A eutectoid phase transformation was exhibited by the perovskite CeCrO when heated in air. The kinetics of the reaction, microstructure of the product, and mechanisms of the transformation were studied using thermogravimetric analysis, X-ray and Raman spectroscopy, X-ray diffraction, and electron microscopy. Fluorite CeO and corundum CrO were formed from the decomposition of CeCrO. The CeO particles were porous and polycrystalline, a consequence of nucleation, growth, and impingent of CeO domains on the CeCrO particles. Anisotropic growth is indicated by the morphology of the CeO grains, while the CrO particles were single crystals without any crystallographic orientation relationship to the parent phase. Unlike the CeAlO eutectoid, the microstructure comprised of CeO and CrO show no characteristics of a microstructure formed by cooperative growth. The disparity between the eutectoid reactions in CeCrO and CeAlO is attributed to a difference in interfacial energy between the fluorite and sesquioxide phases (i.e., CeO/AlO versus CeO/CrO).

Since antiquity, the medicinal properties of naturally sourced biomolecules such as ginger (Zingiber officinale) extract are documented in the traditional Indian and Chinese medical systems. However, limited work is performed to assess the potential of ginger extracts for bone-tissue engineering. Our work demonstrates the direct incorporation of ginger extract on iron oxide-magnesium oxide (FeO and MgO) co-doped hydroxyapatite (HA) for enhancement in the biological properties. The addition of FeO and MgO co-doping system and ginger extract with HA increases the osteoblast viability up to ~ 1.4 times at day 11. The presence of ginger extract leads to up to ~ 9 times MG-63 cell viability reduction. The co-doping does not adversely affect the release of ginger extract from the graft surface in the biological medium at pH 7.4 for up to 28 days. Assessment of antibacterial efficacy according to the modified ISO 22196: 2011 standard method indicates that the combined effects of FeO, MgO, and ginger extract lead to ~ 82 % more bacterial cell reduction, compared to the control HA against . These ginger extract-loaded artificial bone grafts with enhanced biological properties may be utilized as a localized site-specific delivery vehicle for various bone tissue engineering applications.

Oxidation of perovskite CeAlO results in the eutectoid transformation to CeO and AlO. This phase transformation was recorded using thermal gravimetric analysis, X-ray diffraction, and scanning transmission electron microscopy. Lamellar features in the resultant microstructure indicates cooperative growth. Processing conditions dictate the lamellae sizes, which can be as small as a few nanometers, and coarsen into large domains with additional high temperature annealing.

In the present study, single crystals and polycrystalline material of KCaSiO were prepared from solid-state reactions between stoichiometric mixtures of the corresponding oxides/carbonates. Heat capacity ( ) measurements above room temperature using a differential scanning calorimeter indicated that two thermal effects occurred at approximately  = 462 K and  = 667 K, indicating the presence of structural phase transitions. The standard third-law entropy of KCaSiO was determined from low-temperature 's measured by relaxation calorimetry using a Physical Properties Measurement System and amounts to °(298K) = 524.3 ± 3.7 J·mol·K. For the 1 transition, the enthalpy change Δ  = 1.48 kJ·mol and the entropy change Δ  = 3.25 J·mol·K, whereas Δ  = 3.33 kJ·mol and Δ  = 5.23 J·mol·K were determined for the 2 transition. The compound was further characterized by in-situ single-crystal X-ray diffraction between ambient temperature and 1063 K. At 773 K, the high-temperature phase stable above has the following basic crystallographic data: monoclinic symmetry, space group 2/,  = 6.9469(4) Å,  = 9.2340(5) Å,  = 12.2954(6) Å, β = 93.639(3)°,  = 787.13(7) Å,  = 2. It belongs to the group of interrupted framework silicates and is based on tertiary (Q-type) [SiO]-tetrahedra. Together with the octahedrally coordinated Ca-cations, a three-dimensional mixed polyhedral network structure is formed, in which the remaining K-ions provide charge balance by occupying voids within the net. The intermediate temperature modification stable between and shows a (3+2)-dimensional incommensurately modulated structure that is characterized by the following q-vectors: q = (0.057, 0.172, 0.379), q = (-0.057, 0.172, -0.379). The crystal structures of the high- and the previously studied ambient temperature polymorph (space group ) are topologically equivalent and show a group-subgroup relationship. The index of the low- in the high-symmetry group is six and involves both, losses in translation as well as point group symmetry. The distortion is based on shifts of the different atom species and tilts of the 4- and 6-fold coordination polyhedra. Actually, for some of the oxygen atoms, the displacements exceed 0.5 Å. A more detailed analysis of the distortions relating to both structures has been performed using mode analysis, which revealed that the primary distortion mode transforms according to the Λ irreducible representation of 2/. However, other modes with smaller distortion amplitudes are also involved.

