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Nanostructured gadolinium-doped ceria microsphere synthesis from ion exchange resin: Multi-scale in-situ studies of solid solution formation

In the current nano-sized material revolution, the main limitations to a large-scale deployment of nanomaterials involve health concerns related to nano-dissemination via air. Developing new chemical routes benefiting from nano-size advantages while avoiding their hazards could overcome these limitations. Addressing this need, a chemical route leading to soft nano-particle agglomerates, i.e., macroscopic precursors presenting the ability to be decomposed into nano-sized materials, was developed and applied to Ce{sub 0.8}Gd{sub 0.2}O{sub 2−δ}. Using cerium/gadolinium-loaded ion exchange resin, the Ce{sub 0.8}Gd{sub 0.2}O{sub 2−δ} solid solution formation as a function of temperature was studied in-situ through X-ray diffraction, X-ray absorption spectroscopy and Raman spectroscopy. Temperatures corresponding to the organic skeleton decomposition and to the mixed oxide crystallization were identified. An optimal heat treatment, leading to nanostructured soft agglomerates, was established. Microsphere processing capabilities were evaluated and particle size distribution measurements were recorded. A very low fracture strength was calculated, and a nanometric particle size distribution (170 nm) was determined. - Graphical abstract: The elaboration of micro-spherical precursors leading to the formation of nano-oxide soft agglomerates was studied and approved through the use of ion exchange resin loaded with cerium and gadolinium. The formation of the solid solution was followed through in-situ measurements such as XAS, XRD, Raman, TGA and DSC. Key temperatures were identified for the formation of the mixed-oxide. Following this study, the microstructure and particle size of oxide microspheres formed highlight the formation of soft nano-arrangments. - Highlights: • Soft microspherical agglomerates able to be decomposed into nano-sized materials. • In situ study of cerium/gadolinium-loaded ion exchange resin conversion in oxide. • In situ multi-scale study through Raman spectroscopy, XAS and HT-XRD. • Monodisperse nanometric particle synthesis suitable for ceramic processing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Comparison of structural and magnetic properties of Zn{sub x}Mg{sub 1.5-x}Mn{sub 0.5}FeO{sub 4} and MgAl{sub x}Cr{sub x}Fe{sub 2-2x}O{sub 4} spinel oxides

The spinel oxides Zn{sub x}Mg{sub 1.5-x}Mn{sub 0.5}FeO{sub 4} (x = 0.0 to 0.6) and MgAl{sub x}Cr{sub x}Fe{sub 2-2x}O{sub 4} (x = 0.0 to 0.6) abbreviated as ZMMFO and MACFO respectively, were synthesized by standard ceramic processing. The compositional purity of all the specimens was checked by EDAX technique. The X-ray diffractometry was employed to determine the lattice constants and distribution of cations in the interstitial voids. The initial decrease of cell edge parameter (a) for ZMMFO up to x = 0.2 and thereafter expected rise in the ‘a’ and the initial slower rate of reduction in the lattice constant for MACFO are explained as basic of cation occupancy. The magnetic ordering in both systems is explained by invoking statistical canting models. The compositional variation of magneton number (n{sub B}) for ZMMFO could be very well explained by Localized canting of spin (LCS) model while Random canting of spin (RCS) model was used for MACFO system.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Microstructure and Magnetic Properties of Ba{sub 0.95}Y{sub 0.05}Fe{sub 12−x}Co{sub x}O{sub 19} Hexaferrites

Magnetoplumbite-type (M-type) barium ferrites doped with different Y–Co doping content Ba{sub 0.95}Y{sub 0.05}Fe{sub 12−x}Co{sub x}O{sub 19} (x = 0, 0.1, 0.2, 0.3, 0.4, and 0.5) were successfully prepared by ceramic process and investigated in this paper for the first time. X-ray diffraction were used to analyze the phase of the prepared sample. The scanning electron microscopy (SEM) was used to measure the morphology, and magnetic properties were measured by vibrating sample magnetometer (VSM). The results of XRD show that the single phase of M-type barium ferrites was obtained with the increase of Co content (x), but α-Fe{sub 2}O{sub 3} occurred when x exceeds 0.3. The SEM results exhibit the uniform plane hexagonal structures of M-type ferrites with all range of Co doping content. VSM results display that magnetization (M{sub s}) and coercivity (H{sub c}) show the same tendency that their values first increase and then decrease with the increase of Co content.

