Performance of an ionomer blend-nanocomposite as an effective gas barrier material for organic devices

A new, flexible, gas barrier material has been synthesized by exfoliating organically modified nano-clays (MMT) in the blends of Surlyn (PEMA) using a copolymer of vinyl alcohol (EVOH) and demonstrated as a gas barrier material. The materials were characterized by Fourier transform infra red (FTIR) and UV-visible spectroscopy, differential scanning calorimetry (DSC), thermo-gravimetric analysis (TGA) and tensile studies. The oxygen and water-vapor permeabilities of the fabricated films were determined by calcium degradation test and a novel permeability setup based on cavity ring down spectroscopy, respectively. Hierarchical simulations of these materials helped us to understand the effect of intermolecular interactions on diffusivities of oxygen and water molecules in these materials. Schottky structured poly(3-hexylthiophene) based organic devices were encapsulated with the fabricated films and aging studies were carried under accelerated conditions. Based on permeability test results and accelerated aging studies, the fabricated PEMA/EVOH/MMT composites were found to be effective in decreasing the permeabilities for gases by about two orders of magnitude and maintaining the lifetime of organic devices.

The influence of mesoporous silica in low T-g cyclic olefin copolymer nanocomposite films: Mechanical and moisture barrier studies

In this study, mesoporous silica-cyclic olefin copolymer nanocomposite films were fabricated by solution casting. With an increase in silica loading, the stiffness of the matrix increased. The nanocomposite film shows increased strain to failure with moisture after aging by matrix plasticization. The storage modulus and loss factor for samples with silica content show better results compared with pristine polymer, as indicated by dynamic mechanical analysis. The interaction between filler-polymer chain exhibit hydrophobicity compared to the neat polymer. Water absorption studies at room temperature and near the T-g of the polymer (similar to 64 degrees C) were carried out. The nanocomposites up to 4 wt% filler reduces the water diffusion by forming hydrogen and chemical bonding. The result by calcium degradation test method for moisture permeability and Schottky structured organic device encapsulation under weathering condition confirms the effective reinforcement effect of silica particles in the matrix. (C) 2014 Elsevier Ltd. All rights reserved.

Characterizing Frictional Contact Loading via Isochromatics

Isochromatic patterns in the vicinity of frictional contacts furnish vital clues for characterizing friction. Though friction effects are evident in a diametrally loaded circular disk, three-point loading provides better results towards highlighting friction. In this paper, a new method of characterizing friction at loading contacts using photoelastic isochromatics patterns is presented. Location of isotropic points (IPs) formed in three-point and four-point loadings of circular disk is used as a main tool to quantify the friction component using theoretical analysis. Bifurcation of isochromatic fringe loops near the distributed loads is explained by the presence of anti-symmetric Hertzian shear traction in addition to Hertzian normal traction. The classical solution by Flamant for point load at the edge of half plane is used to derive stresses in circular disk for all required loading configurations. A semicircualr ring under three-point loading is examined using photoelasticity to understand the isochromatics pattern theoretically by considering normal and shear traction components at loaded regions.

Total internal reflection Raman spectroscopy of poly(alpha-olefin) oils in a lubricated contact

The rheology of a poly(alpha-olefin) base oil (PAO) in a sliding point contact has been investigated by total internal reflection (TIR) Raman spectroscopy. TIR Raman has the sensitivity to analyse nanometer-thick lubricant films in a tribological contact. The Raman signal generated from the sliding contact was used to determine the lubricant film thickness. The experimentally obtained film thicknesses were compared with theoretical calculations and a transition from Newtonian to non-Newtonian behaviour was observed at high shear rates. The Raman spectra showed no significant changes in the conformation of the PAO chains under the applied conditions of pressure and shear, but the polarisation dependence of the spectra revealed a preferred orientation of the hydrocarbon side chains in the shear-thinned region. Monolayers formed by a boundary lubricant, arachidic acid, dissolved in the PAO could be detected on the surfaces in the elastohydrodynamic regime.

Effect of contact stresses on shape recovery of NiTiCu thin films

Permanent plastic deformation induced by mechanical contacts affects the shape recovery of shape memory alloys. To understand the shape recovery of NiTiCu thin films subjected to local contact stresses, systematic investigations are carried out by inducing varying levels of contact stresses using nanoindentation. The resulting indents are located precisely for imaging using a predetermined array consisting of different sized indents. Morphology and topography of these indents before and after shape recovery are characterized using Scanning Electron Microscope and Atomic Force Microscope quantitatively. Shape recovery is found to be dependent on the contact stresses at the low loads while the recovery ratio remains constant at 0.13 for higher loads. Shape recovery is found to occur mainly in depth direction of the indent, while far field residual stresses play very little role in the recovery. (C) 2014 Elsevier B.V. All rights reserved.

