Ionically-Mediated Electromechanical Hysteresis in Transition Metal Oxides

Nanoscale electromechanical activity, remanent polarization states, and hysteresis loops in paraelectric TiO2 and SrTiO3 thin films are observed using scanning probe microscopy. The coupling between the ionic dynamics and incipient ferroelectricity in these materials is analyzed using extended Landau-Ginzburg-Devonshire (LGD) theory. The possible origins of electromechanical coupling including ionic dynamics, surface-charge induced electrostriction, and ionically induced ferroelectricity are identified. For the latter, the ionic contribution can change the sign of first order LGD expansion coefficient, rendering material effectively ferroelectric. The lifetime of these ionically induced ferroelectric states is then controlled by the transport time of the mobile ionic species and well above that of polarization switching. These studies provide possible explanation for ferroelectric-like behavior in centrosymmetric transition metal oxides.

Direct assembly of three-dimensional mesh plasmonic rolls

A direct-assembly method to construct three-dimensional (3D) plasmonic nanostructures yields porous plasmonic rolls through the strain-induced self-rolling up of two-dimensional metallic nanopore films. This route is scalable to different hole sizes and film thicknesses, and applicable to a variety of materials, providing general routes towards a diverse family of 3D metamaterials with nano-engineerable optical properties. These plasmonic rolls can be dynamically driven by light irradiation, rolling or unrolling with increasing or decreasing light intensity. Such dynamically controllable 3D plasmonic nanostructures offer opportunities both for sensing and feedback in active nano-actuators. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4711923]

Tunable 3D Plasmonic Swiss Rolls

Novel 3D plasmonic rolls are fabricated through strain-induced self-rolling of metallic nanopore sheets attached to elastomeric thin films, with optical properties tunable by varying the size and thickness of nanopores, and dynamically by light irradiation.

Microabrasion-corrosion of cast CoCrMo alloy in simulated body fluids

Wear and corrosion of metal-on-metal hip replacements results in wear debris and metal-ion release in vivo, which may subsequently cause pain and hypersensitivity for patients. Retrieved metal-on-metal hip replacements have revealed that two-body sliding wear and three-body abrasive wear are the predominant wear mechanisms. However, there is a lack of understanding of the combined effects of wear/corrosion, especially the effect of abrasion-corrosion.

This study investigates the sliding-corrosion and abrasion-corrosion performance of a cast CoCrMo alloy in simulated hip joint environments using a microabrasion rig integrated with an electrochemical cell. Tests have been conducted in 0.9% NaCl, phosphate buffered saline solution, 25% and 50% bovine serum solutions with 0 or 1 g cm(-3) SiC at 37 degrees C. Experimental results reveal that under abrasion-corrosion test conditions, the presence of proteins increased the total specific wear rate. Conversely, electrochemical noise measurements indicated that the average anodic current levels were appreciably lower for the proteinaceous solutions when compared with the inorganic solutions. A severely deformed nanocrystalline layer was identified immediately below the worn surface for both proteinaceous and inorganic solutions. The layer is formed by a recrystallisation process and/or a strain-induced phase transformation that occurs during microabrasion-corrosion. (C) 2008 Elsevier Ltd. All rights reserved.

Micro- and Nano-scale Tribo-Corrosion of Cast CoCrMo

Previous studies have established that some of the wear damage seen on cast CoCrMo joint surface is caused by entrained third-body hard particles. In this study, wet-cell micro-indentation and nano-scratch tests have been carried out with the direct aim of simulating wear damage induced by single abrasive particles entrained between the surfaces of cast CoCrMo hip implants. In situ electrochemical current noise measurements were uniquely performed to detect and study the wear-induced corrosion as well as the repassivation kinetics under the micro-/nano-scale tribological process. A mathematical model has been explored for the CoCrMo repassivation kinetics after surface oxide film rupture. Greater insights into the nature of the CoCrMo micro-/nano-scale wear-corrosion mechanisms and deformation processes are determined, including the identification of slip band formation, matrix/carbide deformation, nanocrystalline structure formation and strain-induced phase transformation. The electrochemical current noise provides evidence of instantaneous transient corrosion activity at the wearing surface resulting from partial oxide rupturing and stripping, concurrent with the indent/scratch.

