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.

Plastic crystal phases with high proton conductivity

The addition of up to 4 mol% of the strong acids, trifluoromethane sulfonic acid (TfOH) and bis-trifluoromethanesulfonyl imide [HN(Tf) 2], to the organic ionic plastic crystal (OIPC) [Choline][DHP] has been shown to dramatically increase the ionic conductivity by up to three orders of magnitude whilst still retaining the crystalline structure of the OIPC matrix. This enhanced proton diffusivity led to a significant proton reduction reaction in the electrochemical measurements. Powder XRD and DSC thermal analyses strongly suggest that these mixtures are single phase, crystalline materials. The work here also confirms that an increase in TfOH acid concentration (8 mol% and 12 mol%) results in a higher content of the amorphous phase as previously observed for the H 3PO 4/[Choline][DHP] system. © 2012 The Royal Society of Chemistry.

Finite element analysis of plastic deformation in variable lead axisymmetric forward spiral extrusion

A modified axisymmetric forward spiral extrusion (AFSE) has been proposed recently to enhance the strain accumulation during the process. The new technique is called variable lead axisymmetric forward spiral extrusion (VLAFSE) that features a variable lead along the extrusion direction. To assess the effect of design modification on plastic deformation, a comprehensive study has been performed here using a 3D transient finite element (FE) model. The FE results established the shear deformation as the dominant mode of deformation which has been confirmed experimentally. The variable lead die extends strain accumulation in the radial and longitudinal directions over the entire grooved section of the die and eliminates the rigid body rotation which occurs in the case of a constant lead die, AFSE. A comparison of forming loads for VLAFSE and AFSE proved the advantages of the former design in the reduction of the forming load which is more pronounced under higher frictional coefficients. This finding proves that the efficiency of VLAFSE is higher than that of AFSE. Besides, the significant amount of accumulated shear strain in VLAFSE along with non-axisymmetric distribution of friction creates a surface feature in the processed sample called zipper effect that has been investigated. © 2012 Springer Science+Business Media New York.

Structure and transport properties of a plastic crystal ion conductor : Diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate

Understanding the ion transport behavior of organic ionic plastic crystals (OIPCs) is crucial for their potential application as solid electrolytes in various electrochemical devices such as lithium batteries. In the present work, the ion transport mechanism is elucidated by analyzing experimental data (single-crystal XRD, multinuclear solid-state NMR, DSC, ionic conductivity, and SEM) as well as the theoretical simulations (second moment-based solid static NMR line width simulations) for the OIPC diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate ([P1,2,2,4][PF6]). This material displays rich phase behavior and advantageous ionic conductivities, with three solid–solid phase transitions and a highly “plastic” and conductive final solid phase in which the conductivity reaches 10–3 S cm–1. The crystal structure shows unique channel-like packing of the cations, which may allow the anions to diffuse more easily than the cations at lower temperatures. The strongly phase-dependent static NMR line widths of the 1H, 19F, and 31P nuclei in this material have been well simulated by different levels of molecular motions in different phases. Thus, drawing together of the analytical and computational techniques has allowed the construction of a transport mechanism for [P1,2,2,4][PF6]. It is also anticipated that utilization of these techniques will allow a more detailed understanding of the transport mechanisms of other plastic crystal electrolyte materials.

A study of plastic deformation during axisymmetric forward spiral extrusion and its subsequent mechanical property changes

Axisymmetric forward spiral extrusion (AFSE) accumulates large strains in its sample while extruding it through a die with engraved spiral grooves. A three-dimensional finite element model of AFSE has been developed using ABAQUS to investigate the deformation mode in detail, including the effect of groove geometry and the heterogeneity of plastic deformation. The numerical results demonstrated that the strain distribution in the AFSE sample cross section is linear in the radial direction within a concentric core while the distribution, outside the core, in the vicinity of the grooves is non-linear and non-axisymmetric. Mechanical properties and grain structure changes of the deformed sample were investigated. Improvements of mechanical properties in the processed samples can be attributed to the domination of the shear deformation mode in a plane normal to the extrusion axis and consequently the elongation of grains in the tangential direction

Thin and flexible solid-state organic ionic plastic crystal-polymer nanofibre composite electrolytes for device applications

All solid-state organic ionic plastic crystal–polymer nanofibre composite electrolytes are described for the first time. The new composite materials exhibit enhanced conductivity, excellent thermal, mechanical and electrochemical stability and allow the production of optically transparent, free-standing, flexible, thin film electrolytes (10’s lms thick) for application in electrochemical devices. Stable cycling of a lithium cell incorporating the new composite electrolyte is demonstrated, including cycling at lower temperatures than previously possible with the pure material.