New insights into the thermal behaviour of organic ionic plastic crystals: magnetic resonance imaging of polycrystalline morphology alterations induced by solid-solid phase transitions

Organic ionic plastic crystals (OIPCs) show strong potential as solid-state electrolytes for lithium battery applications, demonstrating promising electrochemical performance and eliminating the need for a volatile and flammable liquid electrolyte. The ionic conductivity (σ) in these systems has recently been shown to depend strongly on polycrystalline morphology, which is largely determined by the sample's thermal history. [K. Romanenko et al., J. Am. Chem. Soc., 2014, 136, 15638]. Tailoring this morphology could lead to conductivities sufficiently high for battery applications, so a more complete understanding of how phenomena such as solid-solid phase transitions can affect the sample morphology is of significant interest. Anisotropic relaxation of nuclear spin magnetisation provides a new MRI based approach for studies of polycrystalline materials at both a macroscopic and molecular level. In this contribution, morphology alterations induced by solid-solid phase transitions in triisobutyl(methyl)phosphonium bis(fluorosulfonyl)imide (P1444FSI) and diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate (P1224PF6) are examined using magnetic resonance imaging (MRI), alongside nuclear magnetic resonance (NMR) spectroscopy, diffusion measurements and conductivity data. These observations are linked to molecular dynamics and structural behaviour crucial for the conductive properties of OIPCs. A distinct correlation is established between the conductivity at a given temperature, σ(T), and the intensity of the narrow NMR signal that is attributed to a mobile fraction, fm(T), of ions in the OIPC. To explain these findings we propose an analogy with the well-studied relationship between permeability (k) and void fraction (θ) in porous media, with k(θ) commonly quantified by a power-law dependence that can also be employed to describe σ(fm).

Crystal structures and textures in the hot-forged Ni-Mn-Ga shape memory alloys

Three ferromagnetic shape-memory alloys with the chemical compositions of Ni₅₃Mn₂₅Ga₂₂, Ni₄₈Mn₃₀Ga₂₂, and Ni₄₈Mn₂₅Ga₂₂Co₅ were prepared by the induction-melting and hot-forging process. The crystal structures were investigated by the neutron powder diffraction technique, showing that Ni₅₃Mn₂₅Ga₂₂ and Ni₄₈Mn₂₅Ga₂₂Co₅ have a tetragonal, 14/mmm martensitic structure at room temperature, while Ni₄₈Mn₃₀Ga₂₂ has a cubic, L2₁ austenitic structure at room temperature. The development of textures in the hot-forged samples shows the in-plane plastic flow anisotropy from the measured pole figures by means of the neutron diffraction technique. Significant texture changes were observed for the Ni₄₈Mn₂₅Ga₂₂Co₅ alloy after room temperature deformation, which is due to the deformation-induced rearrangements of martensitic variants. An excellent shape-memory effect (SME) with a recovery ratio of 74 pct was reported in this Ni₄₈Mn₂₅Ga₂₂Co₅ polycrystalline alloy after annealing above the martensitic transformation temperature, and the “shape-memory” influence also occurs in the distributions of grain orientations.

Influence of grain size and training temperature on strain of polycrystalline Ni50Mn29Ga21 samples

The alloy Ni-Mn-Ga aroused great interest for application as a magnetic shape memory (MSM) material. This effect is caused by reorientation of twin variants by an external magnetic field. So far, most of the experiments were concentrated on single crystals. But, the MSM effect can also be realised in polycrystals which can be prepared much more efficiently. Here, polycrystalline samples were prepared by directional solidification with a <100> fibre texture of the high temperature cubic austenitic phase parallel to the heat flow. Afterwards, a heat treatment was applied for chemical homogenisation and stress relaxation in the austenitic state. Then the samples were heated up to the austenitic state and cooled down under load. The microstructure was analysed by Electron Back Scatter Diffraction (EBSD) before and after that treatment. Mechanical training at room temperature and 40°C was tracked by recording stress-strain curves. By increasing the number of training cycles the strain also increases. The influence of different training temperatures was investigated on samples with different grain sizes.