Hot deformation characteristics of a nitride strengthened martensitic heat resistant steel

Constitutive equations including an Arrhenius term have been applied to analyze the hot deformation behavior of a nitride-strengthened (NS) martensitic heat resistant steel in temperature range of 900–1200 °C and strain rate range of 0.001–10 /s. On the basis of analysis of the deformation data, the stress–strain curves up to the peak were divided into four regions, in sequence, representing four processes, namely hardening, dynamic recovery (DRV), dynamic strain induced transformation (DSIT), and dynamic recrystallization (DRX), according to the inflection points in ∂θ/∂σ∂θ/∂σ and ∂(∂θ/∂σ)/∂σ∂(∂θ/∂σ)/∂σ curves. Some of the inflection points have their own meanings. For examples, the minimum of ∂θ/∂σ∂θ/∂σ locates the start of DRV and the maximum of it indicates the start of DRX. The results also showed that the critical strain of DRX was sensitive to ln(Z) below 40, while the critical stress of DRX was sensitive to it above 40. The final microstructures under different deformation conditions were analyzed in terms of softening processes including DRV, DRX, metadynamic crystallization (MDRX) and DSIT.

Analysis of deformation behavior and workability of advanced 9Cr-Nb-V ferritic heat resistant steels

Hot compression tests were carried out on 9Cr–Nb–V heat resistant steels in the temperature range of 600–1200 °C and the strain rate range of 10−2–100 s−1 to study their deformation characteristics. The full recrystallization temperature and the carbon-free bainite phase transformation temperature were determined by the slope-change points in the curve of mean flow stress versus the inverse of temperature. The parameters of the constitutive equation for the experimental steels were calculated, including the stress exponent and the activation energy. The lower carbon content in steel would increase the fraction of precipitates by increasing the volume of dynamic strain-induced (DSIT) ferrite during deformation. The ln(εc) versus ln(Z) and the ln(σc) versus ln(Z) plots for both steels have similar trends. The efficiency of power dissipation maps with instability maps merged together show excellent workability from the strain of 0.05 to 0.6. The microstructure of the experimental steels was fully recrystallized upon deformation at low Z value owing to the dynamic recrystallization (DRX), and exhibited a necklace structure under the condition of 1050 °C/0.1 s−1 due to the suppression of the secondary flow of DRX. However, there were barely any DRX grains but elongated pancake grains under the condition of 1000 °C/1 s−1 because of the suppression of the metadynamic recrystallization (MDRX).

Constitutive modeling, microstructure evolution, and processing map for a nitride-strengthened heat-resistant steel

A constitutive equation was established to describe the deformation behavior of a nitride-strengthened (NS) steel through isothermal compression simulation test. All the parameters in the constitutive equation including the constant and the activation energy were precisely calculated for the NS steel. The result also showed that from the stress-strain curves, there existed two different linear relationships between critical stress and critical strain in the NS steel due to the augmentation of auxiliary softening effect of the dynamic strain-induced transformation. In the calculation of processing maps, with the change of Zener-Hollomon value, three domains of different levels of workability were found, namely excellent workability region with equiaxed-grain microstructure, good workability region with “stripe” microstructure, and the poor workability region with martensitic-ferritic blend microstructure. With the increase of strain, the poor workability region first expanded, then shrank to barely existing, but appeared again at the strain of 0.6.

