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Tape casting and characterizations of MgO ceramics

Herein we report a high density MgO ceramic substrate produced by the tape casting technology. The tape casting formulation and process produced a uniform tape free of cracking. Y 2 O 3 and SiO 2 were used as the sintering aid for the pressureless sintering of the green tape. X-ray diffraction phase identification indicates that MgO is the main phase, while both Y 2 O 3 and SiO 2 sintering aids react with MgO to form MgY 4 Si 3 O 13 as the second phase. Liquid phase sintering occurs in the temperature range from 1030°C to ~1500°C, which is confirmed by the simultaneous Thermal Gravitation Analysis/ Differential Scanning Calorimeter (TGA/DSC) and the percent linear shrinkage and densification. A 96.5% theoretical density was achieved by presureless sintering at 1650°C for 2 hours, which was further increased to a fully dense structure using hotisostatic- pressing(HIP) at 1650°C and 207 MPa in argon. Scanning electron microscopy (SEM) and energy dispersive(EDS) spectroscopic analysis on the HIP’ed sample show that MgY 4 Si 3 O 13 is located at the MgO grain boundary and the sample has a fully dense structure. The refractive indices and extinction coefficient were measured on the HIP’ed sample along with thermal properties and dielectric properties. Thermal diffusivity and heat capacity were measured to calculate the thermal conductivity.

36 MATERIALS SCIENCE↗

Cross-Flow Filtration of Multiple Algal Strains and Mixed Populations Using Embedded Membranes

The objective of this research is to analytically assess cross-flow membrane filtration (CFF) technology as an algal harvesting approach that will debottleneck the water recovery/nutrient recovery/recycling processes. Specifically, the focus of this investigation will be INL-developed, ceramic-embedded, erosion-resistant membrane technology, comprising stainless steel micro- and ultra-filters with controlled pore sizes to reduce membrane fouling and enhance filtration permeation properties. Parameters such as shear/face velocity and transmembrane pressure will be varied to assess impact on filtration efficiency. Detrimental effects such as cell lysis must also be considered. The project is an opportunity to analytically investigate the level of shear (cross-flow face velocity level) needed to accomplish dewatering by filtration in an economic manner while gaining insight into membrane fouling mechanisms. Furthermore, testing of the membranes with different starting concentrations of algae, as well as with a variety of membranes and filtration conditions, will allow us to establish the boundary conditions where membrane technologies are appropriate for application in an overall algal harvesting strategy.

09 BIOMASS FUELS↗

Iotron development of Cu67 radioisotope

The collaboration has developed a method of producing the Cu-67 medical isotope for beta therapy of cancers such as non-Hodgkins melanoma. In particular we have used electron linac production of intense gamma ray beams to convert Zn-68 into Cu-67 in metal targets. The targets are subsequently processed by separating the Cu isotope from the Zn metal using sublimation, with ceramic components to avoid contamination of the final product.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Automated Mini-Tubular Ceramic Production (Final Design Review)

Researchers at Lawrence Livermore National Laboratory need a way to increase the rate of manufacturing of mini-tubular ceramics to be used in testing particulate air filters. This document outlines our process from researching and writing an initial scope of work all the way to fabricating and testing a final prototype. This journey takes us through the background research, ideation process and selection of a final design. We also detail the desired engineering specifications and our concept selection process. We dedicate a significant portion of this report to discussion of our final design. We delve into how it was manufactured as well as the tests we performed and its successes and failures. We also propose potential areas for further development and next steps for sponsors. Overall, this document provides the reader with a comprehensive understanding of our design process and results.

