Nanometer-scale mapping of irreversible electrochemical nucleation processes on solid Li-ion electrolytes

Electrochemical processes associated with changes in structure, connectivity or composition typically proceed via new phase nucleation with subsequent growth of nuclei. Understanding and controlling reactions requires the elucidation and control of nucleation mechanisms. However, factors controlling nucleation kinetics, including the interplay between local mechanical conditions, microstructure and local ionic profile remain inaccessible. Furthermore, the tendency of current probing techniques to interfere with the original microstructure prevents a systematic evaluation of the correlation between the microstructure and local electrochemical reactivity. In this work, the spatial variability of irreversible nucleation processes of Li on a Li-ion conductive glass-ceramics surface is studied with ~30 nm resolution. An increased nucleation rate at the boundaries between the crystalline AlPO4 phase and amorphous matrix is observed and attributed to Li segregation. This study opens a pathway for probing mechanisms at the level of single structural defects and elucidation of electrochemical activities in nanoscale volumes.

The partially reversible formation of Li-metal particles on a solid Li electrolyte:applications toward nanobatteries

The feasibility of large-scale implementation of Li-air batteries (LABs) hinges on understanding the thermodynamic and kinetic factors that control charge-discharge rates, efficiency and life times. Here, the kinetics of bias-induced reactions is explored locally on the surface of Li-ion conductive glass ceramics, a preferred electrolyte for LABs, using direct current-voltage and strain spectroscopies. Above a critical bias, particle growth kinetics were found to be linear in both the bias and time domains. Partial reversibility was observed for Li particles as evidenced by the presence of anodic peaks following the Li(+) reduction, as well an associated reduction in particle height. The degree of reversibility was highest for the smallest particles formed. These observations thus suggest the possibility of producing nanobatteries with an active anode volume of the order of 0.1 al.

A computational study of the mechanism of CO oxidation by a ceria supported surface rhodium oxide layer

A mechanism of CO oxidation by a thin surface oxide of Rh supported on ceria is proposed: CO is oxidized by the Rh-oxide film, which is subsequently reoxidized by a ceria surface O atom. The proposed mechanism is supported by in situ Raman spectroscopic investigations.

A Lead-Free and High-Energy Density Ceramic for Energy Storage Applications

In this work, we demonstrate a very high-energy density and high-temperature stability capacitor based on SrTiO3-substituted BiFeO3 thin films. An energy density of 18.6 J/cm3 at 972 kV/cm is reported. The temperature coefficient of capacitance (TCC) was below 11% from room temperature up to 200°C. These results are of practical importance, because it puts forward a promising novel and environmentally friendly, lead-free material, for high-temperature applications in power electronics up to 200°C. Applications include capacitors for low carbon vehicles, renewable energy technologies, integrated circuits, and for the high-temperature aerospace sector. © 2013 Crown copyright

A theoretical assessment of surface defect machining and hot machining of nanocrystalline silicon carbide

In this paper, a newly proposed machining method named “surface defect machining” (SDM) [Wear, 302, 2013 (1124-1135)] was explored for machining of nanocrystalline beta silicon carbide (3C-SiC) at 300K using MD simulation. The results were compared with isothermal high temperature machining at 1200K under the same machining parameters, emulating ductile mode micro laser assisted machining (µ-LAM) and with conventional cutting at 300 K. In the MD simulation, surface defects were generated on the top of the (010) surface of the 3C-SiC work piece prior to cutting, and the workpiece was then cut along the <100> direction using a single point diamond tool at a cutting speed of 10 m/sec. Cutting forces, sub-surface deformation layer depth, temperature in the shear zone, shear plane angle and friction coefficient were used to characterize the response of the workpiece. Simulation results showed that SDM provides a unique advantage of decreased shear plane angle which eases the shearing action. This in turn causes an increased value of average coefficient of friction in contrast to the isothermal cutting (carried at 1200 K) and normal cutting (carried at 300K). The increase of friction coefficient however was found to aid the cutting action of the tool due to an intermittent dropping in the cutting forces, lowering stresses on the cutting tool and reducing operational temperature. Analysis shows that the introduction of surface defects prior to conventional machining can be a viable choice for machining a wide range of ceramics, hard steels and composites compared to hot machining.

Piezoelectric properties of PbTiO(3) thin films characterized with piezoresponse force and high resolution transmission electron microscopy

In this paper we investigate the piezoelectric properties of PbTiO(3) thin films grown by pulsed laser deposition with piezoresponse force microscopy and transmission electron microscopy. The as-grown films exhibit an upward polarization, inhomogeneous distribution of piezoelectric characteristics concerning local coercive fields, and piezoelectric coefficient. In fact, the data obtained reveal imprints during piezoresponse force microscopy measurements, nonlinearity in the piezoelectric deformation, and limited polarization reversal. Moreover, transmission electron microscopy shows the presence of defects near the film/substrate interface, which can be associated with the variations of piezoelectric properties.

