On the strength of dislocation interactions and their effect on latent hardening in pure Magnesium

This study is dedicated to the quantification of latent hardening and its effect on the plasticity of pure hexagonal magnesium. To this end, discrete dislocation dynamics simulations are used to (1) extract latent hardening parameters coupling different slip systems, and to (2) assess the validity of two existing constitutive models linking slip system strength to dislocation densities on all slip systems. As hexagonal materials deform via activation of different slip modes, each with different mobilities and lattice friction stress, the effects of the latter on latent hardening evolution are also investigated. It is found that the multi-slip formulation proposed by Franciosi and Zaoui gives accurate predictions when multiple interactions are involved while the formulation suggested by Lavrentev and Pokhil systematically overestimates the flow stress. Similar to FCC materials, it is also found that collinear interactions potentially contribute the most to latent hardening. Basal/pyramidal c + a interactions are found to be very strong, while interactions involving second-order pyramidal c + a primary dislocations appear to be the weakest ones. Finally, the latent hardening parameters, extracted from the discrete dislocation dynamics simulations, are used in polycrystal simulations and the impact of finely accounting for latent hardening on predictions of the macroscopic anisotropic response is shown to be of significant importance.

The effect of high yttrium solute concentration on the twinning behaviour of magnesium alloys

The deformation behaviour of two single phase binary alloys, Mg-5Y and Mg-10Y, have been examined. In compression, two twin types were observed, the common {101¯2} twin as well as the less common {112¯1} extension twin. It is shown that the {112¯1} twin is much less sensitive to solute concentration than the {101¯2} twin, and it is suggested that the simple atomic shuffle of the {112¯1} twin reduces the solute strengthening imparted by Y additions. The common {101¯2} twin showed significant hardening as a result of alloying with Y. An analysis of solute behaviour has indicated that of the four chemical parameters investigated, i.e. atomic size, shear modulus, electronegativity and solute distribution, it appears to be the larger atomic radius of Y compared to Mg that increases the stress required to activate the {101¯2} twin. It is suggested that the large atomic radius inhibits the atomic shuffling process which accompanies the twinning shear in this twin type.

Evaluating the effect of yttrium as a solute strengthener in magnesium using in situ neutron diffraction

In situ neutron diffraction of two binary Mg alloys, Mg-0.5 wt.% Y and Mg-2.2 wt.% Y have been carried out in compression. The experimental data has been modelled using the elastoplastic self-consistent methodology in order to determine the critical resolved shear stress for basal slip, second-order 〈c + 〉 pyramidal slip and {101̄2} twinning. It was found that the addition of Y strengthens all three of the deformation modes examined. However, increasing the Y concentration from 0.5% to 2.2% showed no additional hardening in the basal slip and {101̄2} twinning modes, indicating that solute strengthening of these deformation modes is already exhausted by a concentration of 0.5% Y. Second-order pyramidal slip showed additional solute hardening at the higher concentration. © 2014 Published by Elsevier Ltd. on behalf of Acta Materialia Inc. All rights reserved.

Corrosion behavior of Mg-5Al-xZn alloys in 3.5 wt.% NaCl solution

Five types of Mg-5Al alloys with different weight percentages of Zn ranging from 0 to 4 wt.% were examined using electrochemical techniques and surface analysis. The electrochemical results indicated that the Mg-5Al alloys containing Zn have a lower corrosion and hydrogen evolution rates than the Mg-5Al based specimens with a decrease of value being observed with the decrease in Zn content. Zn addition induced the precipitation of Mg-Al and Mg-Zn phases in the Mg matrix along with grain refinement and increased an interaction of Zn oxide with Mg and Al products serving as a corrosion barrier. © 2014 Elsevier B.V. All rights reserved.

