In-situ synthesized poly(vinyl butyral)/MMT-clay nanocomposites: The role of degree of acetalization and clay content on thermal, mechanical and permeability properties of PVB matrix

Poly(vinyl butyral) - MMT clay nanocomposites were synthesized in situ with three different degrees of acetalization and with varying clay content for each vinyl butyral polymer ratio. The clay nano-platelet galleries were expanded, as determined by X-ray diffraction and TEM analysis. The glass transition temperature of the polymer nanocomposites were found to be similar to 56 degrees C and similar to 52 degrees C for the neat polymer and the 4% clay loaded samples, respectively. The 4 wt% clay loaded film showed higher strength and low strain to failure. The dynamic mechanical analysis also confirmed the improved stability of the matrix. The matrix with 0.5 butyral to alcohol ratio for 4 wt% clay exhibited good water vapor transmission compared to all other compositions. The encapsulated devices with 2.5 and 4 wt% clay loaded films increases the device life time and the efficiencies of these films were 50% higher than their encapsulated pristine polymer films. (C) 2015 Elsevier Ltd. All rights reserved.

Simulations of impinging droplets with surfactant-dependent dynamic contact angle

An arbitrary Lagrangian-Eulerian (ALE) finite element scheme for computations of soluble surfactant droplet impingement on a horizontal surface is presented. The numerical scheme solves the time-dependent Navier-Stokes equations for the fluid flow, scalar convection-diffusion equation for the surfactant transport in the bulk phase, and simultaneously, surface evolution equations for the surfactants on the free surface and on the liquid-solid interface. The effects of surfactants on the flow dynamics are included into the model through the surface tension and surfactant-dependent dynamic contact angle. In particular, the dynamic contact angle (theta(d)) of the droplet is defined as a function of the surfactant concentration at the contact line and the equilibrium contact angle (theta(0)(e)) of the clean surface using the nonlinear equation of state for surface tension. Further, the surface forces are included into the model as surface divergence of the surface stress tensor that allows to incorporate the Marangoni effects without calculating the surface gradient of the surfactant concentration on the free surface. In addition to a mesh convergence study and validation of the numerical results with experiments, the effects of adsorption and desorption surfactant coefficients on the flow dynamics in wetting, partially wetting and non-wetting droplets are studied in detail. It is observed that the effects of surfactants are more in wetting droplets than in the non-wetting droplets. Further, the presence of surfactants at the contact line reduces the equilibrium contact angle further when theta(0)(e) is less than 90 degrees, and increases it further when theta(0)(e) is greater than 90 degrees. Nevertheless, the presence of surfactants has no effect on the contact angle when theta(0)(e) = 90 degrees. The numerical study clearly demonstrates that the surfactant-dependent contact angle has to be considered, in addition to the Marangoni effect, in order to study the flow dynamics and the equilibrium states of surfactant droplet impingement accurately. The proposed numerical scheme guarantees the conservation of fluid mass and of the surfactant mass accurately. (C) 2015 Elsevier Inc. All rights reserved.

COMPOSITE AND MULTI-SCALE COMPLIANT MECHANISMS FOR MANIPULATION AND MECHANICAL CHARACTERIZATION

In this paper, we integrate two or more compliant mechanisms to get enhanced functionality for manipulating and mechanically characterizing the grasped objects of varied size (cm to sub-mm), stiffness (1e5 to 10 N/m), and materials (cement to biological cells). The concepts of spring-lever (SL) model, stiffness maps, and non-dimensional kinetoelastostatic maps are used to design composite and multi-scale compliant mechanisms. Composite compliant mechanisms comprise two or more different mechanisms within a single elastic continuum while multi-scale ones possess the additional feature of substantial difference in the sizes of the mechanisms that are combined into one. We present three applications: (i) a composite compliant device to measure the failure load of the cement samples; (ii) a composite multi-scale compliant gripper to measure the bulk stiffness of zebrafish embryos; and (iii) a compliant gripper combined with a negative-stiffness element to reduce the overall stiffness. The prototypes of all three devices are made and tested. The cement sample needed a breaking force of 22.5 N; the zebrafish embryo is found to have bulk stiffness of about 10 N/m; and the stiffness of a compliant gripper was reduced by 99.8 % to 0.2 N/m.

