Combinatorial effect of rolling and carbonaceous nanoparticles on the evolution of crystallographic texture and structural properties of ultra high molecular weight polyethylene

Ultra high molecular weight polyethylene (PE) is a structural polymer widely used in biomedical implants. The mechanical properties of PE can be improved either by controlled crystalline orientation (texture) or by the addition of reinforcing agents. However, the combinatorial effect has not received much attention. The objective of this study was to characterize the structure and mechanical properties of PE composites incorporating multiwall carbon nanotubes (MWCNT) and reduced graphene oxide (RGO) subjected to hot rolling. The wide angle X-ray diffraction studies revealed that mechanical deformation resulted in a mixture of orthorhombic and monoclinic crystals. Furthermore, the presence of nanoparticles resulted in lower crystallinity in PE with smaller crystallite size, more so in RGO than in MWCNT composites. Rolling strengthened the texture of both orthorhombic and the monoclinic phases in PE. Presence of RGO weakened the texture of both phases of PE after rolling whereas MWCNT only mildly weakened the texture. This resulted in a reduction in the elastic modulus of RGO composites whereas moduli of neat polymer and the MWCNT composite increased after rolling. This study provides new insight into the role of nanoparticles in texture evolution during polymer processing with implications for processing of structural polymer composites.

VAM Applied to Dimensional Reduction of Nonlinear Multifunctional Film-fabric Laminates

This work aims at asymptotically accurate dimensional reduction of non-linear multi-functional film-fabric laminates having specific application in design of envelopes for High Altitude Airships (HAA). The film-fabric laminate for airship envelope consists of a woven fabric core coated with thin films on each face. These films provide UV protection and Helium leakage prevention, while the core provides required structural strength. This problem is both geometrically and materially non-linear. To incorporate the geometric non-linearity, generalized warping functions are used and finite deformations are allowed. The material non-linearity is handled by using hyper-elastic material models for each layer. The development begins with three-dimensional (3-D) nonlinear elasticity and mathematically splits the analysis into a one-dimensional through-the-thickness analysis and a two-dimensional (2-D) plate analysis. The through-the-thickness analysis provides the 2-D constitutive law which is then given as an input to the 2-D reference surface analysis. The dimensional reduction is carried out using Variational Asymptotic Method (VAM) for moderate strains and very small thickness-to-wavelength ratio. It features the identification and utilization of additional small parameters such as ratio of thicknesses and stiffness coefficients of core and films. Closed form analytical expressions for warping functions and 2-D constitutive law of the film-fabric laminate are obtained.

Anomalous Viscosity Reduction and Hydrodynamic Interactions of Polymeric Nanocolloids in Polymers

One of the central dogmas of fluid physics is the no-slip boundary condition, whose validity has come under scrutiny, especially in the fields of micro and nanofluidics. Although various studies show the violation of the no-slip condition its effect on flow of colloidal particles in viscous media has been rarely explored. Here we report unusually large reduction of effective viscosity experienced by polymeric nano colloids moving through a highly viscous and confined polymer, well above its glass transition temperature. The extent of reduction in effective interface viscosity increases with decreasing temperature and polymer film thickness. Concomitant with the reduction in effective viscosity we also observe apparent divergence of the wave vector dependent hydrodynamic interaction function of these colloids with an anomalous power law exponent of similar to 2 at the lowest temperatures and film thickness studied. Such strong hydrodynamic interactions are not expected for polymeric colloidal motion in polymer melts. We suggest hydrodynamics, especially slip present at the colloid-polymer interface which determines the observed reduction in interface viscosity and presence of strong hydrodynamic interactions.