36 MATERIALS SCIENCE↗

Enhanced electrical penetration components meet the high safety standards required for China's HTR-PM Shidaowan and generation mPower small modular reactors - 300

Enhanced glass-to-metal feedthroughs will be used to carry key instrumentation and control (I and C) signals in China's high-temperature, gas-cooled pebble-bed modular reactor (HTR-PM) at Shidaowan, and in Small Modular Reactor (SMR) prototyping. Chinergy Co., Ltd and Jiamusi Electric Machine Co., Ltd will use the feedthroughs, also called electrical penetration assemblies (EPAs), at the Shidaowan twin-reactor high temperature reactor (HTR). These feedthroughs are manufactured using specialized processes that make them far more robust than counterparts made with organic or ceramic materials. Improved EPAs manufactured by SCHOTT are the only feedthrough solution that can be used in the primary loop of an HTR because organic seals cannot withstand the high temperatures and pressures of this environment. Glass-to-metal seals (GTMS) are made using inorganic, non-aging materials which enable a virtually unlimited lifespan in high-temperature, high-radiation and high-pressure applications. This I and C technology package is being enhanced by the development and testing of new mineral-insulated (MI) cable connectors and EPAs made of crystallized glass-ceramic combined with superalloys. The EPAs have a maintenance-free lifespan of over 60 years, preventing any outage time related to these components and subsequently reducing costs associated with shutdowns. They are far more robust than organic seals and provide increased safety at a lower lifetime cost. Resistance against high pressure and high temperature are especially ideal qualities that make EPAs a valuable choice for environments with high standards for fire protection, such as nuclear plants, subsea oil drilling, or any other underwater application. Due to their significant offering of safety-relevant qualities, the EPAs have also been chosen by BWXT for implementation in its mPower SMR. Small modular reactor requirements are complex and very challenging but are met by the new EPA components, which will help form a strong I and C safety chain. Unlike ordinary compression glass-to-metal seals, GTMS with crystallized glass-ceramic have the ability to withstand temperatures of over 350 deg. C / 662 deg. F and operating pressures of 3500 bar. Furthermore, their lifetime is qualified for up to 60 years, including pressure and radiation requirements in accordance with the latest IEC/IEEE standards. Higher-specification EPAs and MI cable connectors have been designed into severe accident I and C instruments, including advanced hydrogen and oxygen sensors that exceed the challenging requirements of both HTR and SMR applications. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Novel ceramic capacitors with ultrahigh energy density and efficiency (Final Technical Report)

Antiferroelectric ceramics are a special class of material that have shown great potential as the dielectric in electrical capacitors due to their high energy- and power-density. During each charge-discharge cycle, the ceramic undergoes transformation to a ferroelectric phase and resumes its antiferroelectric phase. The hysteresis associated with the transitions leads to a mediocre energy efficiency and service lifetime of antiferroelectric capacitors and, hence, their almost absence in commercial products. Under the support of this research project, we first formulated a universal lattice-compatibility theory that included electrostatic polarization energy along with elastic energy and thermal energy to understand the origin of the hysteresis in antiferroelectric oxides. Guided by this compatibility theory, we conducted high-throughput density functional theory (DFT) calculations to assess chemical modifiers and their effect on crystal structures of 400+ PbZrO 3 -based compositions. Down-selected compositions were experimentally validated for their suppressed hysteresis and higher energy efficiency. The verified low-hysteresis compositions were then expanded to an antiferroelectric ceramic library with nearly 500 new compositions (more than 1,500 samples) using high-throughput experiments involving ceramic synthesis and property screening. The large quantity of data generated (theory and experimental) in these tasks were processed by machine-learning techniques and identified trends were fed to the next iteration. In the end, we successfully discovered four compositions with near-zero hysteresis, yielding a world-record energy efficiency of 98.2% at an energy density of 3.0 J/cm 3 . Furthermore, our antiferroelectric ceramic capacitor reaches 79.5 million charge-discharge cycles lifetime, a factor of 80 enhancement over previous antiferroelectric ceramics with large hysteresis. These research accomplishments have not only met the milestones set in the SOPO, but also led to two patent filings, three journal publications (one of them was in Advanced Materials, impact factor 29.4), and nine oral presentations at various venues. Through the course of the project, three postdocs, four Ph.D. students, and one M.S. student were trained. In short, our project established a new methodology in searching next-generation functional ceramics on the fundamental side and discovered several high-efficiency antiferroelectric compositions for capacitors on the applied side. Once fabricated into the multilayer form for commercial applications, these ceramic capacitors can potentially enable the high temperature high power density DC-link capacitors that are critical for the next generation inverters in electric vehicles. The project also significantly contributed to the nation’s workforce development in the STEM fields.

