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At least 73 records · Page 4

Synthesis of the p-type semiconducting ternary oxide CuAlO{sub 2} using the Pechini method

Graphical abstract: - Highlights: • We have prepared single-phase samples of the semiconducting oxide CuAlO{sub 2} using the Pechini method. • Reaction times are reduced relative to conventional solid-state synthesis. • Products have high surface area suitable for ceramic processing. • Product composition is dictated by thermodynamic control; CuAl{sub 2}O{sub 4} is obtained preferentially at lower temperature. - Abstract: The synthesis of the delafossite phase CuAlO{sub 2} using the Pechini method was investigated. Powder X-ray diffraction data showed that pure, single-phase samples were obtained after only 3 h heating at 1100 °C. CuAl{sub 2}O{sub 4}, which contains Cu(II) rather than Cu(I), was the dominant phase between 700 and 1100 °C. Conversion to CuAlO{sub 2} is promoted by the positive entropy change associated with the evolution of oxygen. No mixed Cu–Al oxide was formed below 700 °C.

36 MATERIALS SCIENCE↗

Unlocking anionic redox activity in O3-type sodium 3 d layered oxides via Li substitution

Sodium ion batteries, because of their sustainability attributes, could be an attractive alternative to Li-ion technology for specific applications. However, it remains challenging to design high energy density and moisture stable Na-based positive electrodes. Here, we report an O3-type NaLi 1/3 Mn 2/3 O 2 phase showing anionic redox activity, obtained through a ceramic process by carefully adjusting synthesis conditions and stoichiometry. This phase shows a sustained reversible capacity of 190 mAh g -1 that is rooted in cumulative oxygen and manganese redox processes as deduced by combined spectroscopy techniques. Unlike many other anionic redox layered oxides so far reported, O3-NaLi 1/3 Mn 2/3 O 2 electrodes do not show discernible voltage fade on cycling. This finding, rationalized by density functional theory, sheds light on the role of inter- versus intralayer 3d cationic migration in ruling voltage fade in anionic redox electrodes. Another practical asset of this material stems from its moisture stability, hence facilitating its handling and electrode processing. Altogether, this work offers future directions towards designing highly performing sodium electrodes for advanced Na-ion batteries.

25 ENERGY STORAGE↗

Three-dimensional mapping of crystalline ceramic waste form materials

Here, we demonstrate the use of synchrotron-based, transmission X-ray microscopy (TXM) and scanning electron microscopy to image the 3-D morphologies and spatial distributions of Ga-doped phases within model, single- and two-phase waste form material systems. Gallium doping levels consistent with those commonly used for nuclear waste immobilization (e.g., Ba 1.04 Cs 0.24 Ga 2.32 Ti 5.68 O 16 ) could be readily imaged. This analysis suggests that a minority phase with different stoichiometry/composition from the primary hollandite phase can be formed by the solid-state ceramic processing route with varying morphology (globular vs. cylindrical) as a function of Cs content. Our results represent a crucial step in developing the tools necessary to gain an improved understanding of the microstructural and chemical properties of waste form materials that influence their resistance to aqueous corrosion. This understanding will aid in the future design of higher durability waste form materials.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

(Invited) All-Solid-State Batteries Using Li 7 La 3 Zr 2 O 12 Garnet Electrolyte Framework

All-solid-state batteries (ASSB) using LLZO (variants of Li 7 La 3 Zr 2 O 12 ) garnet solid electrolyte with lithium metal anode potentially offer higher energy density and improved safety. Rational design of cell architecture as well as manufacturing scalability are key aspects to consider as the technology readiness level advances. A thick composite cathode layer attached to a thin solid electrolyte layer is desirable to obtain superior energy densities. Furthermore, the architecture within the composite cathode may be engineered to contain directional conduction paths of lithium ions or electrons for enhanced rate capabilities. Here, we demonstrate a functioning bulk-type LLZO based all-solid-state battery with a practical form factor incorporating the above described design concepts. Freeze-tape-casting (FTC), a scalable and environmentally friendly ceramic processing method, is used to construct 3D porous LLZO scaffolds composed of vertical arrays of LLZO walls. The thin solid-electrolyte layer is fabricated by tape-casting (TC). By sintering the stacks of FTC and TC green tapes, porous/dense bilayers and porous/dense/porous trilayers of LLZO frameworks are obtained. An ASSB was constructed using a porous/dense bilayer by infiltrating LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathode powder and carbon black into the porous layer and adhering lithium metal foil to the dense side. We find it crucial to introduce a plastic crystal based soft solid electrolyte to the porous layer to electrochemically connect all cathode components, obviating the need for co-sintering to establish contact. The soft nature of the plastic crystal based solid-electrolyte may be able to accommodate the volume change of the cathode material as it cycles. In this device, which contained no liquid component, the initial discharge capacities were similar to those observed in a lithium ion battery configuration using the same cathode powder at C/10 rates.