36 MATERIALS SCIENCE↗

Influence of secondary phases on phase and microwave dielectric properties of new Ca{sub 2}Ce{sub 2}Ti{sub 5}O{sub 16} ceramics

Ca{sub 2}Ce{sub 2}Ti{sub 5}O{sub 16} ceramics processed via mix oxide route was investigated. Phase composition and microwave dielectric properties were measured using X-ray diffraction and a cavity method, respectively. CeO{sub 2} and another unidentified phase (that vanishes at ≥1400°C) existed as secondary phases along with the parent Ca{sub 2}Ce{sub 2}Ti{sub 5}O{sub 16} phase. The amount of the parent Ca{sub 2}Ce{sub 2}Ti{sub 5}O{sub 16} phase increased with increasing sintering temperature from 1350°C to 1450 °C accompanied by a decrease in the apparent density. The density decreased but ε{sub r} and Qufo increased with sintering temperature. An ε{sub r} ∼87.2, Qufo ∼5915 GHz and τ{sub f} ∼219 GHz was achieved for the sample sintered at 1450°C.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Continuing the Validation of CCIM Processability for Glass Ceramic HLLW Forms: Plan for Test AFY14CCIM-GC1

This test plan covers test AFY14CCIM-GC1which is the first of two scheduled FY-2014 test runs involving glass ceramic waste forms in the Idaho National Laboratory’s Cold Crucible Induction Melter Pilot Plant. The test plan is based on the successes and challenges of previous tests performed in FY-2012 and FY-2013. The purpose of this test is to continue to collect data for validating the glass ceramic High Level Liquid Waste form processability advantages using Cold Crucible Induction Melter technology. The major objective of AFYCCIM-GC1 is to complete additional proposed crucible pouring and post tapping controlled cooling experiments not completed during previous tests due to crucible drain failure. This is necessary to qualify that no heat treatments in standard waste disposal canisters are necessary for the operational scale production of glass ceramic waste forms. Other objectives include the production and post-test analysis of surrogate waste forms made from separate pours into the same graphite mold canister, testing the robustness of an upgraded crucible bottom drain and drain heater assembly, testing the effectiveness of inductive melt initiation using a resistive starter ring with a square wave configuration, and observing the tapped molten flow behavior in pans with areas identical to standard High Level Waste disposal canisters. Testing conditions, the surrogate waste composition, key testing steps, testing parameters, and sampling and analysis requirements are defined.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

In vitro cytotoxicity tests of ZnO‐Bi{sub 2}O{sub 3}‐Mn{sub 2}O{sub 3}-based varistor fabricated from ZnO micro and nanoparticle powders on L929 mouse cells

The present study investigated the cytotoxicity of ZnO‐Bi{sub 2}O{sub 3}‐Mn{sub 2}O{sub 3}-varistors. To this effect, ZnO‐Bi{sub 2}O{sub 3}‐Mn{sub 2}O{sub 3} varistors fabricated from ZnO micro-and nanoparticle powders are prepared via conventional ceramic processing method. The effects of ZnO particle size on the properties of ZnO varistors are also investigated. The strong solid-state reaction during sintering may be attributed to the high surface area of the 20 nm ZnO nanoparticles that promote strong surface reaction. The intensity of XRD peaks reflected the high degree of crystallinity of the ZnO nanoparticles. However, the width of the peaks in case of ZnO nanoparticles has increased due to the quantum size effect. The cytotoxicity evaluation of ZnO varistor was conducted on mouse connective tissue fibroblast cells (L929) using Trypan Blue Exclusion Assay analysis. The results show that the four types of varistor samples lead to cellular mitochondrial dysfunction, morphological modifications and apoptosis at the various concentration range and the toxic effects are obviously displayed in high concentration samples. 20nm-VDR is the most toxic materials followed by 40nm-VDR, P8-VDR, and W4-VDR in a descending order.