36 MATERIALS SCIENCE↗

Synthesis of Sr{sub 0.9}K{sub 0.1}FeO{sub 3-{delta}} electrocatalysts by mechanical activation

Potassium-substituted SrFeO{sub 3-{delta}} for possible application as oxygen evolution electrode in alkaline or molten salt media was prepared by mechanical activation and characterized by X-ray diffraction, dilatometric and thermogravimetric analysis, Moessbauer spectroscopy, and electrical conductivity measurements. Room temperature mechanical activation of a mixture of oxide precursors with subsequent thermal treatments at 700-900 Degree-Sign C results in the formation of Sr{sub 0.9}K{sub 0.1}FeO{sub 3-{delta}} with tetragonal perovskite-like structure. Such allows to decrease the synthesis temperature, if compared to the conventional solid-state route, and to prevent possible volatilization of potassium. The results of Moessbauer spectroscopy studies indicate that the oxygen nonstoichiometry in the samples annealed in air at 900-1100 Degree-Sign C with subsequent rapid cooling vary in the range {delta}=0.30-0.32. The electrical conductivity in air exhibits a metal-like behaviour at temperatures above 400 Degree-Sign C and semiconductor behaviour in the low-temperature range, reaching 13-30 S/cm under prospective operation conditions for alkaline electrolyzers ({<=}90 Degree-Sign C). - graphical abstract: XRD patterns of Sr{sub 0.9}K{sub 0.1}FeO{sub 3-{delta}} powders, as-prepared and after annealing at different temperatures. Log({sigma}{center_dot}T) vs. 1000/T plot of the electrical conductivity of Sr{sub 0.9}K{sub 0.1}FeO{sub 3-{delta}}. The inset shows the thermal variation of {sigma}. Ceramics used were prepared by mechanical activation followed by a two-step sintering process at 900 Degree-Sign C for 1 h and 1000 Degree-Sign C for 5 h (82% densification). Highlights: Black-Right-Pointing-Pointer Sr{sub 0.9}K{sub 0.1}FeO{sub 3-{delta}} was successfully obtained by mechanical activation of oxide precursors. Black-Right-Pointing-Pointer Synthesis temperature is significantly lower when compared to a conventional solid-state route. Black-Right-Pointing-Pointer Oxygen nonstoichiometry of annealed samples at 900-1100 Degree-Sign C vary in the range {delta}=0.30-0.32. Black-Right-Pointing-Pointer Sr{sub 0.9}K{sub 0.1}FeO{sub 3-{delta}} shows metal and semiconductor behaviour above and below 400 Degree-Sign C, respectively.

36 MATERIALS SCIENCE↗

Repair process and a repaired component

Matrix composite component repair processes are disclosed. The matrix composite repair process includes applying a repair material to a matrix composite component, securing the repair material to the matrix composite component with an external securing mechanism and curing the repair material to bond the repair material to the matrix composite component during the securing by the external securing mechanism. The matrix composite component is selected from the group consisting of a ceramic matrix composite, a polymer matrix composite, and a metal matrix composite. In another embodiment, the repair process includes applying a partially-cured repair material to a matrix composite component, and curing the repair material to bond the repair material to the matrix composite component, an external securing mechanism securing the repair material throughout a curing period, In another embodiment, the external securing mechanism is consumed or decomposed during the repair process.

42 ENGINEERING↗

Structure, upconversion photoluminescence, and dielectric properties of Ho{sup 3+}- and Yb{sup 3+}-codoped tetragonal tungsten bronze Sr{sub 4}La{sub 2}Ti{sub 4}Nb{sub 6}O{sub 30}