Bioinspired Reductionistic Peptide Engineering for Exceptional Mechanical Properties

A simple solution-processing and self-assembly approach that exploits the synergistic interactions between multiple hydrogen bonded networks and aromatic interactions was utilized to synthesize molecular crystals of cyclic dipeptides (CDPs), whose molecular weights (similar to 0.2 kDa) are nearly three orders of magnitude smaller than that of natural structural proteins (50-300 kDa). Mechanical properties of these materials, measured using the nanoindentation technique, indicate that the stiffness and strength are comparable and sometimes better than those of natural fibres. The measured mechanical responses were rationalized by recourse to the crystallographic structural analysis and intermolecular interactions in the self-assembled single crystals. With this work we highlight the significance of developing small molecule based bioinspired design strategies to emulate biomechanical properties. A particular advantage of the successfully demonstrated reductionistic strategy of the present work is its amenability for realistic industrial scale manufacturing of designer biomaterials with desired mechanical properties.

In-plane elastic responses of circular cell honeycombs and bundled circular tubes in a diamond array structure

Assemblages of circular tubes and circular honeycombs in close packed arrangement are presently both competing and complementing regular honeycomb structures (HCS). The intrinsic isotropy of bundled tubes/rings in hexagonal arrays restricts their use to applications with isotopic need. With the aim of extending the utility of tubes/rings assemblages to anisotropic needs, this paper explores the prospects of bundled tubes and circular honeycombs in a general diamond array structure (DAS) to cater these needs. To this end, effective transverse Young's moduli and Poisson's ratio for thick/thin DAS are obtained theoretically. Analysis frameworks including thin ring theory (TRT), curved beam theory (CBT) and elasticity formulations are tested and corroborated by FEA employing contact elements. Results indicate that TRT and CBT are reasonable for thin tubes and honeycombs. Nevertheless, TRT yields compact formulae to study the anisotropy ratio, moduli spectrum and sensitivity of the assemblage as a function of thicknesses and array structure. These formulae supplement designers as a guide to tailor the structures. On the other hand, elasticity formulation can estimate over a larger range including very thick tubes/rings. In addition, this formulation offers to estimate refined transverse strengths of assemblages. (C) 2015 Elsevier Ltd. All rights reserved.

In-plane effective shear modulus of generalized circular honeycomb structures and bundled tubes in a diamond array structure

Use of circular hexagonal honeycomb structures and tube assemblies in energy absorption systems has attracted a large number of literature on their characterization under crushing and impact loads. Notwithstanding these, effective shear moduli (G*) required for complete transverse elastic characterization and in analyses of hierarchical structures have received scant attention. In an attempt to fill this void, the present study undertakes to evaluate G* of a generalized circular honeycomb structures and tube assemblies in a diamond array structure (DAS) with no restriction on their thickness. These structures present a potential to realize a spectrum of moduli with minimal modifications, a point of relevance for manufactures and designers. To evaluate G* in this paper, models based on technical theories - thin ring theory and curved beam theory - and rigorous theory of elasticity are investigated and corroborated with FEA employing contact elements. Technical theories which give a good match for thin HCS offer compact expressions for moduli which can be harvested to study sensitivity of moduli on topology. On the other hand, elasticity model offers a very good match over a large range of thickness along with exact analysis of stresses by employing computationally efficient expressions. (C) 2015 Elsevier Ltd. All rights reserved.

Structure-mechanical property correlations in mechanochromic luminescent crystals of boron difluoride dibenzoylmethane derivatives

The structure and mechanical properties of crystalline materials of three boron difluoride dibenzoylmethane (BF(2)dbm) derivatives were investigated to examine the correlation, if any, among mechanochromic luminescence (ML) behaviour, solid-state structure, and the mechanical behaviour of single crystals. Qualitative mechanical deformation tests show that the crystals of BF(2)dbm(Bu-t)(2) can be bent permanently, whereas those of BF(2)dbm(OMe)(2) exhibit an inhomogeneous shearing mode of deformation, and finally BF(2)dbmOMe crystals are brittle. Quantitative mechanical analysis by nanoindentation on the major facets of the crystals shows that BF(2)dbm(Bu-t)(2) is soft and compliant with low values of elastic modulus, E, and hardness, H, confirming its superior suceptibility for plastic deformation, which is attributed to the presence of a multitude of slip systems in the crystal structure. In contrast, both BF(2)dbm(OMe)(2) and BF(2)dbmOMe are considerably stiffer and harder with comparable E and H, which are rationalized through analysis of the structural attributes such as the intermolecular interactions, slip systems and their relative orientation with respect to the indentation direction. As expected from the qualitative mechanical behaviour, prominent ML was observed in BF(2)dbm(Bu-t)(2), whereas BF(2)dbm(OMe)(2) exhibits only a moderate ML and BF(2)dbmOMe shows no detectable ML, all examined under identical conditions. These results confirm that the extent of ML in crystalline organic solid-state fluorophore materials can be correlated positively with the extent of plasticity (low recovery). In turn, they offer opportunities to design new and improved efficient ML materials using crystal engineering principles.

