Lithium-doped plastic crystal electrolytes exhibiting fast ion conduction for secondary batteries

Rechargeable lithium batteries have long been considered an attractive alternative power source for a wide variety of applications. Safety and stability1 concerns associated with solvent-based electrolytes has necessitated the use of lithium intercalation materials (rather than lithium metal) as anodes, which decreases the energy storage capacity per unit mass. The use of solid lithium ion conductors - based on glasses, ceramics or polymers - as the electrolyte would potentially improve the stability of a lithium metal anode while alleviating the safety concerns. Glasses and ceramics conduct via a fast ion mechanism, in which the lithium ions move within an essentially static framework. In contrast, the motion of ions in polymer systems is similar to that in solvent-based electrolytes - motion is mediated by the dynamics of the host polymer, thereby restricting the conductivity to relatively low values. Moreover, in the polymer systems, the motion of the lithium ions provides only a small fraction of the overall conductivity2, which results in severe concentration gradients during cell operation, causing premature failure3. Here we describe a class of materials, prepared by doping lithium ions into a plastic crystalline matrix, that exhibit fast lithium ion motion due to rotational disorder and the existence of vacancies in the lattice. The combination of possible structural variations of the plastic crystal matrix and conductivities as high as 2 3 1024 S cm21 at 60 8C make these materials very attractive for secondary battery applications.

Deformation and frictional heating in relation to wear in sheet metal stamping

In the automotive industry, press production rates often need to be reduced in order to minimize tool wear issues and successfully stamp advanced high strength steels. This indicates that heating affects may be important. This paper examines friction and deformational heating at the die radius during sheet metal stamping, using finite element analysis. The results show that high temperatures, of up to 130°C, can occur at the die radius surface. Such behavior has not been previously reported in the literature, for what is expected to be ‘cold’ sheet metal stamping conditions. It will be shown that the temperature rise is due to the increased contact stresses and increased plastic work, associated with stamping AHSS. Consequently, new insights into the local contact conditions in sheet metal stamping were obtained. The outcomes of this work may impact the wear models and tests employed for future tool wear analyses in sheet metal stamping.

Sensitivity of deformation twinning to grain size in titanium and magnesium

The impact of grain size on deformation twinning in commercial purity titanium and magnesium alloy Mg–3Al–1Zn (AZ31) is investigated. Tensile tests were carried out for the titanium samples; compression testing was employed for the magnesium specimens. Average values of the true twin length, true twin thickness and the number density of twins were determined using stereology. A key difference between these two materials is that twinning contributes little to the plastic strain in the titanium while it accounts for nearly all of the early plastic strain in the magnesium. In some respects (e.g. volume fraction and number density) the phenomenology of twinning differed between the two materials, while in others (e.g. twin shape and size) both materials showed a similar response. It is found that in both materials, twins span the entirety of their parent grains only for grain sizes less than ∼30 μm. Both the nucleation density per unit of nucleating interface (i.e. grain and twin boundaries) and the aspect ratio of twins scale with applied stress. The impact of grain size on twin volume fraction is modelled analytically.

Effect of grain size on deformation twinning in a magnesium alloy and commercial purity titanium

This data collection contains several optical microstructure images, EBSD maps and stress-strain curves. The research involves collecting data from samples with different grain sizes at several values of plastic strains to measure some important twinning parameters such as twin volume fraction and number of twins per grain. The aim of this study is to investigate the effect of grain size on deformation twinning behaviour in two hcp metals i.e. commercial purity titanium and AZ31 magnesium alloy.

The effect of deformation twinning on stress localization in a three dimensional TWIP steel microstructure

We present an investigation of the effect of deformation twinning on the visco-plastic response and stress localization in a low stacking fault energy twinning-induced plasticity (TWIP) steel under uniaxial tension loading. The three-dimensional full field response was simulated using the fast Fourier transform method. The initial microstructure was obtained from a three dimensional serial sectionusing electron backscatter diffraction. Twin volume fraction evolution upon strain was measured so the hardening parameters of the simple Voce model could be identified to fit both the stress-strain behavior and twinning activity. General trends of texture evolution were acceptably predicted including the typical sharpening and balance between the 1 1 1 fiber and the 1 0 0 fiber. Twinning was found to nucleate preferentially at grain boundaries although the predominant twin reorientation scheme did not allow spatial propagation to be captured. Hot spots in stress correlated with the boundaries of twinned voxel domains, which either impeded or enhanced twinning based on which deformation modes were active locally.

