Fabrication and characterization of gold coated hollow silicon microneedle array for drug delivery

In this paper, we present the fabrication and characterization of Ti and Au coated hollow silicon microneedles for transdermal drug delivery applications. The hollow silicon microneedles are fabricated using isotropic etching followed by anisotropic etching to obtain a tapered tip. Silicon microneedle of 300 mu m in height, with 130 mu m outer diameter and 110 mu m inner diameter at the tip followed by 80 mu m inner diameter and 160 mu m outer diameter at the base have been fabricated. In order to improve the biocompatibility of microneedles, the fabricated microneedles were coated with Ti (500 nm) by sputtering technique followed by gold coating using electroplating. A breaking force of 225 N was obtained for the fabricated microneedles, which is 10 times higher than the skin resistive force. Hence, fabricated microneedles can easily be inserted inside the skin without breakage. The fluid flow through the microneedles was studied for different inlet pressures. A minimum inlet pressure of 0.66 kPa was required to achieve a flow rate of 50 mu l in 2 s with de-ionized water as a fluid medium. (C) 2014 Elsevier B.V. All rights reserved.

Isotropic finite volume discretization

Finite volume methods traditionally employ dimension by dimension extension of the one-dimensional reconstruction and averaging procedures to achieve spatial discretization of the governing partial differential equations on a structured Cartesian mesh in multiple dimensions. This simple approach based on tensor product stencils introduces an undesirable grid orientation dependence in the computed solution. The resulting anisotropic errors lead to a disparity in the calculations that is most prominent between directions parallel and diagonal to the grid lines. In this work we develop isotropic finite volume discretization schemes which minimize such grid orientation effects in multidimensional calculations by eliminating the directional bias in the lowest order term in the truncation error. Explicit isotropic expressions that relate the cell face averaged line and surface integrals of a function and its derivatives to the given cell area and volume averages are derived in two and three dimensions, respectively. It is found that a family of isotropic approximations with a free parameter can be derived by combining isotropic schemes based on next-nearest and next-next-nearest neighbors in three dimensions. Use of these isotropic expressions alone in a standard finite volume framework, however, is found to be insufficient in enforcing rotational invariance when the flux vector is nonlinear and/or spatially non-uniform. The rotationally invariant terms which lead to a loss of isotropy in such cases are explicitly identified and recast in a differential form. Various forms of flux correction terms which allow for a full recovery of rotational invariance in the lowest order truncation error terms, while preserving the formal order of accuracy and discrete conservation of the original finite volume method, are developed. Numerical tests in two and three dimensions attest the superior directional attributes of the proposed isotropic finite volume method. Prominent anisotropic errors, such as spurious asymmetric distortions on a circular reaction-diffusion wave that feature in the conventional finite volume implementation are effectively suppressed through isotropic finite volume discretization. Furthermore, for a given spatial resolution, a striking improvement in the prediction of kinetic energy decay rate corresponding to a general two-dimensional incompressible flow field is observed with the use of an isotropic finite volume method instead of the conventional discretization. (C) 2014 Elsevier Inc. All rights reserved.

Glass, Gel, and Liquid Crystals: Arrested States of Graphene Oxide Aqueous Dispersions

Colloidal systems with competing interactions are known to exhibit a range of dynamically arrested states because of the systems' inability to reach its underlying equilibrium state due to intrinsic frustration. Graphene oxide (GO) aqueous dispersions constitute a class of 2D-anisotropic colloids with competing interactions long-range electrostatic repulsion, originating from ionized groups located on the rim of the sheets, and weak dispersive attractive interactions originating from the unoxidized graphitic domains. We show here that aqueous dispersions of GO exhibit a range of arrested states, encompassing fluid, glass, and gels that coexist with liquid-crystalline order with increasing volume fraction. These states can be accessed by varying the relative magnitudes of the repulsive and attractive forces. This can be realized by changing the ionic strength of the medium. We observe at low salt concentrations, where long-range electrostatic repulsion dominates, the formation of a repulsive Wigner glass, while at high salt concentrations, when attractive forces dominate, the formation of gels exhibits a nematic to columnar liquid-crystalline transition. The present work highlights how the chemical structure of GO hydrophilic ionizable groups and hydrophobic graphitic domains coexisting on a single sheet gives rise to a rich and complex array of arrested states.