Highlights: • TTB-type SLTN: Ho-Ybx with space group P4/mbm was determined. • UC photoluminescence of SLTN: Ho-Ybx ceramics was first reported. • Bright UC green emission was observed at room temperature. • Two-photon energy transfer process was confirmed for the UC processes. • Temperature stability of dielectric permittivity was improved for SLTN: Ho-Ybx. - Abstract: Ho{sup 3+}- and Yb{sup 3+}-codoped Sr{sub 4}La{sub 2}Ti{sub 4}Nb{sub 6}O{sub 30} (Sr{sub 4}La{sub 1.94–x}Ho{sub 0.06}Yb{sub x}Ti{sub 4}Nb{sub 6}O{sub 30}, abbreviated as SLTN: Ho-Ybx) ceramics have been synthesized, and their structural, up-conversion (UC) photoluminescence, and dielectric properties have been carefully investigated. Through Rietveld structural refinement, SLTN: Ho-Ybx samples are determined as single tetragonal tungsten bronze (TTB) phase with space group P4/mbm in which larger Sr{sup 2+} ions fill the A{sub 2}-sites, relative smaller La{sup 3+}, Ho{sup 3+}, and Yb{sup 3+} ions occupy the A{sub 1}-sites, while Ti{sup 4+} and Nb{sup 4+} ions fill the B-sites. Under 980 nm near infrared (NIR) excitation, bright UC green emission, relatively weak red and near-infrared (NIR) emissions, originating from {sup 5}F{sub 4}/{sup 5}S{sub 2} → {sup 5}I{sub 8}, {sup 5}F{sub 5} → {sup 5}I{sub 8}, and {sup 5}F{sub 4}/{sup 5}S{sub 2} → {sup 5}I{sub 7} transitions of Ho{sup 3+} ions, are confirmed for SLTN: Ho-Ybx. Two-photon energy transfer process is proved through pumping laser power dependence of emission intensity measurement. Furthermore, the influence of Ho{sup 3+}- and Yb{sup 3+}- ions on the dielectric properties of SLTN: Ho-Ybx is also investigated and the temperature stability of dielectric permittivity is improved.

36 MATERIALS SCIENCE↗

Poly(vinylidene fluoride)/ CaCu{sub 3}Ti{sub 4}O{sub 12} and La doped CaCu{sub 3}Ti{sub 4}O{sub 12} composites with improved dielectric and mechanical properties

Highlights: • High ϵ′ PVDF/CCTO and La doped CCTO composites prepared by Extrusion. • With addition of ceramic, there is substantial increase in the ϵ′ of matrix PVDF. • Composites exhibit double relaxation behavior. - Abstract: Melt extrusion process has been used to prepare high relative permittivity, ϵ' PVDF–CCTO and PVDF–LaCCTO composites. Phase composition has been studied using powder X-ray diffraction (XRD). Microstructural, dielectric and mechanical properties have also been studied. Young's modulus of PVDF increases with the ceramic reinforcement. Dielectric measurements are made in the frequency range 10{sup −2}–10{sup 6} Hz using two probe Novocontrol impedance analyser (ZG4) from room temp to 120 °C to study the dielectric relaxation. There is a substantial increase in ϵ' of the matrix PVDF on addition of LaCCTO.

36 MATERIALS SCIENCE↗

Ferroelectric, dielectric and piezoelectric properties of Sr{sub 0.6}(BiNa){sub 0.2}Bi{sub 2}Nb{sub 2}O{sub 9} ceramics

Graphical abstract: The oxygen vacancy was confirmed by the left figure and the role of oxygen vacancy on the piezoelectric properties was discussed. - Highlights: • The d{sub 33}, ρ and T{sub c} were found to be 22 pC/N, ρ ∼ 10{sup 6} Ω cm and 586 °C. • The electromechanical properties: k{sub p} ∼ 5.0%, k{sub t} ∼ 8.7% and Q{sub m} ∼ 651. • The oxygen vacancy is responsible for electrical properties at high temperature. - Abstract: Aurivillius-type ceramic, Sr{sub 0.6}(BiNa){sub 0.2}Bi{sub 2}Nb{sub 2}O{sub 9} (SBNBN), was synthesized by using conventional solid-state processing. Phase structure and microstructural morphology were confirmed by X-ray diffraction analyses (XRD) and the scanning electron microscopy (SEM). Dielectric, piezoelectric and electromechanical properties of the SBNBN ceramic were investigated in detail. Curie temperature (T{sub c}), piezoelectric coefficient (d{sub 33}), electromechanical coupling coefficient k{sub p}, k{sub t} and quality factor Q{sub m} of the SBNBN ceramic were found to be 586.5 °C, 22 pC/N, 5.0%, 8.7% and 651, respectively. In addition, the reasons for varieties of the resistivity and dielectric properties at high temperature were also discussed.