Deployment strategy for controlled morphologies in sessile, mixed colloidal droplets

Colloidal systems offer an effective medium to micro-engineer complex structures without involving sophisticated fabrication procedures. This article presents a deployment strategy of multiple droplets of different colloidal composition and utilizes the inherent capillary flow driven self assembly of nanoparticles to construct stacks of multiple materials on a given glass substrate. Here we used aqueous nano-crystalline titania and nano-amorphous silica solutions as the two materials. Initially, a pure nanotitania (nanosilica) droplet is deployed and allowed to dry partially. Subsequently, a second droplet of pure nanosilica (nanotitania) is deployed co-axially on the partially dried precipitate. The proposed deployment strategy allowed significant morphological differences when the deployment order of nanosilica and nanotitania were interchanged. Compositional analysis performed using EDX (Energy Dispersive X-ray spectroscopy) showed preferential deposition of nanosilica and nanotitania along the radial as well as the axial plane of the final deposit pattern. The underlying mechanism for such a phenomenon could be attributed to the contact line dynamics of a sessile double droplet. We also observe heteroaggregation of the nanosilica-nanotitania interaction along a narrow interface which resulted in nanotitania particles clustering into isolated islands embedded into a matrix of nanosilica particles. Overall, this work elucidates the evaporation driven dynamics of a mixed colloidal system which displays both macroscopic as well as microscopic phenomena. Such a system could be used to generate ordered arrays of functional materials with engineered micro to nano-scale properties.

Effect of combined treatment with zoledronic acid and propranolol on mechanical strength in an rat model of disuse osteoporosis

Objectives: A model that uses right hind-limb unloading of rats is used to study the consequences of skeletal unloading during various conditions like space flights and prolonged bed rest in elderly. This study was aimed to investigate the additive effects of antiresorptive agent zoledronic acid (ZOL), alone and in combination with propranolol (PRO) in a rat model of disuse osteoporosis. Methods: In the present study, 3-month-old male Wistar rats had their right hind-limb immobilized (RHLI) for 10 weeks to induce osteopenia, then were randomized into four groups: 1-RHLI positive control, 2-RHLI plus ZOL (50 mu g/kg, i.v. single dose), 3-RHLI plus PRO (0.1 mg/kg, s.c. 5 days per week), 4-RHLI plus PRO (0.1 mg/kg, s.c. 5 days per week) plus ZOL (50 mu g/kg, i.v. single dose) for another 10 weeks. One group of non-immobilized rats was used as negative control. At the end of treatment, the femurs were removed and tested for bone porosity, bone mechanical properties, and bone dry and ash weight. Results: With respect to improvement in the mechanical strength of the femoral mid-shaft, the combination treatment with ZOL plus PRO was more effective than ZOL or PRO monotherapy. Moreover, combination therapy using ZOL plus PRO was more effective in improving dry bone weight and preserved the cortical bone porosity better than monotherapy using ZOL or PRO in right hind-limb immobilized rats. Conclusions: These data suggest that this combined treatment with ZOL plus PRO should be recommended for the treatment of disuse osteoporosis. (C) 2014 Elsevier Editora Ltda. All rights reserved.

Physical Insights on the Ambiguous Metal-Graphene Interface and Proposal for Improved Contact Resistance

The ambiguous behavior of metal-graphene interface has been addressed in this paper using density functional theory and nonequilibrium Green's function formalism. For the first time, the fundamental chemistry of metal-graphene interface, in particular role of sp-hybridized and sp(2)-hybridized carbon atoms, has been emphasized and discussed in detail in this paper. It was discovered that the sp-hybridized sites at the edge of a graphene monolayer contribute to 40% of current conduction when compared with sp(2)-hybridized atom sites in the graphene-metal overlap region. Moreover, we highlighted the insignificance of an additional metal layer, i.e., sandwiched contact, due to lacking sp-hybridized carbon sites. A fundamental way of defining the contact resistance, while keeping chemical bonding in mind, has been proposed. The bonding insight has been further used to propose the novel ways of interfacing metal with graphene, which results in a 40% reduction in contact resistance.

