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The chemical and structural stability of two commercial multicomponent silicate glasses (SCN and G6) in contact with yttria-stabilized zirconia (YSZ) was investigated after exposure times of up to 40,000 hours in air at 800 °C. With exposure time, interfacial layers develop at the SCN-YSZ and G6-YSZ interfaces, which were characterized in detail using both quantitative chemical analysis and atomic-resolution imaging. At the SCN-YSZ interface, a Ca-Ba-Si-O reaction phase was found to grow by diffusion control. In G6-YSZ, Raman spectroscopy and electron microscopy revealed a disorganized interfacial reaction later between G6 and YSZ, and the occurrence of cubic to tetragonal to monoclinic phase transformations in YSZ. This microstructural evolution is discussed in terms of devitrification resistance of glass and diffusion processes at interfaces.

A sustainable closed-loop manufacturing would become reality if commodity plastics can be upcycled into higher-performance materials with facile processability. Such circularity will be realized when the upcycled plastics can be (re)processed into custom-designed structures through energy/resource-efficient additive manufacturing methods, especially by approachable and scalable fused filament fabrication (FFF). Here, we introduce a circular model epitomized by upcycling a prominent thermoplastic, acrylonitrile butadiene styrene (ABS) into a recyclable, robust adaptive dynamic covalent network (ABS-vitrimer) (re)printable via FFF. The full FFF processing of ABS-vitrimer overcomes the major challenge of (re)printing cross-linked materials and produces stronger, tougher, solvent-resistant three-dimensional objects directly reprintable and separable from unsorted plastic waste. This study thus offers an imminently adoptable approach for advanced manufacturing toward the circular plastics economy.

A metal matrix composite powder of molybdenum (Mo) + TiC was produced by mechanical alloying (MA) and used in additive manufacturing by electron beam powder bed fusion along with pure Mo powder to form sandwich structures. The Mo + TiC solid layers formed mixed structures of Mo with discrete TiC particles, eutectic Mo + TiC, and Mo dendrites. Thermodynamic modeling showed that the system contained an invariant eutectic reaction in the composition range used and indicated that the system was highly sensitive to changes in composition and temperature.

Extrusion based big area additive manufacturing process is utilized for fabrication of dense anisotropic bonded magnets. High loading fraction (≥70 vol%) of magnequench anisotropic Nd–Fe–B powder in nylon is used for preparing anisotropic bonded magnets. A higher energy product of ~143.2 kJ/m3 is obtained for the post printed magnetic field aligned at 1 Tesla. These findings make an important step towards the fabrication of gap magnets with energy product between ferrite and Nd–Fe–B sintered magnets. Moreover, printed bonded magnets exhibited better thermal stability, mechanical properties and superior magnetic properties compared to commercial injection molded magnets.

The thermal expansion of a thermally sprayed coating material is an important design-relevant property from both processing and application service points of view. High thermal stresses and residual strains can arise during deposition, and thermal exposure in service. The linkage to process conditions which can impact both physical and chemical attributes of the microstructure and consequently its expansion behavior is of great importance. The observed dilation response of various coatings is discussed based on the processing effects that induce differences in microstructural features and the impact of residual strain and annealing of defects on the dilation behavior during first thermal exposure. The coefficient of thermal expansion (CTE) of coatings was found to approach the bulk when the material is not sensitive to oxidation in-flight. For those materials sensitive to oxidation, mathematical models used to describe effective properties of composite materials were adopted to describe the CTE property. A large irreversible dilation change was found in the first heating cycle due to defect annealing (referred to as thermal shakedown). Several reasons are hypothesized for the magnitude of such dilation change. Together, the paper presents a comprehensive analysis of thermal expansion behavior of a diversity of thermal spray processed materials.

Thermal insulation materials are crucial to improve the energy performance of buildings and industrial applications. We report an approach to create hermetically vacuum-sealed silica-based hollow microspheres that can lower the thermal conductivity of closed-cell insulation materials. The wall structure of these hollow microspheres includes a reticulated network of pores or channels that extend through the thickness of the wall. When a thin layer of glass material is applied to the wall exterior, followed by a vacuum-assisted thermal treatment process, the coated microsphere surfaces display a highly dense conformal coverage and near-complete elimination of surface porosity. The sealing efficiency of these microspheres is verified by trapping argon within their cavities as well as through evacuating their hollow cores. Notably, incorporating the evacuated microspheres into a polymer matrix resulted in ∼27% enhancement in its thermal insulation performance and no notable loss of performance was observed following three months of exposure to ambient conditions. Thus, we believe that the present study offers a commercially viable strategy that opens the door to applications of such inorganic hollow particles in areas ranging from vacuum-based thermal insulation systems to catalysis, separation technologies, and medical fields.

