Finite element analysis of residual stresses in metallic coatings through a compound casting

Al and Mg alloys are widely used in industry as main lightweight alloys. They have excellent properties, such as low density, high ductility, and high specific strength, and so on. Generally speaking, Mg alloys are better than Al alloys. However the corrosion of Mg alloys is much more difficult to control compared Al alloys. Therefore to combine these two lightweight alloys, a composite-like structure is an ideal solution since Al alloys can be used as protective coatings for Mg alloys. Compound casting is a realistic technique to get this coating system. In the current study, we numerically study the compound casting using finite element method (FEM) to make these two alloys, a composite-like structure, satisfy requirements to resist corrosion required from industry, in which the aluminum layer is acting as a protective coating for the magnesium substrate. Several finite element models have been developed by using the birth and death element technique and we focus on compound casting-induced residual stresses in the compounded structure. The numerical results obtained from the proposed finite element models show the distribution profiles of thermal residual stresses. We found the major factors influencing the residual stresses are the temperature to pre-heating the Al substrate and the thickness of Mg deposits. © (2014) Trans Tech Publications, Switzerland.

Severe plastic deformation of TWIP steel

The severe plastic deformation of a Twinning Induced Plasticity (TWIP), 0.61C-22.3Mn-0.19Si-0.14Ni-0.27Cr (wt. %) steel by Equal Channel Angular Pressing (ECAP) at elevated temperatures was used to study the deformation mechanism as a function of accumulated strain and processing parameters. The relationship between the microstructures after different deformation schedules of ECAP at the temperatures of 200, 300 and 400oC, strain hardening behavior and mechanical properties was studied. The best balance between strength and ductility (1702 MPa and 24%) was found after 2 passes at 400oC and 300oC of ECAP. It was due to the formation of deformation microbands and twins in the microstructure. The twinning was observed after all deformation schedules except after 1 pass at 400oC. The important finding was the formation of twins in the ultrafine grains. Moreover, the stacking faults were observed in the subgrains with the size of 50nm. It is also worth mentioning the formation of nano- twins within the micro-twins at the same time. It was found that the deformation schedule affects the dislocation substructure with formation of deformation bands, cells, subgrains, two variants of twins that, in turn, influence the strain-hardening behavior and mechanical properties. Keywords: Twinning Induced Plasticity steels; Equal Channel Angular Pressing; mechanical properties; transmission electron microscopy; micro/nano twins; dislocation substructure.

Monitoring cathodic shielding and corrosion under disbonded coatings

This work presents a novel corrosion monitoring probe designed for simulating the conditions developed under disbonded coatings and for measuring current densities and their distribution over a simulated pipeline surface. The probe’s concept was experimentally evaluated via immersion tests under Cathodic Protection (CP) in high resistivity aqueous solution. Under the disbonded area, anodic currents as well as cathodic currents were both measured. Anodic current densities were used to calculate metal losses by means of Faraday’s law. Calculated corrosion patterns were compared with corrosion damage observed at the probe’s surface after a period of test. The probe’s working principles are explained in terms of simple electrochemistry.

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.

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).

Evaluation of coatings for mg alloys for biomedical applications

The aim of this work was to assess a number of coatings developed for Mg for biomedical applications. The Mg substrates were high-purity (HP) Mg and ME10, an alloy recently developed for improved extrudability. The research utilized the new fishing-line specimen configuration to allow direct comparison to our recent in vivo and in vitro measurements. The in vitro measurements were immersion tests of fishing-line specimens immersed in Nor's solution at 37 °C. Tests of substantial duration are needed because the corrosion rates of uncoated samples are low. Nor's solution is the designation given to Hank's solution through which CO2 is bubbled at a partial pressure of 0.009 atm. In this solution, pH is maintained constant by the interaction of CO2 and the bicarbonate ions in the solution. This is the same buffer as that which maintains the pH of blood. Coatings examined were: (i) an anodization using a bio-friendly alkaline electrolyte consisting of phosphate, borate, and metasilicate, (ii) octyltrimethoxysilane (OSi), (iii) 1,2-bis[triethoxysilyl]ethane (BTSE), (iv) anodization+OSi, and (v) anodization + BTSE. The performance of coated samples was comparable to or better than that of the uncoated samples, and there was a substantially better performance for the ME10 samples after anodization+OSi. Reasons for the various performances are discussed.