Analysis of asymmetrical cold rolling with varying coefficients of friction

In this research, asymmetrical cold rolling was produced by the difference in the coefficient of friction between rolls and sheets rather than the difference of roll radius or rotation speeds. The influence of friction coefficient ratio on the cross shear deformation, rolling pressure and torque was investigated using slab analysis. The results showed that the shear deformation zone length increased with the increase of the friction coefficient ratio. The rolling force decreased only under the condition that the friction coefficient ratio increased while the sum of the friction coefficients was held constant. As the reduction per pass was increased, the shear deformation zone length increased and the rolling force also increased. An increase of the front tension resulted in a decrease of the shear deformation zone length. An increase of back tension, however, led to an increase of the shear deformation zone length. The reduction of rolling torque for the work roll with higher surface roughness was greater than that for the work roll with lower surface roughness. (C) 2002 Elsevier Science B.V. All rights reserved.

Electrocatalytic reduction of dioxygen at chemically modified electrodes

The kinetics of the reduction of O₂ by Ru(NH₃)₆⁺² as catalyzed by cobalt(II) tetrakis(4-N-methylpyridyl)porphyrin are described both in homogeneous solution and when the reactants are confined to Nafion coatings on graphite electrodes. The catalytic mechanism is determined and the factors that can control the total reduction currents at Nafion-coated electrodes are specified. A kinetic zone diagram for analyzing the behavior of catalyst-mediator-substrate systems at polymer coated electrodes is presented and utilized in identifying the current-limiting processes. Good agreement is demonstrated between calculated and measured reduction currents at rotating disk electrodes. The experimental conditions that will yield the optimum performance of coated electrodes are discussed, and a relationship is derived for the optimal coating thickness.

The relation between the reduction potentials of adsorbed and unadsorbed cobalt(III) tetrakis(4-N-methylpyridyl)porphyrin and those where it catalyzes the electroreduction of dioxygen is described. There is an unusually large change in the formal potential of the Co(III) couple upon the adsorption of the porphyrin on the graphite electrode surface. The mechanism in which the (inevitably) adsorbed porphyrin catalyzes the reduction of O₂ is in accord with a general mechanistic scheme proposed for most monomeric cobalt porphyrins.

Four new dimeric metalloporphyrins (prepared in the laboratory of Professor C. K. Chang) have the two porphyrin rings linked by an anthracene bridge attached to meso positions. The electrocatalytic behavior of the diporphyrins towards the reduction of O₂ at graphite electrodes has been examined for the following combination of metal centers: Co-Cu, Co-Fe, Fe-Fe, Fe-H₂. The Co-Cu diporphyrin catalyzes the reduction of O₂ to H₂O₂ but no further. The other three catalysts all exhibit mixed reduction pathways leading to both H₂O₂ and H₂O. However, the pathways that lead to H₂O do not involve H₂O₂ as an intermediate. A possible mechanistic scheme is offered to account for the observed behavior.

Rolling of thin strip and foil: Application of a tribological model for "mixed" lubrication

A mechanical model of cold rolling of foil is coupled with a sophisticated tribological model. The tribological model treats the "mixed" lubrication regime of practical interest, in which there is "real" contact between the roll and strip as well as pressurized oil between the surfaces. The variation of oil film thickness and contact ratio in the bite is found by considering flattening of asperities on the foil and the build-up of hydrodynamic pressure through the bite. The boundary friction coefficient for the contact areas is taken from strip drawing tests under similar tribological conditions. Theoretical results confirm that roll load and forward slip decrease with increasing rolling speed due to the decrease in contact ratio and friction. The predictions of the model are verified using mill trials under industrial conditions. For both thin strip and foil, the load predicted by the model has reasonable agreement with the measurements. For rolling of foil, forward slip is overestimated. This is greatly improved if a variation of friction through the bite is considered.