We report on the influence of sintering gas atmosphere on the thermoelectric (TE) performance of Ca3Co4O9 + δ ceramics made from precursor powders synthesized using chemical sol–gel route. Two sets of polycrystalline pellets were sintered in air and oxygen atmosphere, respectively. Sintering gas atmosphere and sintering temperature were found to have great influence on the Ca3Co4O9 + δ crystal orientation and formation of the Co3O4 secondary phase. All samples, regardless of sintering atmosphere, had similar Seebeck coefficients S that increased with measurement temperature. By contrast, the electrical resistivity ρ changed dramatically as the sintering temperature and atmosphere changed. For samples sintered in air, when the sintering temperature is above 1193 K, ρ increased as the sintering temperature increased. For samples sintering in oxygen, ρ decreased monotonically as the sintering temperature increased up to 1253 K. Benefited from the reduced ρ, the electrical power factor of the sample sintered in the oxygen at 1253 K is 0.539 mW m−1 K−2, and 40% greater than that from the sample sintered at 1193 K in air. Dimensionless figure-of-merit ZT of the sample sintered at 1253 K in oxygen is 0.28 at 1073 K, which is 20% greater than that of samples sintered in air at 1193 K. Overall, the highest TE performance was obtained for Ca3Co4O9 + δceramics sintered in oxygen at 1253 K, which is significantly higher than the Ca3Co4O9 + δ decomposition temperature of 1199 K in air.

Brittleness is a key barrier for poly(lactic acid) (PLA) toward broader applications. Supertough PLA was achieved by simply mixing a low amount (0.5–1 wt %) of organoalkoxysilane with PLA. Three organosilanes, (3-aminopropyl)triethoxysilane (APTES), 3-(triethoxysilyl)propyl isocyanate (ICPTES), and trimethoxymethylsilane (MTMS), were selected for this study to understand how the functional group on a silane affects the behavior of the PLA-silane hybrids. Remarkable improvements in ultimate tensile strain (up to 12 folds) and tensile toughness (up to 10 folds) were observed in APTES- and ICPTES-modified PLA without any loss in tensile strength and modulus. Glass transition temperatures measured by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) did not show any obvious decrease. We propose that in situ condensation of organosilane and grafting of PLA to form a silica-PLA core–shell nanocomplex may be the reason for the improved mechanical properties. Scanning electron microsco...

The present work demonstrates the feasibility of increasing the values of Seebeck coefficient S and power factor of calcium cobaltite Ca3Co4O9 ceramics through competing dopant grain boundary segregation. The nominal chemistry of the polycrystalline material system investigated is Ca3−xBixBayCo4O9 with simultaneous stoichiometric substitution of Bi for Ca and non-stoichiometric addition of minute amounts of Ba. There is continuous increase of S due to Bi substitution and Ba addition. The electrical resistivity also changes upon doping. Overall, the power factor of best performing Bi and Ba co-doped sample is about 0.93 mW m−1 K−2, which is one of the highest power factor values ever reported for Ca3Co4O9, and corresponds to a factor of 3 increase compared to that of the baseline composition Ca3Co4O9. Systematic nanostructure and chemistry characterization was performed on the samples with different nominal compositions. When Bi is the only dopant in Ca3Co4O9, it can be found at both the grain interior and the grain boundaries GBs as a result of segregation. When Bi and Ba are added simultaneously as dopants, competing processes lead to the segregation of Ba and depletion of Bi at the GBs, with Bi present only in the grain interior. Bi substitution in the lattice increases the S at both the low and high temperature regimes, while the segregation of Ba at the GBs dramatically increase the S at low temperature regime.