No evidence for mirror system dysfunction in schizophrenia from a multimodal TMS/EEG study

Dysfunctional mirror neuron systems have been proposed to contribute to the social cognitive deficits observed in schizophrenia. A few studies have explored mirror systems in schizophrenia using various techniques such as TMS (levels of motor resonance) or EEG (levels of mu suppression), with mixed results. This study aimed to use a novel multimodal approach (i.e. concurrent TMS and EEG) to further investigate mirror systems and social cognition in schizophrenia. Nineteen individuals with schizophrenia or schizoaffective disorder and 19 healthy controls participated. Single-pulse TMS was applied to M1 during the observation of hand movements designed to elicit mirror system activity. Single EEG electrodes (C3, CZ, C4) recorded brain activity. Participants also completed facial affect recognition and theory of mind tasks. The schizophrenia group showed significant deficits in facial affect recognition and higher level theory of mind compared to healthy controls. A significant positive relationship was revealed between mu suppression and motor resonance for the overall sample, indicating concurrent validity of these measures. Levels of mu suppression and motor resonance were not significantly different between groups. These findings indicate that in stable outpatients with schizophrenia, mirror system functioning is intact, and therefore their social cognitive difficulties may be caused by alternative pathophysiology.

Reduced mu suppression and altered motor resonance in euthymic bipolar disorder: evidence for a dysfunctional mirror system?

Social cognitive difficulties are common in the acute phase of bipolar disorder and, to a lesser extent, during the euthymic stage, and imaging studies of social cognition in euthymic bipolar disorder have implicated mirror system brain regions. This study aimed to use a novel multimodal approach (i.e., including both transcranial magnetic stimulation (TMS) and electroencephalogram (EEG)) to investigate mirror systems in bipolar disorder. Fifteen individuals with euthymic bipolar disorder and 16 healthy controls participated in this study. Single-pulse TMS was applied to the optimal site in the primary motor cortex (M1), which stimulates the muscle of interest during the observation of hand movements (goal-directed or interacting) designed to elicit mirror system activity. Single EEG electrodes (C3, CZ, C4) recorded mu rhythm modulation concurrently. Results revealed that the patient group showed significantly less mu suppression compared to healthy controls. Surprisingly, motor resonance was not significantly different overall between groups; however, bipolar disorder participants showed a pattern of reduced reactivity on some conditions. Although preliminary, this study indicates a potential mirror system deficit in euthymic bipolar disorder, which may contribute to the pathophysiology of the disorder.

Effect of twinning on microstructural evolution during dynamic recrystallisation of hot deformed as-cast austenitic stainless steel

An as-cast austenitic stainless steel was hot deformed at 1173 K, 1223 K, and 1373 K (900 °C, 950 °C, and 1100 °C) to a strain of 1 with a strain rate of 0.5 or 5 s⁻¹. The recrystallised fraction is observed to be dependent on dynamic recrystallisation (DRX). DRX grains nucleated at the initial stages of recrystallization have similar orientation to that of the deformed grains. With increasing deformation, Cube texture dominates, mainly due to multiple twinning and grain rotation during deformation.

Performance enhancement of single-walled nanotube-microwave exfoliated graphene oxide composite electrodes using a stacked electrode configuration

We report the development of a stacked electrode supercapacitor cell using stainless steel meshes as the current collectors and optimised single walled nanotubes (SWNT)-microwave exfoliated graphene oxide (mw rGO) composites as the electrode material. The introduction of mw rGO into a SWNT matrix creates an intertwined porous structure that enhances the electroactive surface area and capacitive performance due to the 3-D hierarchical structure that is formed. The composite structure was optimised by varying the weight ratio of the SWNTs and mw rGO. The best performing ratio was the 90% SWNT-10% mw rGO electrode which achieved a specific capacitance of 306 F g-1 (3 electrode measurement calculated at 20 mV s-1). The 90% SWNT-10% mw rGO was then fabricated into a stacked electrode configuration (SEC) which significantly enhanced the electrode performance per volume (1.43 mW h cm-3, & 6.25 W cm-3). Device testing showed excellent switching capability up to 10 A g-1, and very good stability over 10000 cycles at 1.0 A g-1 with 93% capacity retention. © the Partner Organisations 2014.