High-resolution electron energy-loss spectroscopy of Ba Ti O 3∕ Sr Ti O 3 multilayers

The dielectric properties of BaTiO3 thin films and multilayers are different from bulk materials because of nanoscale dimensions, interfaces, and stress-strain conditions. In this study, BaTiO3/SrTiO3 multilayers deposited on SrTiO3 substrates by pulsed laser deposition have been investigated by high-energy-resolution electron energy-loss spectroscopy. The fine structures in the spectra are discussed in terms of crystal-field splitting and the internal strain. The crystal-field splitting of the BaTiO3 thin layer is found to be a little larger than that of bulk BaTiO3, which has been interpreted by the presence of the internal strain induced by the misfit at the interface. This finding is consistent with the lattice parameters of the BaTiO3 thin layer determined by the selected area diffraction pattern. The near-edge structure of the oxygen K edge in BaTiO3 thin layers and in bulk BaTiO3 are simulated by first-principle self-consistent full multiple-scattering calculations. The results of the simulations are in a good agreement with the experimental results. Moreover, the aggregation of oxygen vacancies at the rough BaTiO3/SrTiO3 interface is indicated by the increased [Ti]/[O] element ratio, which dominates the difference of dielectric properties between BaTiO3 layer and bulk materials.

Characterisation of melt processed nanocomposites of Polyamide 6 subjected to uniaxial-drawing

In this paper, the processing and characterization of Polyamide 6 (PA6) nanocomposites containing graphite nanoplatelets (GNPs) is reported. PA6 nanocomposites were prepared by melt-mixing using an industrial, co-rotating, intermeshing, twin-screw extruder. A bespoke screw configuration was used that was designed in-house to enhance nanoparticle dispersion into a polymer matrix. The effects of nano-filler type (xGnPTM M-5 and xGnPTM C-500), nano-filler content, and extruder screw speed on the bulk properties of the PA6 nanocomposites were investigated. The crystalline structures of PA6 nanocomposites are related to thermal treatment, stress history and the presence of moisture and nanofillers. DSC, Raman and XRD studies show an increase in crystallinity with increasing GNP content and a phase transformation between α-form to γ-form crystals as a result of the heterophase nucleation effect. The effect of uniaxial stretching on PA6 nanocomposites was investigated by drawing specimens heated at temperatures below the melting temperature. DSC and Raman studies on the drawn samples show an increase in yield stress as the GNP content increases due to the strain induced crystallization and γ—β transition during stretching. The rheological response of the nanocomposites resemble that of a ‘pseudo-solid’, rather than a molten liquid, and analysis of the rheological data indicates that a percolation threshold was reached at GNP contents of between 10–15wt%. An increase in tensile modulus of as much as 412% was observed for PA6/C-500 xGnPTM composites, at a filler content of 20wt%. The enhancement of Young’s modulus and yield stress can be attributed to the reinforcing effect of GNPs and their uniform dispersion in the PA6 matrix. The electrical conductivity of the composite also increased with increasing GNP content, with an addition of 15wt% GNP resulting in a 6 order-of-magnitude increase in conductivity. The effects of uniaxial-drawing and the inclusion of multiple nano-filler varieties on the electrical and mechanical properties are currently under investigation.

Processability, structural evolution and properties of melt processed biaxially stretched HDPE/MWCNT nanocomposites

Biaxial stretching of melt mixed high density polyethylene (HDPE)/multiwalled carbon nanotube (MWCNT) nanocomposites was conducted in the melt state at different stretching ratios (SRs). The addition of MWCNTs leads to significant strain hardening in the HDPE, greatly improving the stability and thus processability of the stretching process. Scanning electron microscopy shows that the MWCNTs in the polymer matrix are gradually disentangled and randomly oriented in the stretching plane with increasing SRs. All the stretched samples exhibit an increase in crystallinity (about 10%) due to strain induced crystallization and a broadened distribution of crystallite size according to the XRD and DSC results. The mechanical properties of the composites improve with increasing SRs, while they drop off after a SR of 2.5 for the neat HDPE which is likely to be due to the relaxation of polymer chains prior to solidification. The presence of the MWCNTs appears to inhibit this relaxation thus helping to maintain the orientation and mechanical properties at high SRs. The modulus, yield strength and breaking strength of stretched composites with 8 wt% MWCNTs increase by approximately 54%, 85% and 193% respectively compared with the neat HDPE at a SR of 3. The electrical percolation threshold for the unstretched material occurs at 1.9 wt% MWCNTs. As SR increases, the values of critical concentration increase from 1.9 wt% to 4.9 wt% implying the destruction of conductive networks due to an increased inter-particle distance. A loading of 6 wt% MWCNTs is sufficient to ensure that the sheet conductivity is robust to changes in the SR. Decreased values of critical exponent from 1.9 to 1.1 and morphological investigation reveal a transformation of the system structure from three dimensional to two dimensional as SR increases.