25 ENERGY STORAGE↗

Multiscale Porous High-temperature Heat Exchanger Using Ceramic Co-extrusion

In this project, our MIT, Purdue, and GE team aims to design, model, fabricate, and test a novel high temperature, compact, and durable ceramic heat exchanger to be operated under high temperature and pressure conditions for aerospace applications. Our approach is grounded in introducing multiscale porosity, i.e., centimeter-scale channels embedded with micrometer-scale channels, into the ceramic heat exchanger to significantly improve its heat transfer performance and mechanical strength while maintaining minimal pressure losses. We first developed high-fidelity thermal-fluid-mechanical model capable of precisely capturing the heat transfer rate, temperature profile, pressure drop, and mechanical stress throughout the entire heat exchanger design. Guided by our model, we identified the optimal design parameters for the SiC heat exchanger body and manifolds. Then, we established a completed fabrication procedure to create multiscale features in the ceramic heat exchanger, including co-extrusion, lamination, burnout, and sintering. We fabricated multiple heat exchanger bodies consisting of 6 × 6 and 3 × 3 centimeter-scale channels where each individual centimeter-scale channel comprises 625 crack-free microchannels with 90 μm × 90 μm opening. Owing to the multiscale features, our fabricated heat exchanger bodies exhibited desirable mechanical strength with 156 MPa flexural strength under 1300 Celsius degree. Despite the demonstrated highly tailorable microscopic features and superior mechanical strength, we identified delamination due to the complex interaction among ceramic, polymer, and gas species can be a critical challenge to create fully defect-free heat exchanger, which requires further fundamental investigations in future works. To test the heat exchanger performance, we constructed a high-temperature and high-pressure experimental apparatus that can be safely operated under 400 Celsius degree and 4 bar. With insights gained from mechanistic modeling, material development, and detailed characterization, a cost model was finally developed to understand the market potential of the developed technology, where a cost of $43,000 Celsius degree/kW was envisioned. This project developed a transformative approach to high-performance heat exchanger design. The thermal-fluid-mechanical design approach developed in this project can serve as a generic tool to guide the design of various heat-exchangers operated under high-temperature and high-pressure conditions. The material fabrication approach established in this project can be a useful guide for ceramic processing at extreme length scales.

42 ENGINEERING↗

Additive manufacturing of high‐density silicon carbide ceramics through post‐processing spark plasma sintering

This research advances the field of additive manufacturing (AM) of silicon carbide (SiC) ceramics by integrating spark plasma sintering (SPS) to enhance material density, mechanical strength, and thermal properties. Traditional AM techniques struggle to achieve the high‐density SiC required for demanding applications, such as aerospace engineering, where high thermal conductivity and mechanical strength are paramount. Here, our study addresses these challenges by incorporating SPS as a post‐processing step, achieving near‐theoretical maximum densities and significantly reducing porosity, thereby resulting in outstanding thermal conductivity in SiC ceramics. We developed a specialized SiC ink optimized for 3D printing, ensuring structural integrity after deposition through tailored rheological properties. The application of SPS facilitates rapid, uniform sintering, essential for attaining superior density, mechanical properties, and thermal performance. Our experimental results, confirmed through scanning electron microscopy analysis, demonstrate significant microstructural properties, mechanical strength, and thermal conductivity, showcasing the effectiveness of integrating SPS in AM processes. This innovative approach not only expands the capabilities of AM in producing complex, high‐density ceramic structures but also broadens the potential applications of SiC in demanding environments.

36 MATERIALS SCIENCE↗

Ceramic Waste Form Process for Immobilizing Iodine in Glass-Bonded Iodosodalite

A modified glass-bonded sodalite ceramic waste (CWF) form approach was used to fabricate ACWF-NaI or ACWF-AgI iodosodalite [i.e., Na 8 (AlSiO 4 ) 6 I 2 ] waste forms by occluding either NaI or AgI, respectively, into zeolite 4A at elevated temperatures, adding an NBS-4 glass binder, and firing at 925°C. The phase purity of ACWF-NaI was 82.6 mass% Na 8 (AlSiO 4 ) 6 I 2 (with amorphous remainder) while the ACWF-AgI only had 25.9 mass% Na 8 (AlSiO 4 ) 6 I 2 , despite the iodine being added as AgI; the remainder phases for ACWF-AgI included NaAlSiO 4 (15.1 mass%), AgI (4.5 mass%), and Ag 0 (0.2 mass%). This study shows that, starting from two different iodine salts, that the CWF process could be used for immobilization.