Internal short circuit of large-format Li-ion pouch cells induced by mechanical abuse was simulated using a modified mechanical pinch test. A torsion force was added manually at ∼40% maximum compressive loading force during the pinch test. The cell was twisted about 5° to the side by horizontally pulling a wire attached to the anode tab. The combined torsion-compression force created small failure at the separator yet allowed testing of fully charged large format Li-ion cells without triggering thermal runaway. Two types of commercial cells were tested using 4–6 cells at each state-of-charge (SOC). Commercially available 18 Ahr LiFePO4 (LFP) and 25 Ahr Li(NiMnCo)1/3O2 (NMC) cells were tested, and a thermal runaway risk (TRR) score system was used to evaluate the safety of the cells under the same testing conditions. The aim was to provide the cell manufacturers and end users with a tool to compare different designs and safety features.

High-temperature alloy design requires a concurrent consideration of multiple mechanisms at different length scales. We propose a workflow that couples highly relevant physics into machine learning (ML) to predict properties of complex high-temperature alloys with an example of the 9–12 wt% Cr steels yield strength. We have incorporated synthetic alloy features that capture microstructure and phase transformations into the dataset. Identified high impact features that affect yield strength of 9Cr from correlation analysis agree well with the generally accepted strengthening mechanism. As a part of the verification process, the consistency of sub-datasets has been extensively evaluated with respect to temperature and then refined for the boundary conditions of trained ML models. The predicted yield strength of 9Cr steels using the ML models is in excellent agreement with experiments. The current approach introduces physically meaningful constraints in interrogating the trained ML models to predict properties of hypothetical alloys when applied to data-driven materials.

We have previously reported (Boatner et al., J. Alloys Compd. 691 (2017) 666–671) on the discovery, formation, processing, and application of a new decorative ternary steel. alloy and on its use in a wide range of practical applications including: custom and commercial knives, art objects, jewelry, electronics, and furniture. This decorative property results when polished single crystals of the 70 wt%Fe-15 wt%Ni-15 wt% Cr austenitic alloy are cryo-quenched into the martensitic phase resulting in the formation of a three-dimensional raised pattern of mixed austenitic/martensitic laths. These laths propagate across large dimensions of the material due to the absence of grain boundaries in the single crystal. The macroscopic optically reflective 3-D decorative pattern reproduces the structural symmetry inherent in the single-crystal orientation. This pattern results solely from the metallurgical phase properties of the ternary alloy and is completely distinct from the properties of Damascus steels or more modern so-called pattern-welded steels. Here we use X-ray diffraction, nanoindentation, hardness measurements/scratch testing, tribological measurements, and alloy resistivity and magnetization methods to obtain a more fundamental and comprehensive study of the effects of the austenitic/martensitic phase transition on the structural and physical properties of the 70 wt%Fe-15 wt%Ni-15 wt% Cr alloy. These results reveal new insight into irreversible phenomena that are associated with the inhibited phase transition on heating of the two-phase, mixed austenitic/martensitic structure that is formed subsequent to cryo-quenching the alloy crystal to 77 K.

In this paper, we study the elastic properties of the entropy-stabilized oxide (Mg, Co, Ni, Cu, Zn)O using experimental and first principles techniques. Our measurements of the indentation modulus on grains with a wide range of crystallographic orientations of the entropy-stabilized oxide revealed a high degree of elastic isotropy at ambient conditions. First principles calculations predict mild elastic anisotropy for the paramagnetic structure, which decreases when the system is considered to be non-magnetic. When the antiferromagnetic state of CoO, CuO, and NiO is accounted for in the calculations, a slight increase in elastic anisotropy is observed, suggesting a coupling between magnetic ordering and the orientation dependent elastic properties. Furthermore, an examination of the local structure reveals that the isotropy is favored through local ionic distortions of Cu and Zn—due to their tendencies to form tenorite and wurtzite phases. The relationships between the elastic properties of the multicomponent oxide and those of its constituent binary oxides are reviewed. These insights open up new avenues for controlling isotropy for technological applications through tuning composition and structure in the entropy-stabilized oxide or the high-entropy compounds in general.

