Exceptional Microscale Plasticity in Amorphous Aluminum Oxide at Room Temperature.

Oxide glasses are an elementary group of materials in modern society, but brittleness limits their wider usability at room temperature. As an exception to the rule, amorphous aluminum oxide (a-Al2 O3 ) is a rare diatomic glassy material exhibiting significant nanoscale plasticity at room temperature. Here, it is shown experimentally that the room temperature plasticity of a-Al2 O3 extends to the microscale and high strain rates using in situ micropillar compression. All tested a-Al2 O3 micropillars deform without fracture at up to 50% strain via a combined mechanism of viscous creep and shear band slip propagation. Large-scale molecular dynamics simulations align with the main experimental observations and verify the plasticity mechanism at the atomic scale. The experimental strain rates reach magnitudes typical for impact loading scenarios, such as hammer forging, with strain rates up to the order of 1 000 s-1 , and the total a-Al2 O3 sample volume exhibiting significant low-temperature plasticity without fracture is expanded by 5 orders of magnitude from previous observations. The discovery is consistent with the theoretical prediction that the plasticity observed in a-Al2 O3 can extend to macroscopic bulk scale and suggests that amorphous oxides show significant potential to be used as light, high-strength, and damage-tolerant engineering materials.

Reactive laser interference patterning on titanium and zinc in high pressure CO2.

Direct laser interference patterning (DLIP) is a versatile technique for surface patterning that enables formation of micro-nano sized periodic structures on top of the target material. In this study, DLIP in high pressure, supercritical and liquid CO2 by 4-beam DLIP was used to pattern titanium and zinc targets. Field emission scanning electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy was used to characterize the patterned surfaces. Field emission SEM analysis showed presence of ordered uniform donut ring pattern with hollow centers for both titanium and zinc with a period slightly under 3 µm while topographical images from atomic force microscopy revealed donut rings protruding outwards typically around 200 nm from target surface and consisted of a crevice at the center with a depth typically around 300 nm and 250 nm for titanium and zinc target, respectively. Based on X-ray photoelectron spectroscopic analysis, this is the first study to report formation of TiO2, TiC, ZnCO3, and zinc hydroxy carbonate on the pattern by DLIP in supercritical and liquid CO2 for titanium and zinc targets. Pressurized CO2 is demonstrated as a promising environment with mirror-based DLIP system for reactive patterning. Due to the superior transport properties and solvent power of supercritical CO2, the current study opens possibilities for reactive patterning in environments that may not have been previously possible.

Highly ductile amorphous oxide at room temperature and high strain rate.

Oxide glasses are an integral part of the modern world, but their usefulness can be limited by their characteristic brittleness at room temperature. We show that amorphous aluminum oxide can permanently deform without fracture at room temperature and high strain rate by a viscous creep mechanism. These thin-films can reach flow stress at room temperature and can flow plastically up to a total elongation of 100%, provided that the material is dense and free of geometrical flaws. Our study demonstrates a much higher ductility for an amorphous oxide at low temperature than previous observations. This discovery may facilitate the realization of damage-tolerant glass materials that contribute in new ways, with the potential to improve the mechanical resistance and reliability of applications such as electronic devices and batteries.

Carbon coated TiO2 nanoparticles prepared by pulsed laser ablation in liquid, gaseous and supercritical CO2.

We report on the synthesis of TiO2 nanoparticles using nanosecond pulse laser ablation of titanium in liquid, gaseous and supercritical CO2. The produced particles were observed to be mainly anatase-TiO2 with some rutile-TiO2. In addition, the particles were covered by a carbon layer. Raman and x-ray diffraction data suggested that the rutile content increases with CO2 pressure. The nanoparticle size decreased and size distribution became narrower with the increase in CO2 pressure and temperature, however the variation trend was different for CO2 pressure compared to temperature. Pulsed laser ablation in pressurized CO2 is demonstrated as a single step method for making anatase-TiO2/carbon nanoparticles throughout the pressure and temperature ranges 5-40 MPa and 30 °C-50 °C, respectively.

Synthesis of ZnO nanowires with supercritical carbon dioxide and post heat treatment.

Zinc oxide (ZnO) nanowires are used in applications such as gas sensors and solar cells. This work presents a novel synthesis route for ZnO nanowires using supercritical carbon dioxide (scCO2) and post heat treatment. The method used scCO2 and a precursor solution as reactants to form nanowires on a galvanized surface. After the scCO2 treatment, the substrate was heat-treated. The surfaces were characterized with SEM, TEM, EDS, FTIR, XRD and optical spectroscopy. The FTIR results showed that the surface structure had changed from zinc hydroxycarbonate to ZnO during the heat treatment. The nanowires were slightly bent due to the heat treatment according to the SEM images. The presence of ZnO was further confirmed with XRD. The bandgap of the structure was determined by reflectance measurements and showed a value of 3.23 eV. The synthesis method presented in this study offers a unique approach into the formation of ZnO nanowires in a facile, rapid and environmentally friendly process.

Tailoring of Versatile Surface Morphologies on Hot Dip Galvanized Steel in Wet CO2: Aspects on Formation, Barrier Properties, and Utilization as a Substrate for Coatings.

Zinc carbonate and a mixed-phase zinc carbonate were precipitated selectively on hot dip galvanized steel in the presence of CO2 and water. The zinc carbonate was precipitated as a uniform layer with cubic superficial appearance, while the mixed-phase zinc carbonate was precipitated as nanowires. The distinct structures could be formed separately or as a dual structure with nanowires on the outermost surface. The barrier properties were improved by the both patina forms; a significant increase in surface hydrophobicity was obtained. The dual patina structure was successfully coated with an organic coating, and the intact wet CO2-induced patina with both structures was confirmed within the coating. The formed carbonates can be further converted to zinc oxide by calcination, preserving the delicate structures, which opens a wide range of potential applications for the nanostructured ZnO in a variety of future electronic and optoelectronic devices.