36 MATERIALS SCIENCE↗

A novel freeform extrusion fabrication process for producing solid ceramic components with uniform layered radiation drying

An extrusion-based additive manufacturing process, called the Ceramic On-Demand Extrusion (CODE) process, for producing three-dimensional ceramic components with near theoretical density is introduced in this paper. Heere in this process, an aqueous paste of ceramic particles with a very low binder content (<1 vol%) is extruded through a moving nozzle at room temperature. After a layer is deposited, it is surrounded by oil (to a level just below the top surface of most recent layer) to preclude non-uniform evaporation from the sides. Infrared radiation is then used to partially, and uniformly, dry the just-deposited layer so that the yield stress of the paste increases and the part maintains its shape. The same procedure is repeated for every layer until part fabrication is completed. Several sample parts for various applications were produced using this process and their properties were obtained. The results indicate that the proposed method enables fabrication of large, dense ceramic parts with complex geometries.

36 MATERIALS SCIENCE↗

Cold Sintering Process of Composites: Bridging the Processing Temperature Gap of Ceramic and Polymer Materials

Co-sintering ceramic and thermoplastic polymer composites in a single step with very high volume fractions of ceramics seems unlikely, given the vast differences in the typical sintering temperatures of ceramics versus polymers. These processing limitations are overcome with the introduction of a new sintering approach, namely “cold sintering process” (CSP). CSP utilizes a transient low temperature solvent, such as water or water with dissolved solutes in stoichiometric ratios consistent with the ceramic composition, to control the dissolution and precipitation of ceramics and effect densification between room temperature and ≈200 °C. Under these conditions, thermoplastic polymers and ceramic materials can be jointly formed into dense composites. Three diphasic composite examples are demonstrated to show the overall diversity of composite material design between organic and inorganic oxides, including the microwave dielectric Li 2 MoO 4 –(-C 2 F 4 -) n , electrolyte Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 –(-CH 2 CF 2 -) x [-CF2CF(CF3)-] y, and semiconductor V 2 O 5 –poly(3,4-ethylenedioxythiophene) polystyrene sulfonate composites. Cold sintering is more general and shall have a major impact on the processing of composite materials for many different applications, mechanical, thermal, and electronic, to mention a few possibilities. CSP concepts open up new composite material design and device integration schemes, impacting a wide variety of applications.

36 MATERIALS SCIENCE↗

Smaller feature size impairs densification in digital light processing 3D printed ceramic samples

In this study, we investigate how geometric miniaturization affects the sintering densification behavior of alumina cylinders with various wall thicknesses (down to ∼500 µm in green body) fabricated via digital light processing (DLP). As the wall thickness decreased, the density of the sintered samples consistently declined. Microstructural characterization revealed the presence of a crack-rich surface skin that is ∼500 µm thick. As the wall thickness decreases, the skin's volume fraction rises, and its poor local densification increasingly dominates the part average, leading to an overall decrease in the density of the sintered samples. For the thinnest wall (500 µm) cylinder, macroscopic warping occurred during sintering. We suggest that warping further disrupts particle packing and induces through-thickness nonuniformity, further impairing densification in addition to the skin-fraction effect. These results highlight how geometric miniaturization may adversely influence the sintering behavior and final density of DLP-printed ceramics through distinct densification-limiting mechanisms.

Materials science↗

Tracking copper nanofiller evolution in polysiloxane during processing into SiOC ceramic

Polymer-derived ceramics (PDCs) remain at the forefront of research for a variety of applications including ultra-high-temperature ceramics, energy storage and functional coatings. Despite their wide use, questions remain about the complex structural transition from polymer to ceramic and how local structure influences the final microstructure and resulting properties. This is further complicated when nanofillers are introduced to tailor structural and functional properties, as nanoparticle surfaces can interact with the matrix and influence the resulting structure. The inclusion of crystalline nanofiller produces a mixed crystalline–amorphous composite, which poses characterization challenges. With this study, we aim to address these challenges with a local-scale structural study that probes changes in a polysiloxane matrix with incorporated copper nanofiller. Composites were processed at three unique temperatures to capture mixing, pyrolysis and initial crystallization stages for the pre-ceramic polymer. We observed the evolution of the nanofiller with electron microscopy and applied synchrotron X-ray diffraction with differential pair distribution function (d-PDF) analysis to monitor changes in the matrix's local structure and interactions with the nanofiller. The application of the d-PDF to PDC materials is novel and informs future studies to understand interfacial interactions between nanofiller and matrix throughout PDC processing.