Effect of high temperature, biaxial stretching on the thermal and mechanical properties of HDPE/MWCNT sheet

High density polyethylene (HDPE)/multi-walled carbon nanotube (MWCNT) composites containing 4 wt% MWCNTs were prepared by melt mixing followed by compression moulding into sheet. Compression moulded sheets were heated to just below the melting temperature and biaxially stretched at ratios (SRs) of 2, 2.5 and 3.0. The effect of stretching on the thermal and mechanical properties of the sheet was studied by differential scanning calorimetry (DSC) and tensile testing. DSC results show that the crystallinity of all the stretched samples increases by approximately 13% due to strain induced crystallization. The melting temperature of the biaxially stretched samples increases only slightly while crystallization temperature is not affected. Tensile test results indicate that at a SR of 2.5 the elastic modulus of the stretched composites increases by 17.6% relative to the virgin HDPE, but the breaking strength decreases by 33%. While the elastic modulus and breaking strength of the HDPE/MWCNT samples continue to increase as SR increases they drop off after a SR of 2.5 for the virgin HDPE. This is probably due to the constraining influence of the nanotubes preventing the relaxation of polymer chains caused by adiabatic heating at high SRs. The addition of MWCNTs results in significant strain hardening during deformation. While this will lead to increased energy requirement in forming it will also result in a more stable process and the ability to produce deep draw containers with more uniform wall thickness

Thickness-induced stabilization of ferroelectricity in SrRuO3/Ba0.5Sr0.5TiO3/Au thin film capacitors

Pulsed-laser deposition has been used to fabricate Au/Ba0.5Sr0.5TiO3/SrRuO3/MgO thin film capacitor structures. Crystallographic and microstructural investigations indicated that the Ba0.5Sr0.5TiO3 (BST) had grown epitaxially onto the SrRuO3 lower electrode, inducing in-plane compressive and out- of-plane tensile strain in the BST. The magnitude of strain developed increased systematically as film thickness decreased. At room temperature this composition of BST is paraelectric in bulk. However, polarization measurements suggested that strain had stabilized the ferroelectric state, and that the decrease in film thickness caused an increase in remanent polarization. An increase in the paraelectric-ferroelectric transition temperature upon a decrease in thickness was confirmed by dielectric measurements. Polarization loops were fitted to Landau-Ginzburg-Devonshire (LGD) polynomial expansion, from which a second order paraelectric-ferroelectric transition in the films was suggested at a thickness of similar to500 nm. Further, the LGD analysis showed that the observed changes in room temperature polarization were entirely consistent with strain coupling in the system. (C) 2002 American Institute of Physics.

Ferroelectricity in Strain-Free SrTiO3 Thin Films

Biaxial strain is known to induce ferroelectricity in thin films of nominally nonferroelectric materials such as SrTiO3. By a direct comparison of the strained and strain-free SrTiO3 films using dielectric, ferroelectric, Raman, nonlinear optical and nanoscale piezoelectric property measurements, we conclude that all SrTiO3 films and bulk crystals are relaxor ferroelectrics, and the role of strain is to stabilize longerrange correlation of preexisting nanopolar regions, likely originating from minute amounts of unintentional Sr deficiency in nominally stoichiometric samples. These findings highlight the sensitive role of stoichiometry when exploring strain and epitaxy-induced electronic phenomena in oxide films, heterostructures, and interfaces.