Thermal energy storage (TES) is a broad-based technology for reducing CO2 emissions and advancing concentrating solar, fossil, and nuclear power through improvements in efficiency and economics. Phase change materials (PCMs) are of interest as TES media because of their ability to store large amounts of heat in relatively small volumes. The volume expansion during a phase change, typically between a solid and liquid, can cause breakage of protective coatings. This effort reports on the fabrication of a ceramic encapsulated metal (CEM) high temperature TES technology using a rotary calcining furnace and a fluidized bed chemical vapor deposition coating technique. Aluminum beads were chosen as the PCM because Al has a high melting point (660 °C), low cost, high heat of fusion, and an ability to form a thin, strong alumina layer capable of supporting the Al melt for subsequent processing. Quite remarkably, this study shows that 1 mm diameter Al can be fluidized up to at least 1500 °C in an appropriate atmosphere while maintaining a spheroid geometry. This allowed for producing a first of a kind CEM whereby Al particles were encapsulated in pyro-carbon (PyC) and high purity, dense chemical vapor deposited SiC. The CEM with a PyC only coating was exposed to thermal cycling to test the performance with a differential scanning calorimeter; the melting point and latent heat were measured to be 648.4 ± 2.8 °C and 293.3 ± 6.2 J/g respectively. It was demonstrated that the CEM design is possible to produce, laying the foundation for manufacturing of high temperature, tunable, TES media.

The efficiency of generating electricity from heat using concentrated solar power plants (which use mirrors or lenses to concentrate sunlight in order to drive heat engines, usually involving turbines) may be appreciably increased by operating with higher turbine inlet temperatures, but this would require improved heat exchanger materials. By operating turbines with inlet temperatures above 1,023 kelvin using closed-cycle high-pressure supercritical carbon dioxide (sCO2) recompression cycles, instead of using conventional (such as subcritical steam Rankine) cycles with inlet temperatures below 823 kelvin1–3, the relative heat-to-electricity conversion efficiency may be increased by more than 20 per cent. The resulting reduction in the cost of dispatchable electricity from concentrated solar power plants (coupled with thermal energy storage4–6) would be an important step towards direct competition with fossil-fuel-based plants and a large reduction in greenhouse gas emissions7. However, the inlet temperatures of closed-cycle high-pressure sCO2 turbine systems are limited8 by the thermomechanical performance of the compact, metal-alloy-based, printed-circuit-type heat exchangers used to transfer heat to sCO2. Here we present a robust composite of ceramic (zirconium carbide, ZrC) and the refractory metal tungsten (W) for use in printed-circuit-type heat exchangers at temperatures above 1,023 kelvin9. This composite has attractive high-temperature thermal, mechanical and chemical properties and can be processed in a cost-effective manner. We fabricated ZrC/W-based heat exchanger plates with tunable channel patterns by the shape-and-size-preserving chemical conversion of porous tungsten carbide plates. The dense ZrC/W-based composites exhibited failure strengths of over 350 megapascals at 1,073 kelvin, and thermal conductivity values two to three times greater than those of iron- or nickel-based alloys at this temperature. Corrosion resistance to sCO2 at 1,023 kelvin and 20 megapascals was achieved10 by bonding a copper layer to the composite surface and adding 50 parts per million carbon monoxide to sCO2. Techno-economic analyses indicate that ZrC/W-based heat exchangers can strongly outperform nickel-superalloy-based printed-circuit heat exchangers at lower cost. A robust ceramic/refractory metal (ZrC/W)-based composite for use in heat exchangers in concentrated solar power plants above 1,023 kelvin is described, having attractive high-temperature thermal, mechanical and chemical properties combined with cost-effective processing.

Phase change materials are identified for their ability to rapidly alternate between amorphous and crystalline phases and have large contrast in the optical/electrical properties of the respective phases. The materials are primarily used in memory storage applications, but recently they have also been identified as potential thermoelectric materials. Many of the phase change materials researched today can be found on the pseudo-binary (GeTe)1-x(Sb2Te3)x tie-line. While many compounds on this tie-line have been recognized as thermoelectric materials, here we focus on Ge4SbTe5, a single phase compound just off of the (GeTe)1-x(Sb2Te3)x tie-line, that forms in a stable rocksalt crystal structure at room temperature. We find that stoichiometric and undoped Ge4SbTe5 exhibits a thermal conductivity of ~1.2 W/m-K at high temperature and a large Seebeck coefficient of ~250 μV/K. The resistivity decreases dramatically at 623 K due to a structural phase transition which lends to a large enhancement in both thermoelectric power factor and thermoelectric figure of merit at 823 K. In a more general sense the research presents evidence that phase change materials can potentially provide a new route to highly efficient thermoelectric materials for power generation at high temperature.

