic. Research shows that the intercrystallite corrosion of cutting-ceramic inserts may be attributed to the stress arising in the surface layers of the grains as a result of carbide or nitride deposition. Heating cutting-ceramic inserts at 650–800°С lowers this stress and restores their resistance to intercrystallite corrosion. Research also shows that chromomanganese cutting-ceramic inserts are less susceptible to intercrystallite corrosion than are chromium–manganese–nickel inserts, while chromium–manganese–nickel cutting-ceramic inserts are less susceptible than are chromonickel inserts. The benefits of chromium–manganese–nickel cutting-ceramic inserts are especially pronounced with relatively brief machining of 12Kh18N10Т, 40Kh13, 14Kh17N2, and other such steels, in rigorous conditions, with a temperature of 600–650°С in the workpiece–tool contact zone. A new theory of the intercrystallite corrosion of VOK-60M modified cutting ceramic is based on the role of the kinetic factor at the relatively low tempering temperatures associated with the deposition of metastable carbide, although this does not lead to maximum change in free energy of the system but only to a relative change. In the cutting ceramic, this carbide may be chromium carbide (Cr, Тi){sub 23}C{sub 6}, which is greatly enriched with titanium. With increase in tempering temperature, the deposited carbide tends toward the stable composition Cr{sub 23}С{sub 6}. Prolonged holding at the tempering temperature also tends to favor thermodynamic equilibrium. In other word, the chromium carbide is gradually enriched to reach the stable composition Cr{sub 23}С{sub 6}. This process is more rapid at higher temperatures. Obviously, the variation in composition of the carbide deposited at the grain boundaries in VOK-60M cutting ceramic with change in temperature and holding time will affect the kinetics of electrochemical solution of the system consisting of the carbide in contact with a solid solution. Research shows that vacuum sintering and annealing markedly improve the thermal stability. For the cutting ceramic, this is explained not only by the removal of fusible impurities but also by the larger quantity of aluminum and other alloying elements that remain in the strengthening phase, rather than being bound in oxides. Sintering in vacuum ensures greater plasticity of cutting ceramic based on nickel and cobalt in cutting 12Kh18N10Т and 14Kh17N2 steel at high speeds, with high temperatures in the machining zone. In addition, on sintering in vacuum furnaces, the content of small nonmetallic inclusions in the basic structure is 5–7 times less than in regular cutting ceramic. That significantly improves the deformability of the ceramic inserts.

36 MATERIALS SCIENCE↗

Performance of Ceramics in Severe Environments

Ceramics are generally stable to higher temperatures than most metals and alloys. Thus the development of high temperature structural ceramics has been an area of active research for many years. While the dream of a ceramic heat engine still faces many challenges, niche markets are developing for these materials at high temperatures. In these applications, ceramics are exposed not only to high temperatures but also aggressive gases and deposits. In this chapter we review the response of ceramic materials to these environments. We discuss corrosion mechanisms, the relative importance of a particular corrodent, and, where available, corrosion rates. Most of the available corrosion information is on silicon carbide (SIC) and silicon nitride (Si3N4) monolithic ceramics. These materials form a stable film of silica (SO2) in an oxidizing environment. We begin with a discussion of oxidation of these materials and proceed to the effects of other corrodents such as water vapor and salt deposits. We also discuss oxidation and corrosion of other ceramics: precurser derived ceramics, ceramic matrix composites (CMCs), ceramics which form oxide scales other than silica, and oxide ceramics. Many of the corrosion issues discussed can be mitigated with refractory oxide coatings and we discuss the current status of this active area of research. Ultimately, the concern of corrosion is loss of load bearing capability. We discuss the effects of corrosive environments on the strength of ceramics, both monolithic and composite. We conclude with a discussion of high temperature wear of ceramics, another important form of degradation at high temperatures.

Jacobson, Nathan S.↗

Integration Science and Technology of Advanced Ceramics for Energy and Environmental Applications

The discovery of new and innovative materials has been known to culminate in major turning points in human history. The transformative impact and functional manifestation of new materials have been demonstrated in every historical era by their integration into new products, systems, assemblies, and devices. In modern times, the integration of new materials into usable products has a special relevance for the technological development and economic competitiveness of industrial societies. Advanced ceramic technologies dramatically impact the energy and environmental landscape due to potential wide scale applications in all aspects of energy production, storage, distribution, conservation, and efficiency. Examples include gas turbine propulsion systems, fuel cells, thermoelectrics, photovoltaics, distribution and transmission systems based on superconductors, nuclear power generation, and waste disposal. Robust ceramic integration technologies enable hierarchical design and manufacturing of intricate ceramic components starting with geometrically simpler units that are subsequently joined to themselves and/or to metals to create components with progressively higher levels of complexity and functionality. However, for the development of robust and reliable integrated systems with optimum performance under different operating conditions, the detailed understanding of various thermochemical and thermomechanical factors is critical. Different approaches are required for the integration of ceramic-metal and ceramic-ceramic systems across length scales (macro to nano). In this presentation, a few examples of integration of ceramic to metals and ceramic to ceramic systems will be presented. Various challenges and opportunities in design, fabrication, and testing of integrated similar (ceramic-ceramic) and dissimilar (ceramic-metal) material systems will be discussed. Potential opportunities and need for the development of innovative design philosophies, approaches, and integrated system testing under simulated application conditions will also be presented.

Singh, M.↗