36 MATERIALS SCIENCE↗

The emergence of magnetic properties in (Pb{sub 0.845}Sm{sub 0.08}Fe{sub 0.035})(Ti{sub 0.98}Mn{sub 0.02})O{sub 3} and (Pb{sub 0.88}Nd{sub 0.08})(Ti{sub 0.98}Mn{sub 0.02})O{sub 3} perovskite ceramics

The emergence of magnetic properties and quadratic magnetoelectric coupling in a material with outstanding ferroelectric properties has been pursued. Thus, the multiferroicity driven by the substitution of rare earth R{sup 3+} ions (R = Sm, Nd) on the A-site of PbTiO{sub 3} perovskite ceramics has been investigated. In some samples, a transition element with large ionic radius, like Fe{sup 2+}, has been also added on the A site. Polycrystalline ceramic samples with composition (Pb{sub 1-3x/2-y}R{sub x}Fe{sub y}) (Ti{sub 0.98}Mn{sub 0.02})O{sub 3} (R = Sm; x = 0.08, y = 0.035) and (Pb{sub 1−3x/2}R{sub x})(Ti{sub 0.98}Mn{sub 0.02})O{sub 3} (R = Nd, x = 0.08) have been prepared by conventional solid state ceramic processing, starting from reagent grade oxide powders. X-ray diffraction analysis confirmed the obtaining of a crystalline phase with tetragonal P4 mm symmetry. Transmission electron microscopy and high resolution transmission electron microscopy investigations have been carried out in order to analyze the local structure. Temperature dependence of dielectric permittivity revealed a strong anomaly at the temperature T{sub c} of the paraelectric-ferroelectric phase transition. Transition temperature values depend on the R ion type and are lower than in pure lead titanate by 80–100 K. A broad anomaly of dielectric permittivity is found below 140–180 K, where magnetization also increases due to the quadratic magnetoelectric coupling between ferroelectric and magnetic states. For the (Pb{sub 0.845}Sm{sub 0.08}Fe{sub 0.035})(Ti{sub 0.98}Mn{sub 0.02})O{sub 3} composition, the piezoelectric charge coefficient at room temperature was d{sub 31} ∼−6.5 pC/N and the remanent magnetization M{sub r} at room temperature was about 0.1 emu/g.

36 MATERIALS SCIENCE↗

Synthesis and characterization of mixed phases in the Ca–Co–O system using the Pechini method

Highlights: ► We have prepared mixed Ca–Co–O phases 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 both kinetic and thermodynamic control. ► A revised phase diagram of the Ca–Co–O system is proposed. - Abstract: The synthesis of mixed phases in the Ca–Co–O system using the Pechini method was investigated. The phases CaCo{sub 2}O{sub 4}, Ca{sub 3}Co{sub 4}O{sub 9} and Ca{sub 3}Co{sub 2}O{sub 6}, which can be expressed in terms of the molar ratios of the binary oxides (CaO:Co{sub 2}O{sub 3}) as (1:1), (3:2) and (3:1) respectively, were obtained in pure form. Powder X-ray diffraction data showed they are comparable with materials obtained by conventional solid-state synthesis. The mild synthesis conditions of the Pechini method allowed the evolution of the Ca–Co–O phases to be studied as a function of temperature and heating time. Both variables have a strong influence on the composition of the products, indicating that both kinetic and thermodynamic factors play a role, with the former being of more importance at lower temperatures. The (1:1) phase, previously not identified in the phase diagram of the Ca–Co–O system, was obtained preferentially across the composition range below ca. 650 °C. The (3:2) phase was preferred until ca. 800 °C. At even higher temperatures, the (3:1) phase is obtained. The upper thermal stability limit of mixed phases in the Ca–Co–O system increases with the Ca:Co ratio. An updated phase diagram for the Ca–Co–O system is proposed.

36 MATERIALS SCIENCE↗

Structural, Bulk Permittivity, and Magnetic Properties of Lead-Free Electronic Material: Ba{sub 1}Bi{sub 1}Cu{sub 1}Fe{sub 1}Ni{sub 1}Ti{sub 3}O{sub 12}

In this report, Ba{sub 1}Bi{sub 1}Cu{sub 1}Fe{sub 1}Ni{sub 1}Ti{sub 3}O{sub 12} (BBCFNTO termed further) ceramics were synthesized using a conventional ceramic processing route. The formation of multiple phases has been confirmed from by the XRD pattern at room temperature. The surface micrograph indicates the uniform distribution of grains with distinct grain boundary. The co-relation between the impedance and dielectric parameters was realized by using a phase sensitive meter over a good temperature and frequency range. The temperature- and frequency-dependent dielectric properties are linked to the conduction mechanism. The dielectric constant (K) and loss (tanδ) are increased sharply at high-temperature region, which is expected to be the onset of dipolar relaxation phenomena. The contribution of grain boundary (GBs) and grain (Gs) effects can be identified using the complex impedance spectroscopy. This synthesized material is investigated to model multifunctional devices.