36 MATERIALS SCIENCE↗

Influence of Thermal Treatment on Preceramic Polymer Grafted Nanoparticle Network Formation: Implications for Thermal Protection Systems and Aerospace Propulsion Components

Preceramic polymer grafted nanoparticles (PCP GNPs) offer potential advantages in the production of polymer-derived ceramic composites compared to neat preceramic polymers (PCPs), such as reduced thermal shrinkage and increased char yield. In comparison to traditional composites (particles + free polymer), PCPs avoid issues of compatibility, agglomeration, and phase separation during processing and provide routes to control nanoparticle arrangement. Prior literature has established that the conversion efficiency of PCPs and PCP GNPs to ceramics and ceramic composites is linked to the thermal pretreatment of these precursor polymers (e.g., curing). In this paper, we investigate the material transformations that occur when exposing PCP GNPs to a low-temperature thermal treatment (≤250 °C) prior to pyrolysis. The PCP GNPs explored in this study possessed silica nanoparticle cores but were distinct in their PCP coronas, having poly(1,1-dimethylpropylsilane) (allyl-GNP)- or poly(1,1-dimethylbenzylethylsilane) (styryl-GNP)-grafted polymers. After undergoing low-temperature thermal treatment, these PCP GNPs exhibited increased char yield at 800 °C; however, unlike commercial PCPs (e.g., allylhydridopolycarbosilane (SMP-10)), obvious cross-linkable sites are not present in the PCP corona structure. Differential scanning calorimetry, oscillatory rheology, and X-ray photon correlation spectroscopy were utilized to elucidate the thermally induced material changes in the allyl- and styryl-GNPs. Thermally induced changes to the structure and behavior of the PCP GNPs were determined to be linked to the chemical structure of the grafted polycarbosilane chains. Styryl-GNPs experienced a curing event between 180 and 250 °C, effecting the formation of a network, which contributed to char yield improvement (at 800 °C). The nanoscale dynamics of this material also shows a transition from diffuse behavior to ballistic behavior because of the cross-linking event. Conversely, the allyl-GNPs did not exhibit a curing event under heat treatment but did show an increase in thermally induced physical cross-linking. The allyl-GNP physical network is stronger after the first cycle of thermal treatment, and it is considered that this contributed to the improvement in char yield post thermal treatment. The advancements in the understanding of the cross-linking behavior of these hybrid materials are expected to advance the application of these materials to turbine engine, advanced friction, and heat-shielding components.

36 MATERIALS SCIENCE↗

The production of advanced glass ceramic HLW forms using cold crucible induction melter

Cold Crucible Induction Melters (CCIM) will favorably change how High-Level radioactive Waste (from nuclear fuel recovery) is treated in a near future. Unlike the existing Joule-Heated Melters (JHM) currently in operation for the glass-based immobilization of High-Level Waste (HLW), CCIM offers unique material features that will increase melt temperatures, increase throughput, increase mixing, increase loading in the waste form, lower melter foot prints, eliminate melter corrosion and lower costs. These features not only enhance the technology for producing HLW forms, but also provide advantageous attributes to the waste form by allowing more durable alternatives to glass. It is concluded that glass ceramic waste forms that are tailored to immobilize fission products of HLW can be can be made from the HLW processed with the CCIM. The advantageous higher temperatures reached with the CCIM and unachievable with JHM allows the lanthanides, alkali, alkaline earths, and molybdenum to dissolve into a molten glass. Upon controlled cooling they go into targeted crystalline phases to form a glass ceramic waste form with higher waste loadings than achievable with borosilicate glass waste forms. Natural cooling proves to be too fast for the formation of all targeted crystalline phases.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Development of Agile and Cost Effective Routes for Manufacturing Reliable Ceramic Components for SOFC Systems

Additive manufacturing routes were explored and developed to enable the low to medium volume manufacturing of ceramic components with a short lead time, flexibility for iterative design, and without the high CAPEX and tooling costs associated with green machining or injection molding. Agile manufacturing route of gelcasting and 3D printing were selected and work focused on the production of ceramic manifold components utilized in the balance of plant for Saint-Gobain’s all ceramic SOFC stack. This work showed that both gelcasting and a specific version of 3D printing were able to create parts with the proper fidelity and at lower cost than traditional powder processing followed by green machining.