In situ scanning electron microscope (SEM) experiments, where small-scale mechanical tests are conducted on micro- and nanosized specimens, allow direct visualization of elastic and plastic responses over the entirety of the volume being deformed. This enables precise spatial and temporal correlation of slip events contributing to the plastic flow evidenced in a stress–strain curve. A new pin-loading methodology has been employed, in situ within the SEM, to conduct microtensile tests on thin polycrystalline metal foils. This approach can be tailored to a specific foil whose particular grain size may range from microns to tens of microns. Manufacture of the specialized pin grip was accomplished via silicon photolithography-based processing followed by subsequent focused ion beam finishing. Microtensile specimen preparation was achieved by combining a stencil mask methodology employing broad ion beam sputtering along with focused ion beam milling in the study of several metallic foil materials. Finite-element analyses were performed to characterize the stress and strain distributions in the pin grip and micro-specimen under load. Under appropriately conceived test conditions, uniaxial stress–strain responses measured within these foils by pin-load microtensile testing exhibit properties consistent with larger scale tests.

A revolutionary impact on the performance of many optical systems and components can come from the integrative design of multifunctional coatings. Such coatings should be mechanically robust, and combine user-defined optical and wetting functions with scalable fabrication formulations. By taking cues from the properties of some natural biological structures, we report here the formation of low-refractive index antireflective glass films that embody omni-directional optical properties over a wide range of wavelengths, while also possessing specific wetting capabilities. The coatings comprise an interconnected network of nanoscale pores surrounded by a nanostructured silica framework. These structures result from a novel fabrication method that utilizes metastable spinodal phase separation in glass-based materials. The approach not only enables design of surface microstructures with graded-index antireflection characteristics, where the surface reflection is suppressed through optical impedance matching between interfaces, but also facilitates self-cleaning ability through modification of the surface chemistry. Based on near complete elimination of Fresnel reflections (yielding >95% transmission through a single-side coated glass) and corresponding increase in broadband transmission, the fabricated nanostructured surfaces are found to promote a general and an invaluable ∼3–7% relative increase in current output of multiple direct/indirect bandgap photovoltaic cells. Moreover, these antireflective surfaces also demonstrate superior resistance against mechanical wear and abrasion. Unlike conventional counterparts, the present antireflective coatings are essentially monolithic, enabling simultaneous realization of graded index anti-reflectivity, self-cleaning capability, and mechanical stability within the same surface. The concept represents a fundamental basis for development of advanced coated optical quality products, especially where environmental exposure is required.

Under the sponsorship of the U.S. National Science Foundation, a workshop on emerging research opportunities in ceramic and glass science was held in September 2016. Reported here are proceedings of the workshop. The report details eight challenges identified through workshop discussions: Ceramic processing: Programmable design and assembly; The defect genome: Understanding, characterizing, and predicting defects across time and length scales; Functionalizing defects for unprecedented properties; Ceramic flatlands: Defining structure-property relations in free-standing, supported, and confined two-dimensional ceramics; Ceramics in the extreme: Discovery and design strategies; Ceramics in the extreme: Behavior of multimaterial systems; Understanding and exploiting glasses and melts under extreme conditions; and Rational design of functional glasses guided by predictive modeling. It is anticipated that these challenges, once met, will promote basic understanding and ultimately enable advancements within multiple sectors, including energy, environment, manufacturing, security, and health care., National Science Foundation (U.S.) (Award DMR-1619666)

Carbide/refractory metal cermets possess attractive combinations of thermal and mechanical properties for ultra-high temperature structural applications. Using a high-throughput computational thermodynamic approach, 16 carbide/refractory metal cermet systems were identified, out of 1808 possible combinations, that could be fabricated by the displacive compensation of porosity (DCP) method using molten copper alloys as infiltrators at 1300 °C. Experimental results for ZrC/W and ZrC/Mo, and other proposed systems in the literature provide a level of validation to this approach. We found that copper alloys are more suitable for DCP than aluminum alloys owing to the low melting temperature of copper alloys (e.g., Zr 2 Cu and Ti 2 Cu), and the minimal chemical reaction as well as very limited mutual solid solubility of copper with refractory metals. Our results show that high-throughput thermodynamics calculation is a robust approach for systematically and thoroughly identifying refractory metal cermets that are suitable for DCP.

