Control of magnesium interfacial reactions in aqueous electrolytes towards a biocompatible battery

A stable magnesium battery has been developed based on a magnesium anode, a poly(dioxyethane thiophene) (PEDOT) cathode and a near-saturated aqueous solution of LiCl, MgCl₂, or mixture of these salts at pH of 11. This combination leads to a low water activity in the electrolyte, which thus suppresses the hydrogen evolution reaction on Mg, as well as producing a stable oxy-hydroxide film which protects the metal surface from freely corroding. The conducting polymer cathode is reduced somewhat during the discharge process, however, appears to be readily re-oxidised (as determined from the resistance) by the oxygen present in the cell. The cell is therefore primarily a Mg/O₂ battery, however, the PEDOT appears to enhance the performance, in particular the discharge voltage.

Biocompatible ionic liquid-biopolymer electrolyte-enabled thin and compact magnesium-air batteries.

With the surge of interest in miniaturized implanted medical devices (IMDs), implantable power sources with small dimensions and biocompatibility are in high demand. Implanted battery/supercapacitor devices are commonly packaged within a case that occupies a large volume, making miniaturization difficult. In this study, we demonstrate a polymer electrolyte-enabled biocompatible magnesium-air battery device with a total thickness of approximately 300 μm. It consists of a biocompatible polypyrrole-para(toluene sulfonic acid) cathode and a bioresorbable magnesium alloy anode. The biocompatible electrolyte used is made of choline nitrate (ionic liquid) embedded in a biopolymer, chitosan. This polymer electrolyte is mechanically robust and offers a high ionic conductivity of 8.9 × 10(-3) S cm(-1). The assembled battery delivers a maximum volumetric power density of 3.9 W L(-1), which is sufficient to drive some types of IMDs, such as cardiac pacemakers or biomonitoring systems. This miniaturized, biocompatible magnesium-air battery may pave the way to a future generation of implantable power sources.

Influence of deformation conditions and texture on the high temperature flow stress of magnesium AZ31

The evolution of hot working flow stress with strain is examined in torsion, uniaxial compression and channel die compression. The flow stress was found to be strongly dependent on texture and deformation mode. At low strains this dependency accounted for a difference in flow stress of up to a factor of two. At higher strains the influence of texture and deformation mode was less marked. The stresses corresponding to an equivalent strain of 0.5 were modelled using a power law expression with an activation energy of 147 kJ/mol and a strain rate exponent of 0.15. The influence of texture and deformation mode on flow stress is rationalised in terms of the influence of prismatic slip, twinning and dynamic recrystallisation on deformation stress and structure.

Quenched and annealed microstructures of hot worked magnesium AZ31

The microstructures of magnesium AZ31 are examined following hot compression testing and annealing. The grain size, fraction dynamically recrystallized and, in a couple of cases, the crystallographic texture are reported. The progress of dynamic recrystallization and the recrystallized grain size were sensitive to processing conditions, as expected. This effect was more marked in the former than in the latter, compared to other metals. It was also found that, for structures containing between 80 and 95% dynamic recrystallization, abnormal grain growth occurred during annealing. Irrespective of the whether or not abnormal grain growth occurred, the annealing step weakened the crystallographic texture.

Recrystallization during and following hot working of magnesium alloy AZ31

The microstructures of magnesium AZ31 are examined following hot compression testing and annealing. The grain size, fraction dynamically recrystallized and, in a couple of cases, the crystallographic texture are reported. It was found that the progress of dynamic recrystallization is strongly sensitive to processing conditions but that the dynamically
recrystallized grain size was less sensitive to stress than in other metals. It was also found that, for structures containing between 80 and 95 % dynamic recrystallization, abnormal grain growth occurs during annealing. The crystallographic texture produced is also sensitive to the deformation conditions.

A Taylor Model Based Description of the proof stress of magnesium AZ31 during hot working

A series of hot-compression tests and Taylor-model simulations were carried out with the intention of developing a simple expression for the proof stress of magnesium alloy AZ31 during hot working. A crude approximation of wrought textures as a mixture of a single ideal texture component and a random background was employed. The shears carried by each deformation system were calculated using a full-constraint Taylor model for a selection of ideal orientations as well as for random textures. These shears, in combination with the measured proof stresses, were employed to estimate the critical resolved shear stresses for basal slip, prismatic slip, ⟨c+a⟩ second-order pyramidal slip, and { } twinning. The model thus established provides a semianalytical estimation of the proof stress (a one-off Taylor simulation is required) and also indicates whether or not twinning is expected. The approach is valid for temperatures between ∼150 °C and ∼450 °C, depending on the texture, strain rate, and strain path.