Structure and dynamics in solid state sodium ion electrolytes based on organic ionic plastic crystals

 The investigation of solid state sodium ion electrolytes based on Organic Ionic Plastic Crystals were carried out for potential use in the electrochemical devices such as batteries.

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.

Facile fabrication of superhydrophobic conductive graphite nanoplatelet/vapor-grown carbon fiber/polypropylene composite coatings

The fabrication of superhydrophobic surfaces with mechanical durability is challenging because the surface microstructure is easily damaged. Herein, we report superhydrophobic conductive graphite nanoplatelet (GNP)/vapor-grown carbon fiber (VGCF)/polypropylene (PP) composite coatings with mechanical durability by a hot-pressing method. The as-prepared GNP/VGCF/PP composite coatings showed water contact angle (WCA) above 150° and sliding angle (SA) less than 5°. The superhydrophobicity was improved with the increase of VGCF content in the hybrid GNP and VGCF fillers. The more VGCFs added in the GNP/VGCF/PP composite coating, the higher porosity on the surface was formed. Compared to the GNP/PP and VGCF/PP composite coatings, the GNP and VGCF hybrid fillers exhibited more remarkable synergistic effect on the electrical conductivity of the GNP/VGCF/PP composite coatings. The GNP/VGCF/PP composite coating with GNP:VGCF = 2:1 possessed a sheet resistance of 1 Ω/sq. After abrasion test, the rough microstructure of the GNP/VGCF/PP (2:1) composite coating was mostly restored and the composite coating retained superhydrophobicity, but not for the VGCF/PP composite coating. When the superhydrophobic surface is mechanically damaged with a loss of superhydrophobicity, it can be easily repaired by a simple way with adhesive tapes. Moreover, the oil-fouled composite surface can regenerate superhydrophobicity by wetting the surface with alcohol and subsequently burning off alcohol.

A study of phase behavior and conductivity of mixtures of the organic ionic plastic crystal N-methyl-N-methyl-pyrrolidinium dicyanamide with sodium dicyanamide

We report on the thermal, structural and conductivity properties of the organic ionic plastic crystal (OIPC) N-methyl-N-methyl-pyrrolidinium dicyanamide [C1mpyr][N(CN)2] mixed with the sodium salt Na[N(CN)2]. The DSC thermal traces indicate that an isothermal transition, which may be a eutectic melting, occurs at ~ 89 °C, below which all compositions are entirely in the solid phase. At 20 mol% Na[N(CN)2], this transition is the final melt for this mixture, and a new liquidus peak grows beyond 20 mol% Na[N(CN)2]. The III- > II solid-solid phase transition continues to be evident at ~- 2 °C. The microstructure for all the mixtures indicated a phase separated morphology where precipitates can be clearly observed. Most likely, these precipitates consist of a Na-rich second phase. This was also suggested from the vibrational spectroscopy and the 23Na NMR spectra. The lower concentrations of Na[N(CN)2] present complex 23Na MAS spectra, suggesting more than one sodium ion environment is present in these mixtures consistent with complex phase behavior. Unlike other OIPCs where the ionic conductivity usually increases upon doping or mixing in a second component, the conductivity of these mixtures remains relatively constant and above 10- 4 S cm- 1 at ∼ 80 °C, even in the solid state. Such high conductivities suggest these materials may be promising to be used for all solid-state electrochemical devices.

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.

Electrochemical method for studying localized corrosion beneath disbonded coatings under cathodic protection

This paper presents a new method for measuring localized corrosion under disbonded coatings by means of an electrochemical sensor, denoted differential aeration sensor (DAS). It measures the distribution of electrochemical currents over an electrode array surface partially covered by a crevice that simulates a disbonded coating. The DAS has been evaluated using immersion tests at open circuit and under cathodic protection (CP) conditions. Under both conditions, anodic as well as cathodic current densities were detected within the crevice. A fundamental understanding for the detection of anodic currents under CP has been explained in terms of basic electrochemistry. Based on the current distribution data provided by the sensor, two different analysis methods have been used to estimate corrosion and its distribution. These methods consisted of a direct application of Faraday's Law to the anodic currents detected by the array, and on a sensor-specific method denoted corrected currents' method. It has been demonstrated that under diffusion controlled conditions this latter method produces a better corrosion estimation than the direct application of Faraday's Law. The corrected currents' method allowed the estimation of corrosion patterns outside the crevice under CP. Good correlation between electrochemical calculations and surface profilometry results has been obtained.