Maintaining particle size in the transformation of anatase to rutile titania nanostructures

We study the temperature-dependent transformation of two distinctly synthesized TiO₂ nanoparticles from the anatase to the rutile phase. These studies are carried out over the temperature range extending from room temperature to an excess of 800 °C where the anatase to rutile conversion is found to occur. Results obtained for both a sol-gel-generated nanocolloid (3-20 nm) and a sol-gel-generated micelle nanostructure (∼40 nm) are evaluated. While the TiO₂ nanocolloid structures aggregate to form larger crystallites as a function of increasing temperature with sizes comparable to the sol-gel-generated micelle structures, the resulting anatase crystallites, which are of a diameter 40-50 nm, appear to transform to comparable or slightly smaller rutile structures at 800 °C. This is in contrast to the transformation to larger rutile structures, observed for larger anatase particles. The importance of kinetic effects is considered as it enhances the rate of anatase to rutile conversion. These characteristics are established using a combination of Raman spectroscopic, X-ray diffraction, and scanning electron microscopy. The relative playoffs of the Raman and X-ray diffraction techniques are considered as they are used for the analysis of particles at the nanoscale, especially when phase transformations are evaluated.     

On the third- and fourth-order constants of incompressible isotropic elasticity

Consider the constitutive law for an isotropic elastic solid with the strain-energy function expanded up to the fourth order in the strain and the stress up to the third order in the strain. The stress-strain relation can then be inverted to give the strain in terms of the stress with a view to considering the incompressible limit. For this purpose, use of the logarithmic strain tensor is of particular value. It enables the limiting values of all nine fourth-order elastic constants in the incompressible limit to be evaluated precisely and rigorously. In particular, it is explained why the three constants of fourth-order incompressible elasticity μ, ā, and D are of the same order of magnitude. Several examples of application of the results follow, including determination of the acoustoelastic coefficients in incompressible solids and the limiting values of the coefficients of nonlinearity for elastic wave propagation.     

Some solutions for a compressible isotropic elastic material

In this article we obtain closed-form solutions for the combined inflation and axial shear of an elastic tube in respect of the compressible isotropic elastic material introduced by Levinson and Burgess. Several other boundary-value problems are also examined, including the bending of a rectangular block and straightening of a cylindrical sector, both coupled with stretching and shearing, and an axially varying twist deformation. Some of the solutions appear in closed form, others are expressible in terms of elliptic functions.     

Lanthanoid/Alkali Metal β‐Triketonate Assemblies: A Robust Platform for Efficient NIR Emitters

The reaction of hydrated lanthanoid chlorides with tribenzoylmethane and an alkali metal hydroxide consistently resulted in the crystallization of neutral tetranuclear assemblies with the general formula [Ln(Ae ? HOEt)( L )₄]₂ (Ln=Eu³⁺, Er³⁺, Yb³⁺; Ae=Na⁺, K⁺, Rb⁺). Analysis of the crystal structures of these species revealed a coordination geometry that varied from a slightly distorted square antiprism to a slightly distorted triangular dodecahedron, with the specific geometrical shape being dependent on the degree of lattice solvation and identity of the alkali metal. The near‐infrared (NIR)‐emitting assemblies of Yb³⁺ and Er³⁺ showed remarkably efficient emission, characterized by significantly longer excited‐state lifetimes (τ_obs≈37–47 μs for Yb³⁺ and τ_obs≈4–6 μs for Er³⁺) when compared with the broader family of lanthanoid β‐diketonate species, even in the case of perfluorination of the ligands. The Eu³⁺ assemblies show bright red emission and a luminescence performance (τ_obs≈0.5 ms, ${{\Phi}{{{\rm L}\hfill \atop {\rm Ln}\hfill}}}$ ≈35–37 %, η_sens≈68–70 %) more akin to the β‐diketonate species. The results highlight that the β‐triketonate ligand offers a tunable and facile system for the preparation of efficient NIR emitters without the need for more complicated perfluorination or deuteration synthetic strategies.     

Acoustically enriching, large-depth aquatic sampler

In marine biology, it is useful to collect water samples when exploring the distribution and diversity of microbial communities in underwater environments. In order to provide, e.g., a miniaturized submersible explorer with the capability of collecting microorganisms, a compact sample enrichment system has been developed. The sampler is 30 mm long, 15 mm wide, and just a few millimetres thick. Integrated in a multilayer steel, polyimide and glass construction is a microfluidic channel with piezoelectric transducers, where microorganism and particle samples are collected and enriched, using acoustic radiation forces for gentle and labelless trapping. High-pressure, latchable valves, using paraffin as the actuation material, at each end of the microfluidic channel keep the collected sample pristine. A funnel structure raised above the surface of the device directs water into the microfluidic channel as the vehicle propels itself or when there is a flow across its hull. The valves proved leak proof to a pressure of 2.1 MPa for 19 hours and momentary pressures of 12.5 MPa, corresponding to an ocean depth of more than 1200 metres. By reactivating the latching mechanism, small leakages through the valves could be remedied, which could thus increase the leak-less operational time. Fluorescent particles, 1.9 μm in diameter, were successfully trapped in the microfluidic channel at flow rates up to 15 μl min(-1), corresponding to an 18.5 cm s(-1) external flow rate of the sampler. In addition, liquid-suspended GFP-marked yeast cells were successfully trapped.     

Initial stresses in elastic solids: Constitutive laws and acoustoelasticity

On the basis of the nonlinear theory of elasticity, the general constitutive equation for an isotropic hyperelastic solid in the presence of initial stress is derived. This derivation involves invariants that couple the deformation with the initial stress and in general, for a compressible material, it requires 10 invariants, reducing to 9 for an incompressible material. Expressions for the Cauchy and nominal stress tensors in a finitely deformed configuration are given along with the elasticity tensor and its specialization to the initially stressed undeformed configuration. The equations governing infinitesimal motions superimposed on a finite deformation are then used to study the combined effects of initial stress and finite deformation on the propagation of homogeneous plane waves in a homogeneously deformed and initially stressed solid of infinite extent. This general framework allows for various different specializations, which make contact with earlier works. In particular, connections with results derived within Biot's classical theory are highlighted. The general results are also specialized to the case of a small initial stress and a small pre-deformation, i.e. to the evaluation of the acoustoelastic effect. Here the formulas derived for the wave speeds cover the case of a second-order elastic solid without initial stress and subject to a uniaxial tension [Hughes and Kelly, Phys. Rev. 92 (1953) 1145] and are consistent with results for an undeformed solid subject to a residual stress [Man and Lu, J. Elasticity 17 (1987) 159]. These formulas provide a basis for acoustic evaluation of the second- and third-order elasticity constants and of the residual stresses. The results are further illustrated in respect of a prototype model of nonlinear elasticity with initial stress, allowing for both finite deformation and nonlinear dependence on the initial stress.     

A "plug-and-play" approach to the preparation of transparent luminescent hybrid materials based on poly(methyl methacrylate), a calix[4]arene cross-linking agent, and terbium ions

A novel methodology to prepare transparent luminescent hybrid materials is reported. Using a calixarene ionophore as a PMMA cross-linker avoids problems, such as phase segregation, and produces a polymer monolith that can be loaded with the metal ion required for luminescence post-synthesis. This approach is versatile and will simplify the production of such materials.