Air microjet system for non-contact force application and the actuation of micro-structures

We demonstrate a non-contact technique to apply calibrated and localized forces in the micro-Newton to milli-Newton range using an air microjet. An electromagnetically actuated diaphragm controlled by a signal generator is used to generate the air microjet. With a nozzle diameter of 150 mu m, the microjet diameter was maintained to a maximum of 1 mm at a distance of 5 mm from the nozzle. The force generated by the microjet was measured using a commercial force sensor to determine the velocity profile of the jet. Axial flow velocities of up to 25 m s(-1) were obtained at distances as long as 6 mm. The microjet exerted a force up to 1 mu N on a poly dimethyl siloxane (PDMS) micropillar (50 mu m in diameter, 157 mu m in height) and 415 mu N on a PDMS membrane (3 mm in diameter, 28 mu m thick). We also demonstrate that from a distance of 6 mm our microjet can exert a peak pressure of 187 Pa with a total force of about 84 mu N on a flat surface with 8 V operating voltage. Out of the cleanroom fabrication and robust design make this system cost effective and durable.

Relationship between entropy and diffusion: A statistical mechanical derivation of Rosenfeld expression for a rugged energy landscape

Diffusion-a measure of dynamics, and entropy-a measure of disorder in the system are found to be intimately correlated in many systems, and the correlation is often strongly non-linear. We explore the origin of this complex dependence by studying diffusion of a point Brownian particle on a model potential energy surface characterized by ruggedness. If we assume that the ruggedness has a Gaussian distribution, then for this model, one can obtain the excess entropy exactly for any dimension. By using the expression for the mean first passage time, we present a statistical mechanical derivation of the well-known and well-tested scaling relation proposed by Rosenfeld between diffusion and excess entropy. In anticipation that Rosenfeld diffusion-entropy scaling (RDES) relation may continue to be valid in higher dimensions (where the mean first passage time approach is not available), we carry out an effective medium approximation (EMA) based analysis of the effective transition rate and hence of the effective diffusion coefficient. We show that the EMA expression can be used to derive the RDES scaling relation for any dimension higher than unity. However, RDES is shown to break down in the presence of spatial correlation among the energy landscape values. (C) 2015 AIP Publishing LLC.

Intrinsic Limit for Contact Resistance in Exfoliated Multilayered MoS2 FET

A new method for the separation of contact resistance (R-contact) into Schottky barrier resistance (R-SB) and interlayer resistance (R-IL) is proposed for multilayered MoS2 FETs. While R-SB varies exponentially with Schottky barrier height (Phi(bn)), R-IL essentially remains unchanged. An empirical model utilizing this dependence of R-contact versus Phi(bn) is proposed and fits to the experimental data. The results, on comparison with the existing reports of lowest R-contact, suggest that the extracted R-IL (1.53 k Omega.mu m) for an unaltered channel would determine the lower limit of intrinsic R-contact even for barrierless contacts for multilayered exfoliated MoS2 FETs.

Insight into the Evaporation Dynamics of a Pair of Sessile Droplets on a Hydrophobic Substrate

In this work, we have demonstrated three unique regimes in the evaporation lifecycle of a pair of sessile droplets placed in variable proximity on a hydrophobic substrate. For small separation distance, the droplets undergo asymmetric spatiotemporal,evaporation leading to contact angle hysteresis and suppressed vaporization. The reduced evaporation has been attributed quantitatively to the existence of a constrained vapor-rich dome between the two droplets. However, a dynamic decrease in the droplet radius due to solvent removal marks a return to symmetry in terms of evaporation and contact angle. We have described the variation in evaporation flux using a universal correction factor. We have also demonstrated the existence of a critical separation distance beyond which the droplets in the, droplet pair do not affect each other. The results are crucial to a plethora of applications ranging from surface patterning to lab-on-a-chip devices.

Experimental study on evaporation of pentane from a heated capillary slot

An experimental investigation of evaporation of a pentane meniscus from a heated capillary slot is presented. A novel aspect of this study is that both the wicking height and steady state evaporation mass flow rate are measured simultaneously. Based on a macroscopic force balance, the apparent contact angle of the evaporating meniscus is experimentally estimated from the wicking height and mass flow rate. This is compared with the results obtained using evaporating thin-film theory. The experimentally estimated contact angle is slightly larger than that obtained from the thin-film model but both show similar trends. Further, it is found that the reduction in the meniscus height is primarily due to an increase in the apparent contact angle. The liquid and vapor pressure drops in the capillary are insignificant relative to the capillary pressure. (C) 2015 Elsevier Ltd. All rights reserved.