A substantial amount of testing and analysis was performed over the 13-year-duration of this Cooperative Research and Development Agreement (CRADA) between Cummins Inc. and the Oak Ridge National Laboratory (ORNL). ORNL's work focused on developing fundamental understanding of the mechanical and physical properties and their relationship to the microstructure of Diesel Particulate Filter (DPF) materials (i.e., cordierite, aluminum titanate, Si-SiC). These materials exhibit significant strain tolerance owing to their highly porous and mircocracked microstructures. That is, while very weak, the porous and compliant microstructure could withstand large strains without failing catastrophically. Substantial knowledge was also gained with respect to preparation of test specimens for evaluation of mechanical properties and the care required. Once the role of the microstructure of the wall material on its mechanical response was understood, the DPF honeycombs themselves were re-examined, and the influence of the honeycomb structure was considered. Cummins s work focused mainly on the apparent strength of the DPF honeycomb structure and using the material properties generated at ORNL for input to their regeneration and performance-predictive models.

Additive manufacturing allows for the production of complex parts with minimum material waste, offering an effective technique for fabricating permanent magnets which frequently involve critical rare earth elements. In this report, we demonstrate a novel method - Big Area Additive Manufacturing (BAAM) - to fabricate isotropic near-net-shape NdFeB bonded magnets with magnetic and mechanical properties comparable or better than those of traditional injection molded magnets. The starting polymer magnet composite pellets consist of 65 vol% isotropic NdFeB powder and 35 vol% polyamide (Nylon-12). The density of the final BAAM magnet product reached 4.8 g/cm3, and the room temperature magnetic properties are: intrinsic coercivity Hci = 688.4 kA/m, remanence Br = 0.51 T, and energy product (BH)max = 43.49 kJ/m3 (5.47 MGOe). In addition, tensile tests performed on four dog-bone shaped specimens yielded an average ultimate tensile strength of 6.60 MPa and an average failure strain of 4.18%. Scanning electron microscopy images of the fracture surfaces indicate that the failure is primarily related to the debonding of the magnetic particles from the polymer binder. The present method significantly simplifies manufacturing of near-net-shape bonded magnets, enables efficient use of rare earth elements thus contributing towards enriching the supply of critical materials.

Many applications, particularly wind turbines and electric motors for tomorrow's vehicles, require the strongest permanent magnets, which contain rare-earth metals. Issues with rare-earth supply and production have led to a quest for powerful magnets without these metals. Exploiting the physics of a solid-solid phase transition under tensile stress, the authors obtain a magnetically hard and anisotropic material made only of abundant, cheap iron and nitrogen. In doing so, they directly observe the coupling between tensile strain and the martensitic transition.

ORNL collaborated with Faurecia Interior Systems to investigate the feasibility of developing a thermomagnetic preventive maintenance program for nickel tooling used in powder slush molding. It was found that thermal treatments at temperatures greater than 500°C can anneal strain hardening in nickel tooling and a range of temperatures and times for effective thermal annealing were identified. It was also observed that magnetic fields applied during thermal annealing do not alter the kinetics of strain hardening annealing. The results obtained in this investigation provide a foundation for establishing a preventive maintenance program for nickel tooling.

In this study, a structural phase transition has been discovered in the synthetic tetrahedrite Cu12Sb4S13 at approximately 88 K. Upon cooling, the material transforms from its known cubic symmetry to a tetragonal unit cell that is characterized by an in-plane ordering that leads to a doubling of the unit cell volume. Specific heat capacity measurements demonstrate a hysteresis of more than two degrees in the associated anomaly. A similar hysteresis was observed in powder x-ray diffraction measurements, which also indicate a coexistence of the two phases, and together these results suggest a first-order transition. This structural transition coincides with a recently-reported metal-insulator transition, and the structural instability is related to the very low thermal conductivity κ in these materials. Inelastic neutron scattering was used to measure the phonon density of states in Cu12Sb4S13 and Cu10Zn2Sb4S13, both of which possess a localized, low-energy phonon mode associated with strongly anharmonic copper displacements that suppress κ. In Cu12Sb4S13, signatures of the phase transition are observed in the temperature dependence of the localized mode, which disappears at the structural transition. In contrast, in the cubic Zn-doped material, the mode is at slightly higher-energy but observable for all temperatures, though it softens upon cooling.