Electrochemistry of tris(2,2′-bipyridyl) cobalt(II) in ionic liquids and aprotic molecular solvents on glassy carbon and platinum electrodes

The tris(2,2′-bipyridyl) complexes of cobalt(II) and (III) ([Co(bpy)3]^2+/3+) produce a redox couple of great interest in thermoelectrochemical cells and dye sensitized solar cells including both types of devices based on ionic liquid electrolytes. We present a systematic study of the electrochemistry of [Co(bpy)3]²⁺ [NTf2]^-2 in two ionic liquids (ILs) based on the 1-ethyl-3-methylimidazolium (C2mim) cation and two ILs based on the 1-butyl-1-methylpyrrolidinium cation (C4mpyr), as well as three aprotic molecular solvents. Platinum (Pt) and glassy carbon (GC) working electrodes were compared. In all solvents better electrochemical responses were observed on GC, which yielded higher currents in the cyclic voltammograms and lower rate constants for the redox reaction. The [Co(bpy)3]^1+/2+ couple is also readily observed, but this redox reaction is chemically irreversible, possibly because the [Co(bpy)3]¹⁺ complex dissociates. However, the [Co(bpy)3]^1+/2+ reaction is chemically reversible in all of the solvents studied, except 3-methoxypropionitrile, if excess of 2,2′-bipyridyl is added to the solution.

Demonstration of the advantages of using bamboo-like nanotubes for electrochemical biosensor applications compared with single walled carbon nanotubes

The modification of glassy carbon electrodes with random dispersions of nanotubes is currently the most popular approach to the preparation of carbon nanotube modified electrodes. The performance of glassy carbon electrodes modified with a random dispersion of bamboo type carbon nanotubes was compared with single walled carbon nanotubes modified glassy carbon electrodes and bare glassy carbon electrodes. The electrochemical performance of all three types for electrode were compared by investigating the electrochemistry with solution species and the oxidation of guanine and adenine bases of surface adsorbed DNA. The presence of edge planes of graphene at regular intervals along the walls of the bamboo nanotubes resulted in superior electrochemical performance relative to SWNT modified electrodes from two aspects. Firstly, with solution species the peak separation of the oxidation and reduction waves were smaller indicating more rapid rates of electron transfer. Secondly, a greater number of electroactive sites along the walls of the bamboo-carbon nanotubes (BCNTs) resulted in larger current signals and a broader dynamic range for the oxidation of DNA bases.

Lithium doped N-methyl-N-ethylpyrrolidiniumbis(trifluoromethanesulfonyl)amide fast-ion conducting plastic crystals

The incorporation of dopant levels of lithium ions (0.5 to 9.3% by mole) in the N-methyl-N-ethylpyrrolidinium bis(trifluoromethanesulfonyl)amide (P₁₂TFSA) plastic crystalline phase results in increases in the solid state ionic conductivity of more than 3 orders of magnitude at 298 K. Conductivities as high as 10^−-4 S cm⁻¹ at 323 K have been measured in these doped plastic crystal phases. These materials can therefore be classified as fast-ion conductors. Higher levels of Li only marginally increase the conductivity, up to around 33 mol%, followed by a slight decrease to 50 mol%. Thermal analysis behaviour has allowed the partial development of the binary phase diagram for the LiTFSA–P₁₂TFSA system between 0–50 mol% LiTFSA, which suggests the presence of a solid solution single phase at concentrations less than 9.3 mol% LiTFSA. There is also strong evidence of eutectic behaviour in this system with a eutectic transition temperature around 308 K at 33 mol% LiTFSA. A model relating ionic conduction to phase behaviour in this system is presented. The increased conductivity upon doping has been associated with lithium ion motion via⁷Li solid state NMR linewidth measurements.

