Modelling of short-range ordering kinetics in dilute multicomponent substitutional solid solutions

ABSTRACT

Short-range ordering as the formation of couples and pairs between solutes is affected by their formation energies. This is not reflected in the standard regular solution model. Here, we present a new thermodynamic model which accounts for the dependence of the molar Gibbs energy on the concentrations of couples and pairs and their formation energies. The model treats kinetics of couples and pairs formation controlled by diffusion. This new model uses tracer diffusion coefficients of solutes and bond formation energies, which can be taken from ab initio calculations. Insofar, the current concept bridges the gap between ab initio methods and non-equilibrium thermodynamics. The reliability of the model is checked by comparison with kinetic Monte Carlo simulations. The model is applied to an Al-Mg-Si-Cu system. Finally, the configurational entropy for a binary system evaluated with the current model is compared with Bethe’s approximation, which allows estimating of applicability limits of the current model.     

Mechanical properties of pyrolysed wood: a nanoindentation study

The present work focuses on changes of mechanical properties in pyrolysed spruce wood as a function of temperature up to 2400°C. Nanoindentation tests are used for the determination of mechanical properties at the scale of single wood cell walls. Hardness, indentation modulus and elasto-plastic/brittle behaviour of the carbonaceous residues are derived as function of pyrolysis temperature. Hardness values increase continuously by more than one order of magnitude to 4.5?GPa at 700°C. The indentation modulus shows complex changes with a minimum of 5?GPa around 400°C and a maximum of 40?GPa around 1000°C. The deformation induced by the indenter is largely visco-plastic in native wood, but it is almost purely elastic in the carbonaceous residue, with particular low values of the indentation ductility index around 700°C. A low density and a strongly cross-linked carbon structure may explain the mechanical behaviour at these intermediate temperatures. A final decrease of the modulus and a slight decrease of ductility for temperatures above 2000°C can be attributed to a continuous structural transition of the material towards graphite-like stacking of carbon sheets and to preferred carbon orientation along the wood cell axis.     

Isolated Cobalt Ions Embedded in Magnesium Oxide Nanostructures: Spectroscopic Properties and Redox Activity

Atomic dispersion of dopants and control over their defect chemistry are central goals in the development of oxide nanoparticles for functional materials with dedicated electronic, optical or magnetic properties. We produced highly dispersed oxide nanocubes with atomic distribution of cobalt ions in substitutional sites of the MgO host lattice via metal organic chemical vapor synthesis. Vacuum annealing of the nanoparticle powders up to 1173 K has no effect on the shape of the individual particles and only leads to moderate particle coarsening. Such materials processing, however, gives rise to the electronic reduction of particle surfaces, which—upon O₂ admission—stabilize anionic oxygen radicals that are accessible to UV/Vis diffuse reflectance and electron paramagnetic resonance (EPR) spectroscopy. Multi-reference quantum chemical calculations show that the optical bands observed mainly originate from transitions into ⁴A_2g (⁴F), ⁴T_1g (⁴P) states with a contribution of transitions into ²T_1g, ²T_2g (²G) states through spin-orbit coupling and gain intensity through vibrational motion of the MgO lattice or the asymmetric ion field. Related nanostructures are a promising material system for single atomic site catalysis. At the same time, it represents an extremely valuable model system for the study of interfacial electron transfer processes that are key to nanoparticle chemistry and photochemistry at room temperature, and in heterogeneous catalysis.     

Modelling of grain refinement driven by negative grain boundary energy

Abstract

Grain refinement can be described by the classical kinetic equation using a negative value of the specific grain boundary Gibbs energy. A respective overview is offered reporting according observations and simulations, particularly linked to grain boundary segregation. Classical grain growth model is used in the treatment of evolution of the distribution function during refinement. The adapted model requires defining nucleation rate of new grains, which significantly influences the kinetics of the system of grains. Moreover, a jump in the distribution function is allowed at a certain value of the grain radius R_J, which separates old grains from newly nucleated ones. Evolution equation for both the critical radius R_c and separation radius R_J (jump position) as well as for the dimension-free distribution (shape) function are derived. Illustrative examples for the evolution of the system parameters under various nucleation rates of newly generated grains are presented.     

Highly Precise Corneal Surgery and All-Optical Histology with Femtosecond Lasers

We present an optimized femtosecond laser system for intrastromal tissue manipulation, application studies of commercial fs-LASIK procedures and results from the first successful demonstration of nonlinear (SHG) imaging of corneal ultrastructure and fs-laser-induced morphology modifications.     

Substrate-Enabled Room-Temperature Electrochemical Deposition of Crystalline ZnMnO3

Mixed transition metal oxides have emerged as promising electrode materials for electrochemical energy storage and conversion. To optimize the functional electrode properties, synthesis approaches allowing for a systematic tailoring of the materials’ composition, crystal structure and morphology are urgently needed. Here we report on the room-temperature electrodeposition of a ternary oxide based on earth-abundant metals, specifically, the defective cubic spinel ZnMnO₃. In this unprecedented approach, ZnO surfaces act as (i) electron source for the interfacial reduction of MnO₄⁻ in aqueous solution, (ii) as substrate for epitaxial growth of the deposit and (iii) as Zn precursor for the formation of ZnMnO₃. Epitaxial growth of ZnMnO₃ on the lateral facets of ZnO nanowires assures effective electronic communication between the electroactive material and the conducting scaffold and gives rise to a pronounced 2-dimensional morphology of the electrodeposit forming – after partial delamination from the substrate – twisted nanosheets. The synthesis strategy shows promise for the direct growth of different mixed transition metal oxides as electroactive phase onto conductive substrates and thus for the fabrication of binder-free nanocomposite electrodes.     

Conformal Coverage of ZnO Nanowire Arrays by ZnMnO3: Room-temperature Photodeposition from Aqueous Solution

Compositionally and structurally complex semiconductor oxide nanostructures gain importance in many energy-related applications. Simple and robust synthesis routes ideally complying with the principles of modern green chemistry are therefore urgently needed. Here we report on the one-step, room-temperature synthesis of a crystalline–amorphous biphasic ternary metal oxide at the ZnO surface using aqueous precursor solutions. More specifically, conformal and porous ZnMnO₃ shells are photodeposited from KMnO₄ solution onto immobilized ZnO nanowires acting not only as the substrate but also as the Zn precursor. This water-based, low temperature process yields ZnMnO₃/ZnO composite electrodes featuring in 1 M Na₂SO₄ aqueous solution capacitance values of 80–160 F g⁻¹ (as referred to the total mass of the porous film i. e. the electroactive ZnMnO₃ phase and the ZnO nanowire array). Our results highlight the suitability of photodeposition as a simple and green route towards complex functional materials.