36 MATERIALS SCIENCE↗

A review of computational modeling techniques in study and design of shape memory ceramics

Shape memory ceramics are a unique family of shape memory materials with a wide variety of applications, such as ultra-high energy dissipation and high-temperature actuation. Along with significant progress in the experimental study of zirconia-based shape memory ceramics in recent years, computational simulations have exhibited powerful capabilities in revealing nano/microstructure-dependent deformation and failure mechanisms in these materials. In this work, we review the recent progress in understanding the phase transformation behavior in shape memory ceramics, focusing on computational modeling of zirconia-based ceramics. Electronic structure calculations have provided new data on the phase stability and surface properties of shape memory ceramics. At the nanometer length scale, molecular dynamics simulations have captured fundamental information about martensitic phase transformation and the effects of grain boundaries and defects on mechanical response of bi- and polycrystalline zirconia-based ceramics. At the micrometer length scale, advanced phase-field models have shown the ability to predict morphological evolution of microstructures and the corresponding mechanical responses in good agreement with experimental observations. Despite the recent multiscale computational advancements, further developments are required to establish processing-structure-property-performance relations that will lead to reliable and practical strategies for designing zirconia-based (or other) ceramics with improved and sustained shape memory responses. This article critically reviews current computational modeling techniques and provides an outlook for the study and design of the next generation of shape memory ceramics.

36 MATERIALS SCIENCE↗

Radiation Effects in Innovative Structural Materials

The extreme radiation environments and demanding structural conditions of next-generation fission and proposed fusion reactors will require high performance materials with very high radiation resistance. Although conventional structural materials such as ferritic/ martensitic steels offer several attractive features, there is value in exploring alternative materials systems that may offer unprecedented radiation stability while also offering good thermomechanical properties. As noted elsewhere, options for designing radiation resistance include (a) the traditional approach of introducing a very high sink strength for recombination of radiation-induced vacancies and interstitials (e.g., Ti-modified stainless steels or 'nano-cluster-strengthened ferritic alloys', (b) utilizing materials with immobile vacancies at the operating temperature (e.g., silicon carbide), and (c) utilizing certain classes of materials that inherently exhibit superior resistance to radiation defect retention and accumulation (e.g., ferritic steels). Three relatively new but promising structural materials systems were selected for investigation, based on their favorable unirradiated mechanical properties and potential for good stability under irradiation: High entropy alloys (HEAs), bulk metallic glass (BMG), and MAX phase ceramics. The high configurational entropy in HEAs might alter point defect (solute and radiation defects) diffusion processes, thus potentially enhancing the recombination of radiation-produced damage. Therefore, HEAs offer the potential of a new class of materials for radiation resistance category (c) mentioned previously. A variety of BMGs such as Zr{sub 52.5}Cu{sub 17.9}Ni{sub 14.6}Al{sub 10}Ti{sub 5} offer good mechanical properties including fracture toughness values that may exceed 100 MPa-m{sup 1/2} and near net shape fabrication potential. The lack of crystallinity in BMGs prohibits the formation of conventional Frenkel pair defects under irradiation and therefore offer the possibility of another new material system for radiation resistance category (c). MAX phase ceramics (e.g., Ti{sub 3}SiC{sub 2}, Ti{sub 3}AlC{sub 2}, Ti{sub 2}AlC) have good mechanical properties and contain a nano-laminate structure that could provide a very high point defect sink strength. Due to their refractory nature, many of the MAX phase ceramics may exhibit negligible vacancy mobility up to high temperatures. Therefore, MAX phase ceramics offer the potential to provide radiation resistance in either categories (a) and (b), depending on the operating temperature. For this study, a novel 27%Fe-27%Mn-28%Ni-18%Cr single phase face centered cubic high entropy alloy was synthesized that exhibited good strength and ductility over a wide temperature range. Zr{sub 52.5}Cu{sub 17.9}Ni{sub 14.6}Al{sub 10}Ti{sub 5} (BAM-11) was selected as a prototypic advanced BMG. Several MAX phase ceramics (e.g., Ti{sub 3}SiC{sub 2}, Ti{sub 3}AlC{sub 2}, Ti{sub 2}AlC) that have good unirradiated thermal and mechanical properties were also investigated. The irradiation damage behaviors of these three novel materials systems have been studied after fission neutron at ∼75 deg. C up to 1 dpa and Ni ion irradiation at 25- 700 deg. C up to 30 dpa (lower temperatures and doses for the BMGs). All three sets of materials generally exhibited good radiation stability within certain temperature regimes. For example, the BMG exhibited only minor (<10%) change in strength that appeared to saturate after a dose of ∼1 dpa. A key shortcoming of current BMGs are that they can not be used at temperatures >>300 deg. C due to glass to crystalline transition at elevated temperature. The MAX phase ceramics irradiated at 400-700 deg. C appeared to be in the 'low temperature' regime where vacancies are immobile and therefore the radiation hardening saturated at relatively low doses. The Ti{sub 3}SiC{sub 2} MAX phase exhibited the best overall radiation stability over a wide temperature range. The HEA exhibited fine scale dislocation loop formation, no observable cavity swelling and reduced amounts of Cr depletion compared to traditional austenitic Fe-Cr-Ni alloys after ion irradiation, which suggests suppressed point defect and solute diffusion behavior. (authors)