Manufacturing dish shaped rings on radial-axial ring rolling mills

Ring rolling is an established method to produce seamless rings of different cross-sectional geometries. For dish shaped rings, there are applications in different areas such as offshore, aeronautics or the energy sector. At the moment, dish shaped rings are produced by machining of rings with rectangular shaped cross section, by (open die) hollow forging on a conical mandrel or by using shaped ring rolling tools. These ways of manufacturing have the disadvantage of high material waste, additional costs for special tools, long process time and limited or inflexible geometries. Therefore, the manufacturing of dish shaped rings on conventional radial-axial ring rolling mills would expand the range of products for ring producers. The aim of this study is to investigate the feasibility of an alternative to the current manufacturing processes, without requiring additional tooling and material costs. Therefore, the intended formation of dish shaped rings-previously regarded as a form error-is investigated. Based on an analysis of geometrical requirements and metal flow mechanisms, a rolling strategy is presented, causing dishing and ring climbing by a large height reduction of the ring. Using this rolling strategy dish shaped rings with dishing angles up to 18° were achieved. In addition to the experiments finite element method (FEM)-simulations of the process have been successfully conducted, in order to analyze the local strain evolution. However, when the contact between ring and main roll is lost in the process the ring starts to oscillate around the mandrel and neither dishing nor ring climbing is observed. © 2013 German Academic Society for Production Engineering (WGP).

Thickness dependent dislocation, electrical and optical properties in InN films grown by MOCVD

InN thin films with different thicknesses are grown by metal organic chemical vapor deposition, and the dislocations, electrical and optical properties are investigated. Based on the model of mosaic crystal, by means of X-ray diffraction skew geometry scan, the edge dislocation densities of 4.2 x 10(10) cm(-2) and 6.3 x 10(10) cm(-2) are fitted, and the decrease of twist angle and dislocation density in thicker films are observed. The carrier concentrations of 9 x 10(18) cm(-3) and 1.2 x 10(18) cm(-3) are obtained by room temperature Hall effect measurement. V-N is shown to be the origin of background carriers, and the dependence of concentration and mobility on film thickness is explained. By the analysis of S-shape temperature dependence of photoluminescence peak, the defects induced carrier localization is suggested be involved in the photoluminescence. Taking both the localization and energy band shrinkage effect into account, the localization energies of 5.05 meV and 5.58 meV for samples of different thicknesses are calculated, and the decrease of the carrier localization effect in the thicker sample can be attributed to the reduction of defects.

Reduction of tensile stress in GaN grown on Si(111) by inserting a low-temperature AlN interlayer

This study describes the growth of a low-temperature AlN interlayer for crack-free GaN growth on Si(111). It is demonstrated that, in addition to the lower growth temperature, growth of the AlN interlayer under Al-rich conditions is a critical factor for crack-free GaN growth on Si(111) substrates. The effect of the AlN interlayer thickness and NH3/TMA1 ratios on the lattice constants of subsequently grown high temperature GaN was investigated by X-ray triple crystal diffraction. The results show that the elimination of micro-cracks is related to the reduction of the tensile stress in the GaN epitaxial layers. This was also coincident with a greater number of pits formed in the AlN interlayer grown under Al rich conditions. It is proposed that these pits act as centers for the generation of misfit dislocations, which in turn leads to the reduction of tensile stress. (C) 2004 Elsevier B.V. All rights reserved.

Threshold reduction in strained-layer InGaAs/GaAs quantum well lasers by liquid phase epitaxy regrowth

When liquid phase epitaxy regrowth at 780 degrees C for 2 h is applied to the samples after molecular beam epitaxy, a decrease of the threshold current density in strained InGaAs/GaAs quantum well lasers by a factor of 3 to 4 is obtained. We suggest that this improvement is attributed to the reduction of nonradiative centers associated with deep levels at the three regions of the active region, the graded layer and the cladding layer. Indeed, a significant reduction of deep center densities has been observed by using minority and majority carrier injection deep level transient spectroscopy measurements. (C) 1998 Elsevier Science B.V. All rights reserved.

THE DEPENDENCE OF THE INVERSION LAYER THICKNESS ON THE FILM THICKNESS IN THIN-FILM SOI STRUCTURES

The dependence of the inversion-layer thickness on the film thickness in thin-film SOI structure is analyzed theoretically by using computer simulation. A new concept and parameter, the critical thickness of thin film all-bulk inversion, is introduced for the design of thin-film MOS/SOI devices. It is necessary to select the film thickness T(s1) close to the all-bulk strong inversion critical thickness in order to get high-speed and high-power operation of ultra-thin film MOS/SOI devices.