Adlayers on C-plane (0001) and R-plane terminated surfaces of corundum phase aluminum oxide were synthesized by annealing mixtures of two oxide powders, aluminum oxide with an additive. Using high-angle annular dark field scanning transmission electron microscopy, the adsorbed layers were characterized, and image simulations aided interpretation of the results. The adlayers were pseudomorphic, one atomic layer thick and with a fractional site occupancy. Atomic positions of the adlayer atoms relaxed and changed relative to the bulk structure, where there is evidence that the magnitude of the relaxation is sensitive to the ionic radius of the adsorbate. The pseudomorphic adlayer structure formed for different elements including, but not limited to, the lanthanides (i.e., Ge, Ba and Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm).

Ion exsolution can be instrumental to engineer intergranular regions inside ceramic microstructures. BaO admixtures that were trapped inside nanometer-sized MgO grains during gas phase synthesis undergo annealing-induced exsolution to generate photoluminescent surface and interface structures. During their segregation from the bulk into the grain interfaces, the BaO admixtures impact grain coarsening and powder densification, effects that were compared for the first time using an integrated characterization approach. For the characterization of the different stages the materials adopt between powder synthesis and compact annealing, spectroscopy measurements (UV-Vis diffuse reflectance, cathodo- and photoluminescence [PL]) were complemented by an in-depth structure characterization (density measurements, X-ray diffraction [XRD], and electron microscopy). Depending on the Ba concentration, isolated impurity ions either become part of low-coordinated surface structures of the MgO grains where they give rise to a characteristic bright PL emission profile around  = 500 nm, or they aggregate to form nanocrystalline BaO segregates at the inner pore surfaces to produce an emission feature centered at  = 460 nm. Both types of PL emission sites exhibit O gas adsorption-dependent PL emission properties that are reversible with respect to its pressure. The here-reported distribution of BaO segregates between the intergranular region and the free pore surfaces inside the MgO-based compacts underlines that solid-based exsolution strategies are well suited to stabilize nanometer-sized segregates of metal oxides that otherwise would coalesce and grow in size beyond the nanoscale.

One-pot synthesized twin perovskite oxide composite of BaCeFeO (BCF), comprising cubic and orthorhombic perovskite phases, shows triple-conducting properties for promising solid oxide electrochemical cells. Phase composition evolution of BCF under various conditions was systematically investigated, revealing that the cubic perovskite phase could be fully/partially reduced into the orthorhombic phase under certain conditions. The reduction happened between the two phases at the interface, leading to the microstructure change. As a result, the corresponding apparent conducting properties also changed due to the difference between predominant conduction properties for each phase. Based on the revealed phase composition, microstructure, and electrochemical properties changes, a deep understanding of BCF's application in different conditions (oxidizing atmospheres, reducing/oxidizing gradients, cathodic conditions, and anodic conditions) was achieved. Triple-conducting property (H/O/e), fast open-circuit voltage response (∼16-∼470 mV) for gradients change, and improved single-cell performance (∼31% lower polarization resistance at 600°C) were comprehensively demonstrated. Besides, the performance was analyzed under anodic conditions, which showed that the microstructure and phase change significantly affected the anodic behavior.

The Hadamard-Rybczynski equation describes the steady-state buoyant rise velocity of an unconfined spherical bubble in a viscous liquid. This solution has been experimentally validated for the case where the liquid viscosity is held constant. Here, we extend this result for non-isothermal conditions, by developing a solution for bubble position in which we account for the time-dependent liquid viscosity, liquid and gas densities, and bubble radius. We validate this solution using experiments in which spherical bubbles are created in a molten silicate liquid by cutting gas cavities into glass sheets, which are stacked, then heated through the glass transition interval. The bubble-bearing liquid, which has a strongly temperature-dependent viscosity, is subjected to various heating and cooling programs such that the bubble rise velocity varies through the experiment. We find that our predictions match the final observed position of the bubble measured in blocks of cooled glass to within the experimental uncertainty, even after the application of a complex temperature-time pathway. We explore applications of this solution for industrial, artistic, and natural volcanological applied problems.

