Crystal structure solution and high-temperature thermal expansion in NaZr2(PO4)3-type materials.

The NaZr2P3O12 family of materials have shown low and tailorable thermal expansion properties. In this study, SrZr4P6O24 (SrO·4ZrO2·3P2O5), CaZr4P6O24 (CaO·4ZrO2·3P2O5), MgZr4P6O24 (MgO·4ZrO2·3P2O5), NaTi2P3O12 [½(Na2O·4TiO2·3P2O5)], NaZr2P3O12 [½(Na2O·4ZrO2·3P2O5)], and related solid solutions were synthesized using the organic-inorganic steric entrapment method. The samples were characterized by in-situ high-temperature X-ray diffraction from 25 to 1500°C at the Advanced Photon Source and National Synchrotron Light Source II. The average linear thermal expansion of SrZr4P6O24 and CaZr4P6O24 was between -1 × 10-6 per °C and 6 × 10-6 per °C from 25 to 1500°C. The crystal structures of the high-temperature polymorphs of CaZr4P6O24 and SrZr4P6O24 with R3c symmetry were solved by Fourier difference mapping and Rietveld refinement. This polymorph is present above ∼1250°C. This work measured thermal expansion coefficients to 1500°C for all samples and investigated the differences in thermal expansion mechanisms between polymorphs and between compositions.

Erratum: Specimen-displacement correction for powder X-ray diffraction in Debye-Scherrer geometry with a flat area detector. Erratum.

[This corrects the article DOI: 10.1107/S1600576722011360.].

Specimen-displacement correction for powder X-ray diffraction in Debye-Scherrer geometry with a flat area detector.

The effect of small changes in the speci-men-to-detector distance on the unit-cell parameters is examined for synchrotron powder diffraction in Debye-Scherrer (transmission) geometry with a flat area detector. An analytical correction equation is proposed to fix the shift in 2θ values due to speci-men capillary displacement. This equation does not require the use of an internal reference material, is applied during the Rietveld refinement step, and is analogous to the speci-men-displacement correction equations for Bragg-Brentano and curved-detector Debye-Scherrer geometry experiments, but has a different functional form. The 2θ correction equation is compared with another speci-men-displacement correction based on the use of an internal reference material in which new integration and calibration parameters of area-detector images are determined. Example data sets showing the effect of a 3.3 mm speci-men displacement on the unit-cell parameters for 25°C CeO2, including both types of displacement correction, are described. These experiments were performed at powder X-ray diffraction beamlines at the National Synchrotron Light Source II at Brookhaven National Laboratory and the Advanced Photon Source at Argonne National Laboratory.

Thermal expansion and phase transformation in the rare earth di-titanate (R2Ti2O7) system.

Characterization of the thermal expansion in the rare earth di-titanates is important for their use in high-temperature structural and dielectric applications. Powder samples of the rare earth di-titanates R2Ti2O7 (or R2O3·2TiO2), where R = La, Pr, Nd, Sm, Gd, Dy, Er, Yb, Y, which crystallize in either the monoclinic or cubic phases, were synthesized for the first time by the solution-based steric entrapment method. The three-dimensional thermal expansions of these polycrystalline powder samples were measured by in situ synchrotron powder diffraction from 25°C to 1600°C in air, nearly 600°C higher than other in situ thermal expansion studies. The high temperatures in synchrotron experiments were achieved with a quadrupole lamp furnace. Neutron powder diffraction measured the monoclinic phases from 25°C to 1150°C. The La2Ti2O7 member of the rare earth di-titanates undergoes a monoclinic to orthorhombic displacive transition on heating, as shown by synchrotron diffraction in air at 885°C (864°C-904°C) and neutron diffraction at 874°C (841°C-894°C).

Development of mechanical properties in dental resin composite: Effect of filler size and filler aggregation state.