Submicrometre scale single-crystalline gold plates of nanometre thickness: synthesis through a nucleobase process and growth mechanism

Synthesis of submicrometre scale single-crystalline gold plates of nanometre thickness in the presence of nucleobase guanine through chemical reduction of HAuCl4 was investigated. The elemental composition of the as-prepared gold nanoplates was estimated using energy-dispersive x-ray spectroscopy. The as-prepared gold plates were composed of essentially (111) lattice planes, as revealed by both x-ray diffraction (XRD) and transmission electron microscopy (TEM) results. It was found that the molar ratio of HAuCl4 to guanine played a very important role in the formation of gold nanoplates. Gold nanoplates could be produced at a molar ratio of [HAuCl4]/[guanine] = 50: 1 while only smaller gold spherical nanoparticles were obtained at molar ratios of [HAuCl4]/[guanine] <= 20:1. A possible growth mechanism of the as-prepared gold nanoplates is proposed and discussed. The results and conclusion presented in this work may be valuable for our further understanding of the roles of precursor ligands in the control of nanoparticles aggregation states and the preparation of shape-controlled nanoparticles.

Electrochemical designing of Au/Pt core shell nanoparticles as nanostructured catalyst with tunable activity for oxygen reduction

Au/Pt core shell nanoparticles (NPs) have been prepared via a layer-by-layer growth of Pt layers on An NPs using underpotential deposition (UPD) redox replacement technique. A single UPD Cu monolayer replacement with Pt(11) yielded a uniform Pt film on Au NPs, and the shell thickness can be tuned by controlling the number of UPD redox replacement cycles. Oxygen reduction reaction (ORR) in air-saturated 0.1 M H2SO4 was used to investigate the electrocatalytic behavior of the as-prepared core shell NPs. Cyclic voltammograms of ORR show that the peak potentials shift positively from 0.32 V to 0.48 V with the number of Pt layers increasing from one to five, suggesting the electrocatalytic activity increases with increasing the thickness of Pt shell. The increase in electrocatalytic activity may originate mostly from the large decrease of electronic influence of Au cores on surface Pt atoms. Rotating ring-disk electrode voltammetry and rotating disk electrode voltammetry demonstrate that ORR is mainly a four-electron reduction on the as-prepared modified electrode with 5 Pt layers and first charge transfer is the rate-determining step.

Synthesis of gold nanoplates by aspartate reduction of gold chloride

Single crystal nanoplates with thickness less than 30 nm, characterized by hexagonal and truncated triangular shapes bounded mainly by {111} facets, were obtained in large quantities by aspartate reduction of gold chloride.

Thickness-dependent molecular chain and lamellar crystal orientation in ultrathin poly(di-n-hexylsilane) films

The molecular chain and lamellar crystal orientation in ultrathin films (thickness < 100 nm) of poly(di-n-hexylsilane) (PDHS) on silicon wafer substrates have been investigated by using transmission electronic microscopy, wide-angle X-ray diffraction, atomic force microscopy, and UV absorption spectroscopy. PDHS showed a film thickness-dependent molecular chain and lamellar crystal orientation. Lamellar crystals grew preferentially in flat-on orientation in the monolayer ultrathin films of PDHS, i.e., the silicon backbones were oriented along the surface-normal direction. By contrast, the orientation of lamellar crystals was preferentially edge-on in ultrathin films thicker than ca. 13 nm, i.e., the silicon backbones were oriented parallel to the substrate surface. We interpret the different orientations of molecular chain and lamellar crystal as due to the reduction of the entropy of the polymer chain near the substrate surface and the particularity of the crystallographic (001) plane of flat-on lamellae, respectively. A remarkable influence of the orientations of the silicon backbone on the UV absorption of these PDHS ultrathin films was observed due to the one-dimensional nature of sigma-electrons delocalized along the silicon backbone.