This work demonstrates how to enhance contact damage resistance of alumina-based ceramics combining tailored microstructures in a multilayer architecture. The multilayer system designed with textured alumina layers under compressive residual stresses embedded between alumina-zirconia layers was investigated under Hertzian contact loading and compared to the corresponding monolithic reference materials. Critical forces for crack initiation under spherical contact were detected through an acoustic emission system. Damage was assessed by combining cross-section polishing and ion-slicing techniques. It was found that a textured microstructure can accommodate the damage below the surface by shear-driven, quasi-plastic deformation instead of the classical Hertzian cone cracking observed in equiaxed alumina. In the multilayer system, a combination of both mechanisms, namely Hertzian cone cracking on the top (equiaxed) surface layer and quasi-plastic deformation within the embedded textured layer, was identified. Further propagation of cone cracks at higher loads was hindered and/or deflected owed to the combined action of the textured microstructure and compressive residual stresses. These findings demonstrate the potential of embedding textured layers as a strategy to enhance the contact damage tolerance in alumina ceramics.

We propose a novel image analysis framework to automate analysis of X-ray microtomography images of sintering ceramics and glasses, using open-source toolkits and machine learning. Additive manufacturing (AM) of glasses and ceramics usually requires sintering of green bodies. Sintering causes shrinkage, which presents a challenge for controlling the metrology of the final architecture. Therefore, being able to monitor sintering in 3D over time (termed 4D) is important when developing new porous ceramics or glasses. Synchrotron X-ray tomographic imaging allows in situ, real-time capture of the sintering process at both micro and macro scales using a furnace rig, facilitating 4D quantitative analysis of the process. The proposed image analysis framework is capable of tracking and quantifying the densification of glass or ceramic particles within multiple volumes of interest (VOIs) along with structural changes over time using 4D image data. The framework is demonstrated by 4D quantitative analysis of bioactive glass ICIE16 within a 3D-printed scaffold. Here, densification of glass particles within 3 VOIs were tracked and quantified along with diameter change of struts and interstrut pore size over the 3D image series, delivering new insights on the sintering mechanism of ICIE16 bioactive glass particles in both micro and macro scales.

Hard and brittle solids with covalent/ionic bonding are used in a wide range of modern-day manufacturing technologies. Optimization of a shaping process can shorten manufacturing time and cost of component production, and at the same time extend component longevity. The same process may contribute to wear and fatigue degradation in service. Educated development of advanced finishing protocols for this class of solids requires a comprehensive understanding of damage mechanisms at small-scale contacts from a materials science perspective. In this article the fundamentals of brittle-ductile transitions in indentation stress fields are surveyed, with distinctions between axial and sliding loading and blunt and sharp contacts. Attendant deformation and removal mechanisms in microcontact processes are analyzed and discussed in the context of brittle and ductile machining and severe and mild wear. The central role of material microstructure in material removal modes is demonstrated.

The effect of a high-performance retarding additive in oil well cements was investigated under elevated temperature (165°C) and pressure (1000 psi) conditions via in situ synchrotron-based X-ray diffraction (XRD) and quasielastic neutron scattering (QENS) techniques. Under these temperature and pressure conditions, crystalline calcium silicate hydrates (C-S-H) are formed through the cement hydration process. From in situ XRD experiments, the retardation effect was observed by a change in the rate of the appearance of 11 Å tobermorites as well as a change in the rate of the α-CSH generation and depletion. QENS analysis revealed that the retardation effect was related to the non-conversion of free water to chemical and constrained water components. A high presence of free water components was attributed to a decrease in 11 Å tobermorites along with slower consumption of the quartz and portlandite phases. Furthermore, QENS results infer that the water molecules experienced confinement in the restricted pore spaces. The retarder inhibited this initial water confinement by slowing the bulk diffusion of free water in the confined region.