36 MATERIALS SCIENCE↗

Quantitative phase separation in multiferroic Bi{sub 0.88}Sm{sub 0.12}FeO{sub 3} ceramics via piezoresponse force microscopy

BiFeO{sub 3} (BFO) is a classical multiferroic material with both ferroelectric and magnetic ordering at room temperature. Doping of this material with rare-earth oxides was found to be an efficient way to enhance the otherwise low piezoelectric response of unmodified BFO ceramics. In this work, we studied two types of bulk Sm-modified BFO ceramics with compositions close to the morphotropic phase boundary (MPB) prepared by different solid-state processing methods. In both samples, coexistence of polar R3c and antipolar P{sub bam} phases was detected by conventional X-ray diffraction (XRD); the non-polar P{sub nma} or P{sub bnm} phase also has potential to be present due to the compositional proximity to the polar-to-non-polar phase boundary. Two approaches to separate the phases based on the piezoresponse force microscopy measurements have been proposed. The obtained fractions of the polar and non-polar/anti-polar phases were close to those determined by quantitative XRD analysis. The results thus reveal a useful method for quantitative determination of the phase composition in multi-phase ceramic systems, including the technologically most important MPB systems.

36 MATERIALS SCIENCE↗

An In Situ Formed, Dual-Phase Cathode with a Highly Active Catalyst Coating for Protonic Ceramic Fuel Cells

Composite cathodes of solid oxide fuel cells (SOFCs) are normally fabricated by mechanical mixing of electronic- and ionic-conducting phases. Here, a dual-phase SOFC cathode, composed of perovskite PrNi 0.5 Mn 0.5 O 3 (PNM) and exsoluted fluorite PrOx particles, produced in situ through a glycine–nitrate solution combustion process, is reported. When applied as the cathode for a BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3 -based protonic ceramic fuel cell, the hybrid cathode displays excellent electrocatalytic activity (area-specific resistance of 0.052 Ω cm 2 at 700 °C) and remarkable long-term stability when operated at a cell voltage of 0.7 V for ≈500 h using H 2 as fuel and ambient air as oxidant. The excellent performance is attributed to the proton-conducting BaPrO 3 -based coating and high-concentration oxygen vacancies of a Ba-doped PNM surface coating, produced by the reaction between the cathode and Ba from the electrolyte (via evaporation or diffusion), as confirmed by detailed X-ray photoelectron spectroscopy, Raman spectroscopy, and density functional theory-based calculations.

36 MATERIALS SCIENCE↗