Chemistry↗

Comparison of structure, morphology, and leach characteristics of multi-phase ceramics produced via melt processing and hot isostatic pressing

Melt processing of multi-phase ceramic waste forms offers potential advantages over traditional solid-state synthesis methods given both the prevalence of melters currently in use and the ability to reduce the possibility of airborne radionuclide contamination. In this work, multi-phase ceramics with a targeted hollandite composition of Ba 1.0 Cs 0.3 Cr 1.0 Al 0.3 Fe 1.0 Ti 5.7 O 16 were fabricated by melt processing at 1675 °C and hot isostatic pressing (HIP) at 1250 and 1300 °C. X-ray diffraction analysis (XRD) confirmed hollandite as the major phase in all specimens. Zirconolite/pyrochlore peaks and weaker perovskite reflections were observed after melt processing, while HIP samples displayed prominent perovskite peaks and low-intensity zirconolite reflections. Melt processing produced specimens with large (>50 μm) well-defined hollandite grains, while HIP yielded samples with a more fine-grained morphology. Elemental analysis showed “islands” rich in Cs and Ti across the surface of the 1300 °C HIP sample, suggesting partial melting and partitioning of Cs into multiple phases. Photoemission data revealed multiple Cs 3d spin-orbit pairs for the HIP samples, with the lower binding energy doublets likely corresponding to Cs located in more leachable phases. Among all specimens examined, the melt-processed sample exhibited the lowest fractional release rates for Rb and Cs. However, the retention of Sr and Mo was greater in the HIP specimens.

36 MATERIALS SCIENCE↗

Fracture toughness of plasma-sprayed thermal barrier ceramics: Influence of processing, microstructure, and thermal aging

Fracture toughness has become one of the dominant design parameters that dictates the selection of materials and their microstructure to obtain durable thermal barrier coatings (TBCs). Much progress has been made in characterizing the fracture toughness of relevant TBC compositions in bulk form, and it has become apparent that this property is significantly affected by process-induced microstructural defects. In this investigation, a systematic study of the influence of coating microstructure on the fracture toughness of atmospheric plasma sprayed (APS) TBCs has been carried out. Yttria partially stabilized zirconia (YSZ) coatings were fabricated under different spray process conditions inducing different levels of porosity and interfacial defects. Fracture toughness was measured on free standing coatings in as-processed and thermally aged conditions using the double torsion technique. Results indicate significant variance in fracture toughness among coatings with different microstructures including changes induced by thermal aging. Comparative studies were also conducted on an alternative TBC composition, Gd 2 Zr 2 O 7 (GDZ), which as anticipated shows significantly lower fracture toughness compared to YSZ. Furthermore, the results from these studies not only point towards a need for process and microstructure optimization for enhanced TBC performance but also a framework for establishing performance metrics for promising new TBC compositions.

36 MATERIALS SCIENCE↗

Chemically Inert Hydrocarbon-Based Slurries for Rapid Laser Sintering of Thin Proton-Conducting Ceramics

The process of rapid laser sintering of thin BaZrO 3 –BaCeO 3 -based proton-conducting electrolytes is being developed for easy fabrication of ceramic fuel cells and electrolyzers. However, cracks on the electrolytes caused by volume change due to chemical reactions between the basic ceramic constituents and the polar solvents during wet processing has been problematic. In order to address this issue, the use of chemically inert saturated-hydrocarbon-based slurries comprised of hexadecane, polybutene, and a long-chain saturated fatty acid were investigated in this work. By optimizing slurry composition and laser sintering conditions, a 20 mm long, 4 mm wide, 13.5-μm-thick and 97%-dense BaCe 0.7 Zr 0.1 Y 0.07 Sm 0.13 O 3-d membrane showing proton conductivity on the order of 10 –4 S•cm –1 at 600 °C was successfully prepared in just three seconds by laser sintering. As a result, the use of saturated-hydrocarbon-based slurries will facilitate wet processing and rapid laser sintering of proton-conducting ceramic electrolytes.

36 MATERIALS SCIENCE↗