The internal friction and creep deformation behavior of La0.8Ca0.2CoO3 and pure LaCoO3 mixed ionic electronic conducting perovskite ceramics have been studied by Dynamic Mechanical Analysis and uniaxial compression under constant applied load, respectively. It was found that both the internal friction and creep strain were almost an order of magnitude higher for Ca2+ doped LaCoO3 as compared to pure undoped LaCoO3. The difference in Ca2+ doped LaCoO3 behavior was attributed to the much higher concentration of point defects (e.g., oxygen vacancies) in the structure and their interaction with other mobile defects, such as ferroelastic domain/twin walls, stacking faults, dislocations, etc. Such interactions of numerous point defects with domain walls produce energetic barriers and slow down the movement of ferroelastic domain walls under applied stress. At the same time, the defects' interactions increase the internal friction resulting in a much higher creep strain of La0.8Ca0.2CoO3 as compared to pure LaCoO3, as the creep strain is determined by the distance between the domain wall and its equilibrium position at the onset of the creep process. Therefore, the high friction will result in the larger distance the wall has to move to reach the equilibrium which in turn results in higher creep strain. The expansion of LaCoO3 under constant applied compressive stress, named here as negative creep, was also discovered to occur during room temperature creep experiments.The internal friction and creep deformation behavior of La0.8Ca0.2CoO3 and pure LaCoO3 mixed ionic electronic conducting perovskite ceramics have been studied by Dynamic Mechanical Analysis and uniaxial compression under constant applied load, respectively. It was found that both the internal friction and creep strain were almost an order of magnitude higher for Ca2+ doped LaCoO3 as compared to pure undoped LaCoO3. The difference in Ca2+ doped LaCoO3 behavior was attributed to the much higher concentration of point defects (e.g., oxygen vacancies) in the structure and their interaction with other mobile defects, such as ferroelastic domain/twin walls, stacking faults, dislocations, etc. Such interactions of numerous point defects with domain walls produce energetic barriers and slow down the movement of ferroelastic domain walls under applied stress. At the same time, the defects' interactions increase the internal friction resulting in a much higher creep strain of La0.8Ca0.2CoO3 as compared to pure LaCo...

The applicability of probabilistic analyses to assess the structural reliability of materials and components for solid-oxide fuel cells (SOFC) is investigated by measuring the failure rate of Ni-YSZ when subjected to a temperature gradient and comparing it with that predicted using the Ceramics Analysis and Reliability Evaluation of Structures (CARES) code. The use of a temperature gradient to induce stresses was chosen because temperature gradients resulting from gas flow patterns generate stresses during SOFC operation that are the likely to control the structural reliability of cell components The magnitude of the predicted failure rate was found to be comparable to that determined experimentally, which suggests that such probabilistic analyses are appropriate for predicting the structural reliability of materials and components for SOFCs. Considerations for performing more comprehensive studies are discussed.

a b s t r a c t One of the main factors responsible for the mechanical and physical properties of nanocomposites is the effectiveness of the interfacial region to transfer loads and mechanical vibrations between the nano- reinforcements and the matrix. Surface functionalization has been the preferred approach to engineer the interfaces in polymer nanocomposites in order to maximize their potential in structural and functional applications. In this study, amine-functionalized cellulose nanofibrils (mCNF-G1) were synthesized via silylation of the hydroxyl groups on the CNF surface using 3-aminopropyltrimethoxysilane (APTMS). To further increase the amine density (mCNF-G2), dendritic polyamidoamine (PAMAM) was grafted onto mCNF-G1 by the Michael addition of methacrylate onto mCNF-G1, followed by the transamidation of the ester groups of methacrylate using ethylenediamine. Compared to native CNF-reinforced, poly(l- lactide) (PLLA) nanocomposites, amine-functionalized CNF exhibited significantly improved dispersion and interfacial properties within the PLLA matrix due to the grafting of PLLA chains via aminolysis. It is also a more effective nucleating agent, with 15% mCNF-G1 leading to a crystallinity of 32.5%, compared to 0.1 and 8.7% for neat PLLA and native CNF-reinforced composites. We have demonstrated that APTMS- functionalized CNF (mCNF-G1) significantly improved the tensile strength compared to native CNF, with 10% mCNF-G1 being the most effective (i.e., >100% increase in tensile strength). However, we also found that excessive amines on the CNF surface (i.e., mCNF-G2) resulted in decreased tensile strength and modulus due to PLLA degradation via aminolysis. These results demonstrate the potential of optimized amine-functionalized CNF for future renewable material applications.