Dissolution-Induced Nanowire Synthesis on Hot-Dip Galvanized Surface in Supercritical Carbon Dioxide.

In this study, we demonstrate a rapid treatment method for producing a needle-like nanowire structure on a hot-dip galvanized sheet at a temperature of 50 °C. The processing method involved only supercritical carbon dioxide and water to induce a reaction on the zinc surface, which resulted in growth of zinc hydroxycarbonate nanowires into flower-like shapes. This artificial patina nanostructure predicts high surface area and offers interesting opportunities for its use in industrial high-end applications. The nanowires can significantly improve paint adhesion and promote electrochemical stability for organic coatings, or be converted to ZnO nanostructures by calcining to be used in various semiconductor applications.

Pulsed Laser Ablation-Induced Green Synthesis of TiO2 Nanoparticles and Application of Novel Small Angle X-Ray Scattering Technique for Nanoparticle Size and Size Distribution Analysis.

This paper aims to introduce small angle X-ray scattering (SAXS) as a promising technique for measuring size and size distribution of TiO2 nanoparticles. In this manuscript, pulsed laser ablation in liquids (PLAL) has been demonstrated as a quick and simple technique for synthesizing TiO2 nanoparticles directly into deionized water as a suspension from titanium targets. Spherical TiO2 nanoparticles with diameters in the range 4-35 nm were observed with transmission electron microscopy (TEM). X-ray diffraction (XRD) showed highly crystalline nanoparticles that comprised of two main photoactive phases of TiO2: anatase and rutile. However, presence of minor amounts of brookite was also reported. The traditional methods for nanoparticle size and size distribution analysis such as electron microscopy-based methods are time-consuming. In this study, we have proposed and validated SAXS as a promising method for characterization of laser-ablated TiO2 nanoparticles for their size and size distribution by comparing SAXS- and TEM-measured nanoparticle size and size distribution. SAXS- and TEM-measured size distributions closely followed each other for each sample, and size distributions in both showed maxima at the same nanoparticle size. The SAXS-measured nanoparticle diameters were slightly larger than the respective diameters measured by TEM. This was because SAXS measures an agglomerate consisting of several particles as one big particle which slightly increased the mean diameter. TEM- and SAXS-measured mean diameters when plotted together showed similar trend in the variation in the size as the laser power was changed which along with extremely similar size distributions for TEM and SAXS validated the application of SAXS for size distribution measurement of the synthesized TiO2 nanoparticles.

Sol-gel derived aluminosilicate coatings on alumina as substrate for osteoblasts.

Rat bone marrow stromal cell differentiation on aluminosilicate 3Al(2)O(3)-2SiO(2) coatings was investigated. Thin ceramic coatings were prepared on alpha-alumina substrates by the sol-gel process and calcined in order to establish an amorphous aluminosilicate ceramic phase with and without nanosized transitional mullite crystals. In addition, coatings of thermally sprayed aluminosilicate and diphasic gamma-alumina-silica nanosized colloids were prepared. Cell culture testing by rat osteoblasts showed good biocompatibility for aluminosilicates with sustained normal osteoblast functions. Despite mutual disparities in physical and chemical nanostructures, the culture findings suggested fairly similar osteoblast response to all tested coatings. The results suggest that topographical frequency parameters and chemical uniformity are important parameters in determining the best conditions for osteoblasts on sol-gel derived aluminosilicate materials.

Surface characterization of plasma sprayed oxide materials: estimation of surface acidity using mass titration.

The aim of this study was to characterize the influence of plasma spraying on the point of zero charge (PZC) of Al2O3-, Cr2O3- and TiO2-based materials. PZC is one of the most important parameter, which describes the acidity of oxide material in aqueous environments. PZC values of several plasma sprayed oxides were determined using mass titration method. Studies were performed for initial spray powders and plasma sprayed coating materials. In addition, mass titration experiments were performed for water-washed and nonwashed samples. It was found that mass titration is a suitable method to estimate the surface acidity of relatively coarse sample powders. It was found for most of the studied materials that the limiting pH values (assumed to be close PZC) were close to those reported in literature for the PZC values of traditionally manufactured oxide materials. On the other hand, mass titration curves of some oxide samples showed unexpected deviation in curve shapes and limiting pH. These deviations were probably due to selective dissolution of sample contaminations or sample material.

Influence of Additives on Capillary Absorption of Aqueous Solutions into Asymmetric Porous Ceramic Substrate.

The mechanisms of absorption of water-based solutions of polyelectrolyte (Na-PMAA) or binder (polyvinylalcohol, PVA) into asymmetric porous compacts were studied. The capillary pressure of each solution was calculated from the absorption rate. An absorption model developed for the two-layered structure was used to correlate the solution properties with the absorption dynamics. Na-PMAA increased the capillary pressure in the pores of the substrate. The influence of the surface on the capillary pressure could be explained by the Laplace equation and the Young equation. Na-PMAA decreases the surface tension and improves the wetting of pore walls according to the Young equation. The addition of PVA decreased the surface without an effect on wetting angle, resulting in lower capillary pressures. The absorption of PVA on the pore walls from the advancing liquid meniscus is probably rather slow and therefore the Young equation is not valid. Copyright 2001 Academic Press.