A recently developed non-destructive method was used to investigate the stress build-up in chemically strengthened lithium aluminosilicate glass. We utilized an updated version of the gradient scattered light method, which now enables more precise determination of the depth coordinates, recovering a more detailed stress profile around the knee. The main motivation of the work was to characterize and optimize the development of the knee-shaped breaking point in stress profile in lithium aluminosilicate glass using Saunders-Kubichan method of 1-step strengthening in a mixture of KNO+NaNO molten salt bath. In the industry, a 2-step process is still commonly used to build such a stress profile. 1-step strengthening will simplify the process as well as save the cost. Compared to previous studies, which used a destructive method based on transmitted light photoelasticity, we found that in the samples ion-exchanged for 24h the knee-shaped breaking points were situated two times deeper whereas the case-depths were 28% shallower. The measured stress profiles were validated by stress equilibrium and by comparison to Na ion concentration profiles.

The primary goal of this study was to characterize the influence of the pore-saturated gas media and their physical properties on the elasticity of porous ceramic materials. Resonant ultrasound spectroscopic measurements were performed on test specimens of alumina with ~40% porosity, zirconia with ~48% porosity, and sintered fully dense zirconia to determine the hydrostatic pressure-dependent macroscopic elasticity. Here, we report the variation of elasticity of porous and full dense samples over approximately five orders of magnitude (800-0.02 psi) in absolute pressure. The time evolution of mechanical equilibrium of the porous materials at low pressure and high-temperature conditions will also be discussed.

Combining sol-gel processing and laser sintering is a promising way for fabricating functional ceramic deposition with high dimensional resolution. In this work, crack-free silica tracks on a silica substrate with a thickness from ~360 nm to ~950 nm, have been obtained by direct exposure to a CO laser beam. At a fixed scanning speed, the density and microstructures of the silica deposition can be precisely controlled by varying the laser output power. The porosity of the laser-sintered silica tracks ranged from close to 0% to ~60%. When the thickness of the silica deposition exceeded the critical thickness (eg, ~2.2 μm before firing), cracks occurred in both laser-sintered and furnace-sintered samples. Cracks propagated along the edge of the laser-sintered track, resulting in the crack-free track. However, for the furnace heat-treated counterpart, the cracks spread randomly. To understand the laser sintering effect, we established a finite element model (FEM) to calculate the temperature profile of the substrate during laser scanning, which agreed well with the one-dimensional analytical model. The FEM model confirmed that laser sintering was the main thermal effect and the calculated temperature profile can be used to predict the microstructure of the laser-sintered tracks. Combining these results, we were able to fabricate, predesigned patterned (Clemson tiger paw) silica films with high density using a galvo scanner.

SiO/SiC coatings were deposited onto ceramics disks using plasma enhanced chemical vapor deposition. The effects of deposition pressure and gas-flow ratio on the refractive index, extinction coefficient, and SiC composition were studied. For the highest studied SiH to CH gas-flow ratio of 1.5, the refractive index increased by 17% from 2.53 (at the wavelength of 845 nm) to 2.96 (at the wavelength of 400 nm). For the lowest studied SiH to CH gas-flow ratio of 0.5, the refractive index only increased by 4% from 2.11 (at the wavelength of 845 nm) to 2.20 (at the wavelength of 400 nm). At higher deposition pressures, the variation in refractive index of the SiC coatings was significantly lower showing a slight increase from 1.93 (at a wavelength of 845 nm) to 1.96 at a wavelength of 400 nm. Except for the case of a low SiH to CH gas-flow ratio of 0.5, for light with wavelengths ≤ 650 nm, the extinction coefficient of the SiC coatings increased significantly. Light with a wavelength > 650 nm had an extinction coefficient near 0 in all cases. After annealing the sample at 400°C for 4 hours, hydrogen-related bonds broke and the stress of the film was reduced from -245 to -71 MPa. By utilizing different thicknesses of SiC, the full standard dental shade guide was matched with the ΔE of each coated disk being less than 3.3 compared to the shade guide.