Development of a laboratory-based transmission diffraction technique for in situ deformation studies of Mg alloys

A laboratory-based transmission X-ray diffraction technique was developed to measure elastic lattice strains parallel to the loading direction during in situ tensile deformation. High-quality transmission X-ray diffraction data were acquired in a time frame suitable for in situ loading experiments by application of a polycapillary X-ray optic with a conventional laboratory Cu X-ray source. Based on the measurement of two standard reference materials [lanthanum hexaboride (NIST SRM 660b) and silicon (NIST SRM 640c)], precise instrumental alignment and calibration of the transmission diffraction geometry were realized. These results were also confirmed by the equivalent data acquired using the standard Bragg-Brentano measurement geometry. An empirical Caglioti function was employed to describe the instrumental broadening, while an axis of rotation correction was used to measure and correct the specimen displacement from the centre of the goniometer axis. For precise Bragg peak position and hkil intensity information, a line profile fitting methodology was implemented, with Pawley refinement used to measure the sample reference lattice spacings (d o (hkil)). It is shown that the relatively large X-ray probe size available (7 × 714mm) provides a relatively straightforward approach for improving the grain statistics for the study of metal alloys, where grain sizes in excess of 114μm can become problematic for synchrotron-based measurements. This new laboratory-based capability was applied to study the lattice strain evolution during the elastic-plastic transition in extruded and rolled magnesium alloys. A strain resolution of 2 × 10-4 at relatively low 2θ angles (20-65° 2θ) was achieved for the in situ tensile deformation studies. In situ measurement of the elastic lattice strain accommodation with applied stress in the magnesium alloys indicated the activation of dislocation slip and twin deformation mechanisms. Furthermore, measurement of the relative change in the intensity of 0002 and 10 3 was used to quantify {10 2} 011 tensile twin onset and growth with applied load.

Deformation field variations in equal channel angular extrusion due to back pressure

Flow lines were analysed in aluminium alloy 6061 during equal channel angular extrusion (ECAE) in a 90° die with and without the application of back pressure during pressing. The lines appeared much more rounded when a back pressure was applied compared to the case of conventional ECAE testing. With the help of an analytic flow function, the deformation field was obtained. It is shown that back pressure slightly lowers the total strain, strongly increases the size of the plastic zone and significantly reduces the plastic strain rate.

Influence of backpressure during ECAP on the monotonic and cyclic deformation behavior of AA5754 and Cu99.5

Ultrafine-grained (UFG) metals produced by equal channel angular pressing (ECAP) exhibit outstanding mechanical properties. They show high strength under monotonic loading as well as strongly enhanced fatigue lives in the Wöhler S-N-plot compared to their coarse grained (CG) counterparts. It could be shown that the fatigue lives can be significantly enhanced further by applying backpressure during ECAP. Besides the positive effect of backpressure on the processability of hard to deform materials via ECAP, the hydrostatic stress induced by backpressure also influences the mechanical properties under monotonic and cyclic loading. Therefore the influence of backpressure on ECAPed Cu99.5 and on the ECAPed aluminum alloy AA5754 was investigated. It is shown that backpressure has no effect on the hardness and grain size in Cu99.5 but changes the grain boundary misorientation to higher fractions of low angle grain boundaries. Also the temperature dependency of the yield strength as well as the hardening behavior under monotonic compression is affected. The cyclic deformation behavior of Cu99.5 is not strongly influenced by backpressure, but the mean stress level changes drastically. The fatigue life increases with the application of backpressure at low plastic amplitudes due to a change in the crack initiation and propagation. Aim of this work is the investigation of the influence of backpressure during equal channel angular pressing (ECAP) on the mechanical properties under monotonic and cyclic loading. Therefore we performed hardness measurements, compression, and fatigue tests on ECAPed Cu99.5 and AA5754. The results are discussed in terms of microstructure and relevant deformation and damage mechanisms.

The effect of ageing on the compressive deformation of Mg-Sn-Zn-Na alloy

The influence of ageing on deformation twinning in an extruded Mg-6Sn-3Zn-0.04Na alloy is investigated. In-situ compression tests have been carried out using high resolution synchrotron X-Ray Diffraction (XRD) to measure the influence of precipitates on twining activity. Synchrotron experiments revealed the increase in the critical resolved shear stress of twinning with ageing. The compressive yield strength (along the extrusion direction) of the aged sample increased by ∼ 150% over the non-aged specimen. To obtain statistical insight into the twinning activity, the microstructure of the non-aged and aged samples (200°C, 24 hours) deformed up to ∼1% plastic strain was studied using optical microscopy. A higher number of thinner twins were observed in the microstructure of the aged sample compared to the non-aged sample.