36 MATERIALS SCIENCE↗

Solid State Reduction Driven Synthesis of Mn Containing Multi-principal Component Alloys

In recent years, high entropy alloys (HEAs), also known as multi-principal component alloys (MPCAs) have emerged as a new and exciting class of materials. This paper reports on the solid state reduction synthesis of a series of CoFeNiMn-based MPCA compositions, starting from a mixture of the corresponding oxides. One of the aims of the study was to test whether the degree of reduction of MnO, a highly stable oxide, could be enhanced by tailoring the alloy composition. Specifically, the influence of Ni content was studied because Ni exhibits a significant negative enthalpy of mixing with Mn. High purity precursor powders of Co(OH) 2 , Fe 2 O 3 , MnO 2 , and NiO were milled and mixed using standard ceramic processing methods. Here, the nominal sample compositions (assuming complete oxide reduction) were (CoFeMn) x Ni (1-x) , for x = 0, 0.083, 0.166, and 0.25. The oxide samples were subjected to a series of isothermal reduction anneals in flowing 3 pct H 2 –Ar at 1100 °C. The resulting microstructures were characterized using scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). The composition of the resulting MPCAs was determined quantitatively using wavelength dispersive spectroscopy (WDS) in the electron microprobe. The study revealed that for each of the initial oxide compositions studied, it was possible to achieve an MPCA with ~ 25 at. pct Mn. These results were found to be consistent with the predictions of a thermodynamic model whereby a negative enthalpy of mixing (ΔH mix ), combined with a contribution from configurational entropy, can offset a positive free energy of reduction (ΔG red ). The incorporation of vibrational entropy into first principles calculations was found to have a significant effect on the predicted crystal structure of the MPCAs.

36 MATERIALS SCIENCE↗

Thin film growth effects on electrical conductivity in entropy stabilized oxides

Entropy stabilization has garnered significant attention as a new approach to designing novel materials. Much of the work in this area has focused on bulk ceramic processing, leaving entropy-stabilized thin films relatively under-explored. Following an extensive multi-variable investigation of polycrystalline (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 )O thin films deposited via pulsed laser deposition (PLD), it is shown here that substrate temperature and deposition pressure have strong and repeatable effects on film texture and lattice parameter. Further analysis shows that films deposited at lower temperatures and under lower oxygen chamber pressure are 40x less electrically resistive than otherwise identical films grown at higher temperature and pressure. Annealing these films in an oxygen-rich environment increases their electrical resistivity to match that of the films grown at higher temperatures and pressures. Because of this, the electric conductivity is hypothesized to be the result of polaron hopping mediated by transition metal valence changes which compensate for oxygen off-stoichiometry.

36 MATERIALS SCIENCE↗

Review of additive manufacturing and densification techniques for the net- and near net-shaping of geometrically complex silicon nitride components

Silicon nitride (Si 3 N 4 ) is an advantageous material due its unique combination of mechanical, thermal, chemical, and electrical properties both at ambient and elevated temperatures. Because of these properties there are a wide range of applications for Si 3 N 4 components. Applications include heat exchangers, environmental barrier coatings, osteointegration scaffolds, radomes, and integrated circuitry. Furthermore, such applications often require geometric complexity for efficient and/or effective operation. However, traditional ceramics processing methods such as hot-pressing or die extrusion are typically limited to simple axis-symmetric shapes. With the advent of additive manufacturing, there has been significant advancement into the forming of geometrically complex Si 3 N 4 components. This review documents additive manufacturing advancements that have demonstrated, or are capable of, fabricating Si 3 N 4 components with complex geometry.

36 MATERIALS SCIENCE↗

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↗

Interdisciplinary research concerning the nature and properties of ceramic materials

Research projects involving the development of ceramic materials are discussed. The following areas of research are reported: (1) refractory structural ceramics, (2) solid electrolyte ceramics, and (3) ceramic processing. The laboratory equipment used and the procedures followed for various development and evaluation techniques are described.

Mueller, J. I.↗