The aim of this work was to study the effect of filler size and filler aggregation state on the mechanical properties of dental resin composites evaluated at filler loadings between 20 wt% and up to 76.5 wt%. Non-aggregated silica nanoparticles (SiNPMPS) (80 nm), doughnut-shaped silica nanoclusters obtained by spray drying (SDSiNPMPS) (3.5 µm) and amorphous barium-alumina borosilicate microparticles (BaAlBoSiMPS) (1.0 µm), functionalized by 3-methacryloxypropyl trimethoxysilane (MPS), were the fillers incorporated into resin matrix dental composites composed of triethylene glycoldimethacrylate (TEGDMA), urethane dimethylacrylate (UDMA), bisphenol A polyethylene glycol diether dimethacrylate (Bis EMA), and bisphenol A glycidyl methacrylate (BisGMA) (0.3:0.7:1:1 weight ratio, respectively). The mechanical properties developed in the resin composites were correlated with the formation of percolated-like particle networks, as observed by scanning electron microscopy (SEM), and volume fraction percolation thresholds (ϕc) calculated from a percolation model. Resin composites with non-aggregated SiNPMPS showed an apparent percolation threshold ϕc = 0.15 (i.e. 27 wt%); above this filler concentration and up to a volume fraction of particles (ϕP) of 0.24 (i.e. 40 wt%) there was an increase in the flexural modulus and the compressive strength of the resin composite. However, a further increase in filler concentration diminished all its mechanical properties due to a decrease in the particle-matrix adhesion strength, demonstrated by the increase in surface roughness and fracture steps as observed by SEM images. On the other hand, a resin composite filled with doughnut-shaped silica nanoclusters (SDSiNPMPS) showed an apparent percolation threshold ϕc = 0.41 (i.e. 60 wt%); increasing filler loading over this concentration generated an improvement in its mechanical properties, except the flexural strength also due to a decrease in the particle-matrix adhesion strength. The resin composites obtained with amorphous individual BaAlBoSiMPS microparticles (1.0 µm) and BaAlBoSiMPS microparticle aggregates (ca. 40.0 µm) showed an apparent percolation threshold ϕc = 0.41 (i.e. 64 wt%) that promoted an improvement in all their mechanical properties. SEM image of BaAlBoSiMPS resin composite at high filler loading (≥ 60 wt%) showed a decrease in fracture steps and no presence of voids, indicating a better adhesion between amorphous BaAlBoSiMPS particles and the polymeric matrix, which explains the improvement of mechanical properties. Resin composites filled exclusively with silica doughnut-shape nanoclusters or amorphous BaAlBoSiMPS microparticles could develop mechanical properties similar to or even better than those obtained by mixing nanofillers with spherical nanoclusters, which are commonly used in commercial resin composites.

Temperature gradients for thermophysical and thermochemical property measurements to 3000 °C for an aerodynamically levitated spheroid.

This study examines thermal gradients in ceramic oxide spheroids being aerodynamically levitated in a conical nozzle levitator (CNL) system equipped with a CO2 laser (10.6 µm wavelength). The CNL system is a versatile piece of equipment that can easily be coupled with advanced thermophysical and thermochemical measuring devices, such as diffraction/scattering (X-ray and neutron), nuclear magnetic resonance, and calorimetry, for the analysis of bulk spheroidal solids and liquids. The thermal gradients of a series of single crystal, polycrystalline solids, and liquid spheroids have been measured spatially in the CNL system, by means of a disappearing filament pyrometer (800-3000 °C) and by X-ray diffraction with reference to an internal standard (Pt: 800-1600 °C). The thermal gradient in a levitated sample being heated by a laser from the top can be minimized by: (i) maximizing the sphericity, (ii) maximizing the density, and (iii) minimizing microstructural features. A spheroid with these properties can be manufactured via machining a perfect sphere from a highly dense, chemically and phase pure pellet. These properties promote rotation of the sample about multiple axes in the air stream, enabling homogeneous heating. This homogeneous heating is the dominant factor in reducing thermal gradients in solid state samples. It was found that the thermal gradient in an ∼3 mm diameter solid sample could be reduced from 1000 °C to 30 °C, by having a perfectly spherical shape that could rotate on multiple axes in a high velocity gas stream (∼1500-2000 cm3/min). These findings will allow accurate thermophysical and thermochemical property measurements of solids in situ at high temperatures, using the CNL system.

