Solid state recycling of 5083 Al alloy by hot extrusion

The machined chips of 5083 Al alloy were recycled by hot extrusion at 723 K with an extrusion ratio of 44:1 in air. Corrosion and mechanical properties of the recycled specimens have been compared with those of a virgin extrusion which was processed from the ingot block. As a result of salt immersion tests, mass loss of the recycled specimen was not less than twice of that of the virgin extrusion. The deterioration in corrosion properties for the recycled specimen was attributed to the excessive contamination of Fe which promoted galvanic corrosion. As a result of tensile tests, the recycled specimen exhibited a good combination of high strength and high elongation to failure at room temperature. The excellent mechanical properties for the recycled specimen were attributed to the refined microstructure. However, the elongation to failure of the recycled specimen at elevated temperatures more than 573 K was lower than that of the virgin extrusion. The contamination of oxide particles is likely to be responsible for the lower elongation in the solid recycled specimen.

The 'filler-effect' in organic ionic plastic crystals : Enhanced conductivity by the addition of nano-sized TiO2

The addition of nano-sized ceramic particles to the plastic crystal ethyl-methyl pyrrolidinium bis(trifluoromethane sulfonyl)amide (P₁₂TFSA) has been investigated by means of DSC and conductivity. The thermal behaviour of the plastic crystal as a function of filler content suggests that the filler particles decrease the onset temperature of the melting slightly at high loadings, however they do not decrease the crystallinity of the material. Furthermore, the IV → III transition decreases in intensity, indicating that the addition of filler increases the possibility for the crystal to remain in metastable rotator phases also at lower temperatures. The conductivity shows a more than one order of magnitude increase with the addition of filler, with a filler concentration dependence that levels out above ~ 10 wt.% TiO₂.

Rotational and translational mobility of a highly plastic salt : Dimethylpyrrolidinium thiocyanate

Thermal analysis, impedance spectroscopy, NMR and Raman spectroscopy have been used to investigate the plastic crystal dimethylpyrrolidinium thiocyanate in order to gain further insight into the properties of organic ionic plastic crystals. This compound has a solid–solid phase transition at 82 °C, and melts at 122 °C. A step increase in conductivity of about one order of magnitude is observed at the phase transition, followed by a decrease in activation energy for conduction. A large entropy gain occurs at the II → I transition, and ¹H NMR linewidth measurements together with second moment calculations showed that the dimethylpyrrolidinium cation goes from a static state, to full isotropic tumbling. Raman measurements confirm that the cation as well as the anion exhibit increased rotational mobility when entering phase I.

Ab initio calculations, Raman and NMR investigation of the plastic crystal di-methyl pyrrolidinium iodide

Above 110 °C the symmetric di-methyl-pyrrolidinium iodide salt forms a plastic crystal phase of interest in the area of new electrolyte materials. In this study ab initio calculations of this material has been conducted in order to assign the vibrational spectra. Raman spectroscopy measurements on the solid salt as well as on the salt dissolved in different solvents has been performed and these have been compared to the theoretical spectra. Furthermore, Raman spectra as a function of temperature have been recorded to investigate possible changes in inter-ionic interaction and/or structure through the phase transition. 1H NMR linewidth measurements as a function of temperature showed a large decrease in linewidth above 100 °C, attributed here to an increase in mobility in agreement with a previously reported phase transition at ~110 °C.

Plastic crystal behaviour in tetraethylammonium dicyanamide

The plastic crystal tetraethylammonium dicyanamide ([N_2,2,2,2][dca]) has been investigated with an emphasis on structure and dynamics in the plastic phase. It was found that almost all of the volume expansion occurs at the II → I transition, with no volume expansion at the melt transition (as normally observed for crystals). The conductivity of this material shows a rapid increase at temperatures below the II → I transition, reaching values ~ 10^{− 3} S/cm in Phase I, and 0.1 S/cm in the melt. The NMR measurements show that there is a sudden onset of rotational motions of the cations at the plastic transition; below this temperature the cations appear static. The rotational motion of the cation in Phase I has been discussed in terms of isotropic tumbling.

High mobility I− / I3− redox couple in a molecular plastic crystal: A potential new generation of electrolyte for solid-state photoelectrochemical cells

A series of new electrolyte materials based on a molecular plastic crystal doped by different iodide salts together with iodine have been prepared and characterized by thermal analysis, ionic conductivity, electrochemical and solid-state NMR diffusion measurements. In these materials, the plastic crystal phase of succinonitrile acts as a good matrix for the quaternary ammonium based iodides and iodine and appears to act in some cases as a solid-state “solvent” for the binary dopants. The materials were prepared by mixing the components in the molten state with subsequent cooling into the plastic crystalline state. This resulted in waxy-solid electrolytes in the temperature range from − 40 to 60 °C. The combination of structural variation of the cations, and fast redox couple diffusion (comparable with liquid-based electrolytes), as well as a high ionic conductivity of up to 3 × 10^{− 3} S cm^{− 1} at ambient temperature, make these materials very attractive for potential use in solid-state photoelectrochemical cells.

Rapid I−/I3− diffusion in a molecular-plastic-crystal electrolyte for potential application in solid-state photoelectrochemical cells

High current-carrying capacity and rapid, liquidlike diffusion were achieved in a dye-sensitized solar cell (DSSC) based on the plastic-crystalline electrolyte succinonitrile and the I⁻/I₃⁻ redox couple (see diagram). This could lead to the development of true solid-state DSSCs without conventional organic-liquid electrolytes, which can cause problems with long-term device stability.

Structure and transport properties in an N,N-substituted pyrrolidinium tetrafluoroborate plastic crystal system

The structure and transport of N-propyl-N-methylpyrrolidinium tetrafluoroborate (P₁₃BF₄) has been investigated over a wide temperature range in consequence to exhibiting properties suitable for potential solid-state superionic electrolyte applications. Prior to melting, the organic salt, P₁₃BF₄, transforms into a plastic crystal phase. Intrinsic conductivity in this solid, phase I (45–65 °C), is comparable to that in the melt (_~10⁻³ S cm⁻¹). Ionic motion and transport properties were investigated by ¹H and ¹¹B nuclear magnetic resonance (NMR) spectroscopy. Pressure-induced plastic flow in this system may accommodate volume changes in device application and to this extent, X-ray diffraction (XRD) has been used. Scanning electron microscopy (SEM) revealed complex surface morphology and lattice imperfections associated with the strong orientational disorder of the plastic state.

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.

N-methyl-N-alkylpyrrolidinium nonafluoro-1-butanesulfonate salts : Ionic liquid properties and plastic crystal behaviour

A series of N-methyl-N-alkylpyrrolidinium nonafluoro-1-butanesulfonate salts were synthesised and characterised. The thermophysical characteristics of this family of salts have been investigated with respect to potential use as ionic liquids and solid electrolytes. N-Methyl-N-butylpyrrolidinium nonafluoro-1-butanesulfonate (p_1,4NfO) has the lowest melting point of the family, at 94 °C. Electrochemical analysis of p_1,4 NfO in the liquid state shows an electrochemical window of ~6 V. All compounds exhibit one or more solid–solid transitions at sub-ambient temperatures, indicating the existence of plastic crystal phases.