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.

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.

Temperature-dependence of mechanical properties of open-cell titanium foam

An open-cell titanium foam with relative density of 0.2 was prepared by powder metallurgical process. The compressive mechanical properties of the foam at the different temperatures in the range of 20-600°C were measured and the temperature-dependence of its mechanical properties was discussed. The results indicate that the foam material exhibit fragile fracture characteristic at room temperature. When it is deformed over 200°C, the stress-strain curves exhibit plastic deformation characteristic, including three distinct regions: the linear elasticity region, the plastic collapse region, and the densification region. The Young's modulus, yield stress and elastic limit decrease with increasing of temperature. The temperature-dependence of these properties can be expressed as E*=1.5217 × 10 9-5.988 × 10 5T, σ cl*=85.7-0.095T, σ ys*=99.1-0.167V7.02 × 10 -5T 2 respectively.

Springback investigation in roll forming of a V-section

To have fuel efficient vehicles with a lightweight structure, the use of High Strength Steels (HSS) and Advanced High Strength Steels (AHSS) in the body of automobiles is increasing. Roll forming is used widely to form AHSS materials. Roll forming is a continuous process in which a flat strip is shaped to the desired profile by passing through numerous sets of rolls. Formability and springback are two major concerns in the roll forming of AHSS materials. Previous studies have shown that the elastic modulus (Young's modulus) of AHSS materials can change when the material undergoes plastic deformation and the main goal of this study is to numerically investigate the effect of a change in elastic modulus during forming on springback in roll forming. Experimental loading-unloading tests have been performed to obtain the material properties of TRIP 700 steel and incorporate those in the material model used in the numerical simulation of the roll forming process. The finite element simulations were carried out using MSC-Marc and two different element types, a shell element and a solid-shell element, were investigated. The results show that the elastic modulus diminution due to plastic strain increases the springback angle by about 60% in the simple V-section roll forming analyzed in this study. © (2014) Trans Tech Publications, Switzerland.

Numerical modeling of dual phase microstructure behavior under deformation conditions on the basis of digital material representation

Development of a digital material representation (DMR) model of dual phase steel is presented within the paper. Subsequent stages involving generation of a reliable representation of microstructure morphology, assignment of material properties to component phases and incorporation of the model into the commercial finite element software are described within the paper. Different approaches used to recreate dual phase morphology in a digital manner are critically assessed. However, particular attention is placed on innovative identification of phase properties at the micro scale by using micro-pillar compression tests. The developed DMR model is finally applied to model influence of micro scale features on failure initiation and propagation under loading conditions.

Numerical investigation of influence of the Martensite Volume Fraction on dp steels fracture behavior on the basis of digital material representation model

Development of the methodology for creating reliable digital material representation (DMR) models of dual-phase steels and investigation of influence of the martensite volume fraction on fracture behavior under tensile load are the main goals of the paper. First, an approach based on image processing algorithms for creating a DMR is described. Then, obtained digital microstructures are used as input for the numerical model of deformation, which takes into account mechanisms of ductile fracture. Ferrite and martensite material model parameters are evaluated on the basis of micropillar compression tests. Finally, the model is used to investigate the impact of the martensite volume fraction on the DP steel behavior under plastic deformation. Results of calculations are presented and discussed in the paper.

Modelling of the stiffness evolution of truss core structures damaged by plastic buckling

A finite element study based on 1D beam element model is performed in order to investigate the mechanical behavior of an elasto-plastic beam loaded in axial compression over its buckling limit. The mode of loading is related to the damage of truss-cored beams in truss-cored laminates. The analysis takes into account the effects of geometry and material properties. The results of the FEM analysis are used for developing a simple mechanical model based on the basic Euler-Bernoulli beam theory and accounts for the beam compressibility. The model uses phenomenological functions containing parameters related to the basic material and geometrical properties. The presented model is developed in the form of closed solution which does not require complex numerical methods or extensive parametric studies. Predictions of the compressive stiffness degradation of truss-cored composites are made with the proposed model and compared with the results of FEM simulations. The error of the stiffness prediction with respect to the FEM results is within 10% over a 5 fold range of stiffness.

Insights into the transport of alkali metal ions doped into a plastic crystal electrolyte

The application of organic ionic plastic crystals (OIPCs) as a new class of solid electrolyte for energy storage devices such as lithium batteries and, more recently, sodium batteries is attracting increasing attention. Key to this is achieving sufficient target ion transport through the material. This requires fundamental understanding of the structure and dynamics of OIPCs that have been doped with the necessary lithium or sodium salts. Here we report, for the first time, the atomic level structure and transport of both lithium and sodium ions in the plastic crystalline phases of an OIPC diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate. These molecular dynamics simulations reveal two types of coordination geometries of the alkali metal ion first solvation shells, which cooperate closely with the metal ion hopping motion. The significantly different ion migration rates between two metal ion doped systems could also be related to the differences in solvation structures.

Yielding behaviour of martensite in steel

Although martensite is recognised as a very strong phase in carbon steels, its initial yielding commences at low stresses and the tensile stress-strain curve shows a smooth, rounded form. Evidence is presented from x-ray diffraction to show that this behaviour is due to the presence of intra-granular stresses that are residues after the shear transformation from austenite to martensite. These internal stresses are reduced in magnitude by plastic deformation and also by tempering. Reduction of internal stress due to plasticity is shown by a decrease in XRD line broadening after deformation. A simple model is presented in which the stress-strain behaviour is controlled by relaxation of the internal stresses almost up to the point of the ultimate tensile strength. It demonstrates that only a very small fraction of the material remaining in a purely elastic state provides a large stabilising effect resisting necking. A corollary of this is that the uniform elongation of martensitic steel actually increases with increase in the strength level. Effects of heat treatment are also reproduced in the model, including the increase in conventional yield stress (Rp0.2) that occurs after low temperature tempering.