Crystal structure solution for the A6B2O17 (A = Zr, Hf; B = Nb, Ta) superstructure.

Zr6Ta2O17, Hf6Nb2O17 and Hf6Ta2O17 crystal structure solutions have been solved using synchrotron X-ray powder diffraction and neutron powder diffraction in conjunction with simulated annealing, charge flipping and Rietveld refinement. These structures have been shown to be isomorphous with the Zr6Nb2O17 superstructure, leading to the classification of the A6B2O17 (A = Zr, Hf; B = Nb, Ta) orthorhombic compound family with symmetry Ima2 (No. 46). The asymmetrical structural units of cation-centred oxygen polyhedra used to build the structure are as follows: (i) one set of symmetry-equivalent six-coordinated polyhedra, (ii) three sets of symmetry-equivalent seven-coordinated polyhedra and (iii) one set of symmetry-equivalent eight-coordinated polyhedra. The potential for cation order and disorder was discussed in terms of cation atomic number contrast in X-ray and neutron powder diffraction as well as the bond valence method. In addition, the structural mechanisms for experimentally observed compositional variations within the solid solution range can be attributed to the addition or removal of a set of symmetry-equivalent seven-coordinated polyhedra accompanied by corresponding oxygen tilts within the A6B2O17 structure.

Predicting failure: acoustic emission of berlinite under compression.

Acoustic emission has been measured and statistical characteristics analyzed during the stress-induced collapse of porous berlinite, AlPO4, containing up to 50 vol% porosity. Stress collapse occurs in a series of individual events (avalanches), and each avalanche leads to a jerk in sample compression with corresponding acoustic emission (AE) signals. The distribution of AE avalanche energies can be approximately described by a power law p(E)dE = E(-ε)dE (ε ~ 1.8) over a large stress interval. We observed several collapse mechanisms whereby less porous minerals show the superposition of independent jerks, which were not related to the major collapse at the failure stress. In highly porous berlinite (40% and 50%) an increase of energy emission occurred near the failure point. In contrast, the less porous samples did not show such an increase in energy emission. Instead, in the near vicinity of the main failure point they showed a reduction in the energy exponent to ~ 1.4, which is consistent with the value reported for compressed porous systems displaying critical behavior. This suggests that a critical avalanche regime with a lack of precursor events occurs. In this case, all preceding large events were 'false alarms' and unrelated to the main failure event. Our results identify a method to use pico-seismicity detection of foreshocks to warn of mine collapse before the main failure (the collapse) occurs, which can be applied to highly porous materials only.

Crackling noise during failure of alumina under compression: the effect of porosity.

We study acoustic emission avalanches during the process of failure of porous alumina samples (Al2O3) under compression. Specimens with different porosities ranging from 30% to 59% have been synthesized from a mixture of fine-grained alumina and graphite. The compressive strength as well as the characteristics of the acoustic activity have been determined. The statistical analysis of the recorded acoustic emission pulses reveals, for all porosities, a broad distribution of energies with a fat tail, compatible with the existence of an underlying critical point. In the region of 35%-55% porosity, the energy distributions of the acoustic emission signals are compatible with a power-law behaviour over two decades in energy with an exponent ϵ = 1.8 ± 0.1.

Inorganic delivery vector for intravenous injection.

Uniform, small-sized (100-200 nm), layered double hydroxides (LDH) were prepared by a conventional, wet chemistry method using different aging times of 1 and 3 days as an inorganic drug or gene delivery carrier. The samples prepared had a hexagonal thin, plate-like shape and TEM/SAD electron microscopy of LDH particles indicated that they were single crystals. In vivo testing of empty LDH administered to adult male Sprague Dawley rats was done to evaluate the possibility of using LDH as an injectable drug delivery vehicle.