Re-analysis of cryoEM data on HCV IRES bound to 40S subunit of human ribosome integrated with recent structural information suggests new contact regions between ribosomal proteins and HCV RNA

In this study, we combine available high resolution structural information on eukaryotic ribosomes with low resolution cryo-EM data on the Hepatitis C Viral RNA (IRES) human ribosome complex. Aided further by the prediction of RNA-protein interactions and restrained docking studies, we gain insights on their interaction at the residue level. We identified the components involved at the major and minor contact regions, and propose that there are energetically favorable local interactions between 40S ribosomal proteins and IRES domains. Domain II of the IRES interacts with ribosomal proteins S5 and S25 while the pseudoknot and the downstream domain IV region bind to ribosomal proteins S26, S28 and S5. We also provide support using UV cross-linking studies to validate our proposition of interaction between the S5 and IRES domains II and IV. We found that domain IIIe makes contact with the ribosomal protein S3a (S1e). Our model also suggests that the ribosomal protein S27 interacts with domain IIIc while S7 has a weak contact with a single base RNA bulge between junction IIIabc and IIId. The interacting residues are highly conserved among mammalian homologs while IRES RNA bases involved in contact do not show strict conservation. IRES RNA binding sites for S25 and S3a show the best conservation among related viral IRESs. The new contacts identified between ribosomal proteins and RNA are consistent with previous independent studies on RNA-binding properties of ribosomal proteins reported in literature, though information at the residue level is not available in previous studies.

Large deformation dynamic finite element analysis of delaminated composite plates using contact-impact conditions

A new C-0 composite plate finite element based on Reddy's third order theory is used for large deformation dynamic analysis of delaminated composite plates. The inter-laminar contact is modeled with an augmented Lagrangian approach. Numerical results show that the widely used ``unconditionally stable'' beta-Newmark method presents instability problems in the transient simulation of delaminated composite plate structures with large deformation. To overcome this instability issue, an energy and momentum conserving composite implicit time integration scheme presented by Bathe and Baig is used. It is found that a proper selection of the penalty parameter is very crucial in the contact simulation. (C) 2014 Elsevier Ltd. All rights reserved.

First principles study of metal contacts to monolayer black phosphorous

Atomically thin layered black phosphorous (BP) has recently appeared as an alternative to the transitional metal dichalcogenides for future channel material in a metal-oxide-semiconductor transistor due to its lower carrier effective mass. Investigation of the electronic property of source/drain contact involving metal and two-dimensional material is essential as it impacts the transistor performance. In this paper, we perform a systematic and rigorous study to evaluate the Ohmic nature of the side-contact formed by the monolayer BP (mBP) and metals (gold, titanium, and palladium), which are commonly used in experiments. Employing the Density Functional Theory, we analyse the potential barrier, charge transfer and atomic orbital overlap at the metal-mBP interface in an optimized structure to understand how efficiently carriers could be injected from metal contact to the mBP channel. Our analysis shows that gold forms a Schottky contact with a higher tunnel barrier at the interface in comparison to the titanium and palladium. mBP contact with palladium is found to be purely Ohmic, where as titanium contact demonstrates an intermediate behaviour. (C) 2014 AIP Publishing LLC.

Water Vapor Barrier Material by Covalent Self-Assembly for Organic Device Encapsulation

Development of barrier materials for organic device encapsulation is of key interest for the commercialization of organic electronics. In this work, we have fabricated barrier films with ultralow water vapor permeabilities by reactive layer-by-layer approach. Using this technique, alternative layers of polyethylene imine and stearic acid were covalently bonded on a Surlyn film. The roughness, transparency and thickness of the films were determined by atomic force microscopy, UV-visible spectroscopy and scanning electron microscopy, respectively. Water vapor transmission rates through these films and the ability of these films to protect the organic photovoltaic devices was investigated. The films with covalently assembled bilayers exhibited lower water vapor transmission rates and maintained higher organic photovoltaic device efficiencies compared to the neat Surlyn film.