A key question in the field of ceramics and catalysis is how and to what extent residual water in the reactive environment of a metal oxide particle powder affects particle coarsening and morphology. With X-ray Diffraction (XRD) and Transmission Electron Microscopy (TEM), we investigated annealing-induced morphology changes on powders of MgO nanocubes in different gaseous HO environments. The use of such a model system for particle powders enabled us to describe how adsorbed water that originates from short exposure to air determines the evolution of MgO grain size, morphology, and microstructure. While cubic nanoparticles with a predominant abundance of (100) surface planes retain their shape after annealing to T = 1173 K under continuous pumping with a base pressure of water p(HO) = 10 mbar, higher water partial pressures promote mass transport on the surfaces and across interfaces of such particle systems. This leads to substantial growth and intergrowth of particles and simultaneously favors the formation of step edges and shallow protrusions on terraces. The mass transfer is promoted by thin films of water providing a two-dimensional solvent for Mg ion hydration. In addition, we obtained direct evidence for hydroxylation-induced stabilization of (110) faces and step edges of the grain surfaces.

Advances in nano-computed X-ray tomography (nCT), nano X-ray fluorescence spectrometry (nXRF), and high-performance computing have enabled the first direct comparison between observations of three-dimensional nanoscale microstructure evolution during cement hydration and computer simulations of the same microstructure using HydratiCA. nCT observations of a collection of triclinic tricalcium silicate (CaSiO) particles reacting in a calcium hydroxide solution are reported and compared to simulations that duplicate, as nearly as possible, the thermal and chemical conditions of those experiments. Particular points of comparison are the time dependence of the solid phase volume fractions, spatial distributions, and morphologies. Comparisons made at 7 h of reaction indicate that the simulated and observed volumes of CaSiO consumed by hydration agree to within the measurement uncertainty. The location of simulated hydration product is qualitatively consistent with the observations, but the outer envelope of hydration product observed by nCT encloses more than twice the volume of hydration product in the simulations at the same time. Simultaneous nXRF measurements of the same observation volume imply calcium and silicon concentrations within the observed hydration product envelope that are consistent with Ca(OH) embedded in a sparse network of calcium silicate hydrate (C-S-H) that contains about 70 % occluded porosity in addition to the amount usually accounted as gel porosity. An anomalously large volume of Ca(OH) near the particles is observed both in the experiments and in the simulations, and can be explained as originating from the hydration of additional particles outside the field of view. Possible origins of the unusually large amount of observed occluded porosity are discussed.

The proton conductivity in functional oxides is crucial in determining electrochemistry and transport phenomena in a number of applications such as catalytic devices and fuel cells. However, single characterization techniques are usually limited in detecting the ionic dynamics at the full range of environmental conditions. In this report, we probe and uncover the links between the microstructure of nanostructured ceria (NC) and parameters that govern its electrochemical reaction and proton transport, by coupling experimental data obtained with time-resolved Kelvin probe force microscopy (tr-KPFM), electrochemical impedance spectroscopy (EIS), and finite element analysis. It is found that surface morphology determines the water splitting rate and proton conductivity at 25 °C and wet conditions, where protons are mainly generated and transported within surface physisorbed water layers. However, at higher temperature (i.e., ≥125 °C) and dry conditions, when physisorbed water evaporates, grain size and crystallographic orientation become significant factors. Specifically, the proton generation rate is negatively correlated with the grain size, whereas proton diffusivity is facilitated by surface {111} planes and additional conduction pathways offered by cracks and open pores connected to the surface.

A procedure is outlined for determining the population of flaws in manufactured ceramics from strength measurements of sampled components. The broad applicability of the procedure is demonstrated in a quantitative manner, using strength measurements from a range of ceramic materials (eg, glass, glass-ceramic, single crystal, and polycrystal) with different flaw types (eg, bulk, surface, and edge). The deconvoluted flaw populations are mostly dominated by small flaws with extended large flaw tails and are all in domains of tens of micrometers. The procedure greatly extends the useful information to be gained by ceramics manufacturers and designers from strength distribution measurements and emphasizes the importance of identifying strength-limiting characteristics within a flaw population.

We report on a recent workshop dedicated to additive manufacturing (AM) of ceramics that was held at the National Institute of Standards and Technology (NIST) in November 2019. This two-day all-invited meeting brought together experts from industry, government agencies and academia to review the state of the field and identify the most pressing applied materials research and metrology issues which, if addressed, could accelerate the incorporation of AM methods into commercial ceramic manufacturing. Besides the AM technologies, the discussions included consideration of the necessary post-processing steps. We highlight some of the successes and challenges for the adoption of ceramics AM on an industrial scale, as viewed by the workshop participants. We also propose actions for the ceramic community to facilitate the wider commercialization of these fabrication methods.