Hot working microstructure map for magnesium AZ31

A thermomechanical processing (TMP) structure map is proposed that plots the critical strains required for dynamic recrystallization along with the grain sizes that result. These maps are useful in identifying the limits to grain refinement and designing hot working processes. They are readily constructed for well studied alloys such as plain carbon steel. In light of the recent interest in the hot working of magnesium, initial steps are taken here to construct a TMP structure map for the most common wrought magnesium alloy, AZ31. The completion of dynamic recrystallization is estimated using a geometrical approach and a twinning region is identified.

Method for determining reaction rate of mild steel containers during melting of magnesium-aluminium alloys and effect of aluminium content on directionally solidified microstructures

A magnesium alloy of eutectic composition (33 wt-'%Al) was directionally solidified in mild steel tubes at two growth rates, 32 and 580 mum s(-1,) in a temperature gradient between 10 and 20 K mm(-1). After directional solidification, the composition of each specimen varied dramatically, from 32'%Al in the region that had remained solid to 18%Al (32 mum s(-1) specimen) and 13%Al (580 mum s(-1) specimen) at the plane that had been quenched from the eutectic temperature. As the aluminium content decreased, the microstructure contained an increasing volume fraction of primary magnesium dendrites and the eutectic morphology gradually changed from lamellar to partially divorced. The reduction in aluminium content was caused by the growth of an Al-Fe phase ahead of the Mg-Al growth front. Most of the growth of the Al-Fe phase occurred during the remelting period before directional solidification. The thickness of the Al-Fe phase increased with increased temperature and time of contact with the molten Mg-Al alloy. (C) 2003 Maney Publishing.

Compressibility of porous magnesium foam: dependency on porosity and pore size

Mechanical properties of porous magnesium with the porosity of 35–55% and the pore size of about 70–400 μm are investigated by compressive tests focusing on the effects of the porosity and pore size on the Young's modulus and strength. Results indicated that the Young's modulus and peak stress increase with decreasing porosity and pore size. The mechanical properties of the porous magnesium were in a range of those of cancellous bone. Therefore, it is suggested that the porous magnesium is one of promising scaffold materials for hard tissue regeneration.

The influence of twinning on the hot working flow stress and microstructural evolution of magnesium alloy AZ31

The microstructural evolution during compression (at 350°C and a strain rate of 0.01s-1) was examined for magnesium alloy AZ31 received in the "as-cast" condition. It was revealed that at low strains, many twins are produced and dynamically recrystallized (DRX) grains form as a necklace along pre-existing grain boundaries. At higher strains, DRX stagnates, most likely due to the accommodation of deformation in the DRX fraction of the material. It was also observed that twin boundaries act as sites for the nucleation of DRX grains. The analysis was repeated for samples pre-compressed to a strain of 0.15 at room temperature prior to the hot deformation step. The idea of these additional tests was to increase the degree of twinning and therefore the density of sites for the nucleation of DRX. It was found that statically recrystallized (SRX) grains developed at the twins during heating to the test temperature. When these samples were deformed, the peak flow stress was reduced by approximately 20% and the development of DRX was enhanced. This can be attributed to the accelerated nucleation of DRX in the refined SRX structure.

Texture, twinning and uniform elongation of wrought magnesium

A small number of crystal plasticity simulations and tensile tests are carried out with the aim of demonstrating that control of twinning can improve the uniform elongation of magnesium based alloys, It is suggested that this can be accomplished through texture manipulation because texture influences both the fraction of grains that undergo twinning and the strain required for the twinning reaction to go to completion.

An analytical constitutive law for twinning dominated flow in magnesium

The progress of “c-axis tension” twinning in magnesium is represented in an analytical framework and this is used as a basis for predicting the flow stress. The difference in the stress–strain curves between tension and compression can thus be modelled with a change to a parameter that reflects the fraction of grains that undergo twinning.