Double Gaussian distribution of barrier height observed in densely packed GaN nanorods over Si (111) heterostructures

GaN nanorods were grown by plasma assisted molecular beam epitaxy on intrinsic Si (111) substrates which were characterized by powder X-ray diffraction, field emission scanning electron microscopy, and photoluminescence. The current-voltage characteristics of the GaN nanorods on Si (111) heterojunction were obtained from 138 to 493K which showed the inverted rectification behavior. The I-V characteristics were analyzed in terms of thermionic emission model. The temperature variation of the apparent barrier height and ideality factor along with the non-linearity of the activation energy plot indicated the presence of lateral inhomogeneities in the barrier height. The observed two temperature regimes in Richardson's plot could be well explained by assuming two separate Gaussian distribution of the barrier heights. (C) 2014 AIP Publishing LLC.

Layer-by-Layer Assembly of Nafion on Surlyn with Ultrahigh Water Vapor Barrier

A layer-by-layer approach was used for the fabrication of multilayer films for ultra high gas barrier applications. The ultra high gas barrier material was designed by incorporating Nafion layer in between bilayers of poly(ethylene imine) and poly(acrylic acid) on a Surlyn substrate. When the barrier film with self-assembled Nafion is exposed to the moist environment, Nafion absorbs and desorbs water molecules simultaneously, thereby reducing the ingress of moisture in to the film. In order to study the effect of Nafion, the fabricated barrier materials with and without the presence of Nafion were tested for water vapor barrier properties. The barrier films were further used for encapsulating organic photovoltaic devices and were evaluated for their potential use in barrier applications. The devices encapsulated with the films containing Nafion exhibited better performance when subjected to accelerated aging conditions. Therefore, this study demonstrates the effectiveness of self-assembled Nafion in reducing the water vapor permeability by nearly five orders of magnitude and in increasing the lifetimes of organic devices by similar to 22 times under accelerated weathering conditions.

Transitory second-order reciprocal connection for two surfaces in point contact

This paper investigates the instantaneous spatial higher pair to lower pair substitute-connection which is kinematically equivalent up to acceleration analysis for two smooth surfaces in point contact. The existing first-order equivalent substitute-connection consisting of a Hooke's joint (U-joint) and a spherical joint (S-joint) connected by an additional link is extended up to second-order. A two step procedure is chalked out for achieving this equivalence. First, the existing method is employed for velocity equivalence. In the second step, the two centers of substitution are obtained as a conjugate relationship involving the principal normal curvatures of the surfaces at the contact point and the screw coordinates of the instantaneous screw axis (ISA) of the first-order relative motion. Unlike the classical planar replacement, this particular substitution cannot be done by merely examining the profiles of the contacting surfaces. An illustrative example of a three-link direct-contact mechanism is presented. (C) 2014 Elsevier Ltd. All rights reserved.

Sphere to ring morphological transformation in drying nanofluid droplets in a contact-free environment

Understanding the transients of buckling in drying colloidal suspensions is pivotal for producing new functional microstructures with tunable morphologies. Here, we report first observations and elucidate the buckling instability induced morphological transition (sphere to ring structure) in an acoustically levitated, heated nanosuspension droplet using dynamic energy balance. Droplet deformation featuring the formation of symmetric cavities is initiated by capillary pressure that is two to three orders of magnitude greater than the acoustic radiation pressure, thus indicating that the standing pressure field has no influence on the buckling front kinetics. With an increase in heat flux, the growth rate of surface cavities and their post-buckled volume increase while the buckling time period reduces, thereby altering the buckling pathway and resulting in distinct precipitate structures. However, irrespective of the heating rate, the volumetric droplet deformation exhibits a linear time dependence and the droplet vaporization is observed to deviate from the classical D-2-law.

Characterization of friction at three contact pairs by photoelastic Isotropic point (IP)

Friction coefficient between a circular-disk periphery and V-block surface was determined by introducing the concept of isotropic point (IP) in isochromatic field of the disk under three-point symmetric loading. IP position on the symmetry axis depends on active coefficient of friction during experiment. We extend this work to asymmetric loading of circular disk in which case two frictional contact pairs out of three loading contacts, independently control the unconstrained IP location. Photoelastic experiment is conducted on particular case of asymmetric three-point loading of circular disk. Basics of digital image processing are used to extract few essential parameters from experimental image, particularly IP location. Analytical solution by Flamant for half plane with a concentrated load, is utilized to derive stress components for required loading configurations of the disk. IP is observed, in analytical simulations of three-point asymmetric normal loading, to move from vertical axis to the boundary along an ellipse-like curve. When friction is included in the analysis, IP approaches the center with increase in loading friction and it goes away with increase in support friction. With all these insights, using experimental IP information, friction angles at three contact pairs of circular disk under asymmetric loading, are determined.