Enhanced ionic mobility in organic ionic plastic crystal - dendrimer solid electrolytes

We report the first study of the characterisation of the organic ionic plastic crystal (OIPC) N-ethyl-N-methylpyrrolidinium tetrafluoroborate (C2mpyrBF4) upon mixing with a dendrimer additive. Whereas previous reports of OIPC composite formation (i.e. with ceramics and polymers) have typically reported a decrease in the conductivity when lithium salt had been added, the addition of dendrimer is shown to lead to a substantial enhancement in the lithium containing system, approaching 3 orders of magnitude at 30°C. Mechanical analysis indicates that dendrimer addition leads to a softer more ductile material while microscopy shows that the dendrimer is uniformly distributed and that the crystal microstructure is substantially disrupted, ultimately adopting a dendritic microstructure at 1mol% dendrimer content. Thermal analysis indicates a new phase in the lithium OIPC system, the crystallisation of which is suppressed in the presence of dendrimer. Instead, a decrease in the phase transition enthalpies indicates a large increase in the amorphous component of the Lithium OIPC, particularly for the most conductive system -C2mpyrBF4 +10mol% LiBF4 +0.1mol% dendrimer. Variable temperature powder X-ray diffraction confirms the presence of a new distinct phase and its absence in the presence of dendrimer. A change in the progression of the thermal phase behaviour of the OIPC in the presence of dendrimer is also shown, exhibiting the phase I (high temperature) structure at temperatures below the phase II-I transition.

Generalized characteristics of photo-elastic birefringence in polymer strip waveguides

This work investigates the material birefringence in a polymer strip waveguide which originates from thermal stress during the fabrication process. The stress is estimated through a comprehensive numerical study based on a realistic finite element model. The characteristics of birefringence are obtained in a generalized form and expressed by an empirical formula, which is applicable to various polymer materials. The developed formula can be employed to specify the photo-elastic birefringence of a polymer strip channel only by knowing the birefringence in its planar film. This will eliminate the necessity of extensive numerical analysis of thermal stress in such polymer waveguides, and accordingly help the management of stress-induced effects efficiently.

Ionic transport through a composite structure of N-ethyl-N-methylpyrrolidinium tetrafluoroborate organic ionic plastic crystals reinforced with polymer nanofibres

The incorporation of polyvinylidene difluoride (PVDF) electrospun nanofibres within N-ethyl-N-methylpyrrolidinium tetrafluoroborate, [C2mpyr][BF4] was investigated with a view to fabricating self-standing membranes for various electrochemical device applications, in particular lithium metal batteries. Significant improvement in mechanical properties and ionic conduction was demonstrated in a previous study, which also demonstrated the remarkably high performance of the lithium-doped composite material in a device. We now seek a fundamental understanding of the role of fibres within the matrix of the plastic crystal, which is essential for optimizing device performance through fine-tuning of the composite material properties. The focus of the current study is therefore a thorough investigation of the phase behaviour and conduction behaviour of the pure and the lithium-doped (as LiBF4) plastic crystal, with and without incorporation of polymer nanofibres. Analysis of the structure of the plastic crystal, including the effects of lithium ions and the incorporation of PVDF fibres, was conducted by means of synchrotron XRD. Ion dynamics were evaluated using VT solid-state NMR spectroscopy. ATR-FTIR spectroscopy was employed to gain insights into the molecular interactions of doped lithium ions and/or the PVDF nanofibres in the matrix of the [C2mpyr][BF4] composites. Preliminary measurements using PALS were conducted to probe structural defects within the pure materials. It was found that ion transport within the plastic crystal was significantly altered by doping with lithium ions due to the precipitation of a second phase in the structure. The incorporation of the fibres activated more mobile sites in the systems, but restricted ion mobility with different trends being observed for each ion species in each crystalline phase. In the presence of the fibres a strong interaction observed between the Li ion and the pyrrolidinium ring disappeared and formation of the second phase was prevented. As a result, an increased number of mobile lithium ions are released into the solid solution structure of the matrix, simultaneously removing the blocking effect of the second phase. Thus, ion conduction was remarkably improved within the Li-doped composite compared to the neat Li-doped plastic crystal.

Study on yield function and plastic potential under non-associated flow for accurate earing prediction in cup drawing

Prediction of more than four ears in a cup drawing process can be successfully achieved by considering r-value and stress directionalities. Yld2004-18p based on associated flow rule and Yld2000-2D based on non-associated flow rule are the examples. The former, however, is more costly in terms of computational efficiency than the latter. In this work, an anisotropic constitutive model based on non-associated flow rule which combines two different functions, Hill (1948) and Yld2000-2d, is implemented to a user defined material model. The accuracy of the anisotropic directionalities (yield stresses and plastic strain ratios) is evaluated. Simulation of a mini-die cup drawing with a body stock alloy predicted eight ears, in good agreement with the experimental results. The use of Hill (1948) model for the yield function and Yld2000-2d for plastic potential under the framework of non-associated flow rule led to accurate prediction of up to eight ears at the lower computational cost.

Severe plastic deformation processes with friction induced shear

Among the known severe plastic deformation (SPD) techniques, there is a special group of processes involving friction-induced shear. One of the sample or work-piece dimensions used in such processes, namely the thickness, is much smaller than the other two dimensions. The well-known process of High Pressure Torsion (HPT) and the relatively new Cone-Cone (CC) method applied to thin conical samples fall into this category of SPD techniques. Wrought aluminium alloy 2124 was used to study the effect of CC processing on microstructure and mechanical properties. The influence of the processing parameters, including the rotation speed and thickness of the conical strip specimens on the microstructure and the mechanical properties of the CC-processed material was investigated.