Single molecule conductance through rigid norbornylogous bridges with zero average curvature

A new homologous series of norbornylogous (NB) bridges has been synthesized in which the average curvature of the bridges is very small. The molecules are rigid and have two thiol moieties at each end to allow them to form self-assembled monolayers (SAMs) and to connect to two gold electrodes to form a molecular junction. The SAMs formed were characterized using electrochemistry to determine the surface coverage of molecules on gold surface and to provide an indication of the packing of the NB bridges while ellipsometry and X-ray photoelectron spectroscopy (XPS) were used to provide an indication of the SAM thickness and orientation. Single molecule conductance of NB bridges was measured as a function of the molecular length. The conductance was found to decrease exponentially with the length with a decay constant that is exactly correlated with photoelectron transfer and other studies at the multiple molecule level. The molecule−electrode contact resistance was determined and compared with that of related alkanedithiol molecular junctions.

Direct measurement of surface forces between sapphire crystals in aqueous solutions

Measurements are presented of the electrical double layer and van der Waals forces between the (0001) surfaces of two single-crystal sapphire platelets immersed in an aqueous solution of NaCl at pH values from 6.7 to 11. The results fit the standard Deryaguin-Landau-Verwey-Overbeek (DLVO) theory, with a Hamaker constant of 6.7 × 10−20 J. These are the first measurements made using the Israelachvili surface forces apparatus without mica as a substrate material, and they demonstrate the possibility of using this technique to explore the surface chemistry of a wider range of materials.

Halogen-free chelated orthoborate ionic liquids and organic ionic plastic crystals

Five halogen-free orthoborate salts comprised of three different cations (cholinium, pyrrolidinium and imidazolium) and two orthoborate anions, bis(mandelato)borate and bis(salicylato)borate, were synthesised and characterised by DSC, X-ray diffraction and NMR. DSC measurements revealed that glass transition points of these orthoborate salts are in the temperature range from −18 to −2 °C. In addition, it was found that [EMPy][BScB] and [EMIm][BScB] salts have solid–solid phase transitions below their melting points, i.e. they exhibit typical features of plastic crystals. Salts of the bis(salicylato)borate anion [BScB]− have higher melting points compared with corresponding salts of the bis(mandelato)borate anion [BMB]−. Single crystal X-ray diffraction crystallography (for [Chol][BScB] crystals) and solid-state multinuclear (13C, 11B and 15N) NMR spectroscopy were employed for the structural characterisation of [Chol][BScB], [EMPy][BScB] and [EMIm][BScB], which are solids at room temperature: a strong interaction between [BScB]− anions and [Chol]+ cations was identified as (i) hydrogen bonding between OH of [Chol]+ and carbonyl groups of [BScB]− and (ii) as the inductive C–Hπ interaction. In the other salt, [EMIm][BScB], anions exhibit ππ stacking in combination with C–Hπ interactions with [EMIm]+ cations. These interactions were not identified in [EMPy][BScB] probably because of the lack of aromaticity in cations of the latter system. Our data on the formation of a lanthanum complex with bis(salicylato)borate in the liquid mixture of La3+(aq) with [Chol][BScB] suggest that this class of novel ILs can be potentially used in the extraction processes of metal ions of rare earth elements.

Organic Solvent-Based Graphene Oxide Liquid Crystals: A Facile Route toward the Next Generation of Self-Assembled Layer-by-Layer Multifunctional 3D Architectures

We introduce soft self-assembly of ultralarge liquid crystalline (LC) graphene oxide (GO) sheets in a wide range of organic solvents overcoming the practical limitations imposed on LC GO processing in water. This expands the number of known solvents which can support amphiphilic self-assembly to ethanol, acetone, tetrahydrofuran, N-dimethylformamide, N-cyclohexyl-2-pyrrolidone, and a number of other organic solvents, many of which were not known to afford solvophobic self-assembly prior to this report. The LC behavior of the as-prepared GO sheets in organic solvents has enabled us to disperse and organize substantial amounts of aggregate-free single-walled carbon nanotubes (SWNTs, up to 10 wt %) without compromise in LC properties. The as-prepared LC GO-SWNT dispersions were employed to achieve self-assembled layer-by-layer multifunctional 3D hybrid architectures comprising SWNTs and GO with unrivalled superior mechanical properties (Young’s modulus in excess of 50 GPa and tensile strength of more than 500 MPa).