Graded/Gradient Porous Biomaterials

Biomaterials include bioceramics, biometals, biopolymers and biocomposites and they play important roles in the replacement and regeneration of human tissues. However, dense bioceramics and dense biometals pose the problem of stress shielding due to their high Young's moduli compared to those of bones. On the other hand, porous biomaterials exhibit the potential of bone ingrowth, which will depend on porous parameters such as pore size, pore interconnectivity, and porosity. Unfortunately, a highly porous biomaterial results in poor mechanical properties. To optimise the mechanical and the biological properties, porous biomaterials with graded/gradient porosity, pores size, and/or composition have been developed. Graded/gradient porous biomaterials have many advantages over graded/gradient dense biomaterials and uniform or homogenous porous biomaterials. The internal pore surfaces of graded/gradient porous biomaterials can be modified with organic, inorganic, or biological coatings and the internal pores themselves can also be filled with biocompatible and biodegradable materials or living cells. However, graded/gradient porous biomaterials are generally more difficult to fabricate than uniform or homogenous porous biomaterials. With the development of cost-effective processing techniques, graded/gradient porous biomaterials can find wide applications in bone defect filling, implant fixation, bone replacement, drug delivery, and tissue engineering.

A '3-body' abrasion wear study of bioceramics for total hip joint replacements

The current study focuses on the effect of the material type and the lubricant on the abrasive wear behaviour of two important commercially available ceramic on ceramic prosthetic systems, namely, Biolox(R) forte and Bioloxl(R) delta (CeramTec AG, Germany). A standard microabrasion wear apparatus was used to produce '3-body' abrasive wear scars with three different lubricants: ultrapure water, 25 vol% new-born calf serum solution and 1 wt% carboxymethyl cellulose sodium salt (CMC-Na) solution. 1 mu m alumina particles were used as the abrasive. The morphology of the wear scar was examined in detail using Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM). Subsurface damage accumulation was investigated by Focused Ion Beam (FIB) cross-sectional milling and Transmission Electron Microscopy (TEM). The effect of the lubricant on the '3-body' abrasive wear mechanisms is discussed and the effect of material properties compared. (C) 2009 Elsevier B.V. All rights reserved.

A low temperature, isothermal gas-phase system for conversion of methane to methanol over Cu-ZSM-5

A low temperature, isothermal, gas-phase, recyclable process is described for the partial oxidation of methane to methanol over Cu–ZSM-5. Activation in NO at 150 °C followed by methane reaction and steam extraction (both at 150 °C) allowed direct observation of methanol at the reactor outlet.

Crush responses of composite cylinder under quasi-static and dynamic loading

Despite the abundance of studies investigating the performance of composite structures under crush loading, disagreement remains in the literature regarding the effect of increased strain rate on the crush response. This study reports an experimental investigation of the behaviour of a carbon-epoxy composite energy absorber under static and dynamic loading with a strain rate of up to 100s^-1. Consistent damage modes and measured force responses were obtained in samples tested under the same strain rate. The energy absorption was found to be independent of strain rate as the total energy absorption appeared to be largely associated with fibre-dominated fracture, which is independent of strain rate within the studied range. The results from this study are beneficial for the design of energy absorbing structures.

Finite element modelling of composite structures under crushing load

This paper details the theory and implementation of a composite damage model, addressing damage within a ply (intralaminar) and delamination (interlaminar), for the simulation of crushing of laminated composite structures. It includes a more accurate determination of the characteristic length to achieve mesh objectivity in capturing intralaminar damage consisting of matrix cracking and fibre failure, a load-history dependent material response, an isotropic hardening nonlinear matrix response, as well as a more physically-based interactive matrix-dominated damage mechanism. The developed damage model requires a set of material parameters obtained from a combination of standard and non-standard material characterisation tests. The fidelity of the model mitigates the need to manipulate, or "calibrate", the input data to achieve good agreement with experimental results. The intralaminar damage model was implemented as a VUMAT subroutine, and used in conjunction with an existing interlaminar damage model, in Abaqus/Explicit. This approach was validated through the simulation of the crushing of a cross-ply composite tube with a tulip-shaped trigger, loaded in uniaxial compression. Despite the complexity of the chosen geometry, excellent correlation was achieved with experimental results.

Selection and characterisation of geological materials for use as geopolymer precursors

Geopolymer binders are generally formed by reacting powdered aluminosilicate precursors with alkali silicate activators. Most research to date has concentrated on using either pulverised fuel ash or high purity dehydroxylated kaolin (metakaolin) in association with ground granulated blast furnace slag as the main precursor material. However, recently, attention has turned to alternative calcined clays that are abundant throughout the globe and have lower kaolinite contents than commercially available metakaolins. Due to the lack of clear and simple screening protocols enabling assessment of such geological resources for use as precursors in geopolymer systems, the present paper presents results from experimental work that was carried out to develop a functional binder using materials containing kaolinite taken from the Interbasaltic Formation of Northern Ireland. The influence of mineralogy has been examined, and a screening process, using three Interbasaltic materials as examples, that will assist in the rapid selection of suitable geopolymeric precursors from such materials is outlined.