Transverse orthotropic elastic moduli of bundled coated thin elliptical tubes

Light weight structures with tailored mechanical properties have evolved beyond regular hexagonal/circular honeycomb topology. For applications which demand anisotropic mechanical properties, elliptical-celled structures offer interesting features. This paper characterizes the anisotropic in-plane elastic response of coated thin elliptical tubes in different array patterns viz, close-packed, diagonal and rectangular patterns under compression. This paper also extends earlier works on elliptical close-packed structure to a more general case of coated tubes. Theoretical framework using thin ring theory provides formulae in terms of geometric and material parameters. These are compared with a series of FE simulations using contact elements. The FE results are presented as graphs to aid in design. (C) 2014 Elsevier Ltd. All rights reserved.

Dynamical facilitation governs glassy dynamics in suspensions of colloidal ellipsoids

One of the greatest challenges in contemporary condensed matter physics is to ascertain whether the formation of glasses from liquids is fundamentally thermodynamic or dynamic in origin. Although the thermodynamic paradigm has dominated theoretical research for decades, the purely kinetic perspective of the dynamical facilitation (DF) theory has attained prominence in recent times. In particular, recent experiments and simulations have highlighted the importance of facilitation using simple model systems composed of spherical particles. However, an overwhelming majority of liquids possess anisotropy in particle shape and interactions, and it is therefore imperative to examine facilitation in complex glass formers. Here, we apply the DF theory to systems with orientational degrees of freedom as well as anisotropic attractive interactions. By analyzing data from experiments on colloidal ellipsoids, we show that facilitation plays a pivotal role in translational as well as orientational relaxation. Furthermore, we demonstrate that the introduction of attractive interactions leads to spatial decoupling of translational and rotational facilitation, which subsequently results in the decoupling of dynamical heterogeneities. Most strikingly, the DF theory can predict the existence of reentrant glass transitions based on the statistics of localized dynamical events, called excitations, whose duration is substantially smaller than the structural relaxation time. Our findings pave the way for systematically testing the DF approach in complex glass formers and also establish the significance of facilitation in governing structural relaxation in supercooled liquids.

Synthesis and photocatalytic performance of quasi-fibrous ZnO

The combustion of oxidizer zinc nitrate and fuel oxalic acid results in quasi-fibrous zinc oxide. The processing parameters including oxidizer to fuel ratio, time and temperature were optimized for the resultant crystal structure and morphology. Pure hexagonal phase formation does not depend on the fuel ratio, but a stoichiometric ratio of oxidizer to fuel at 450 degrees C and 30 min results in highly crystalline ZnO with 3 mu m length and 0.5 mu m width. This quasi-fiber originates from partial fusion of near spherical, similar to 60 nm particles during the rapid rate of reaction in the combustion process. Transmission electron microscopic analysis confirms the anisotropic primary particle orientation and pore distribution within the developed quasi-fibrous particles. The degradation of methyl orange was assessed by degrading the dye in the presence of the synthesized ZnO (2.95 eV) under both UV and visible light. Quasi-fibrous zinc oxide exhibits effective photocatalytic efficiency under visible light irradiation.

Semipolar and nonpolar GaN epi-films grown on m-sapphire by plasma assisted molecular beam epitaxy

We hereby report the development of non-polar epi-GaN films of usable quality, on an m-plane sapphire. Generally, it is difficult to obtain high-quality nonpolar material due to the planar anisotropic nature of the growth mode. However, we could achieve good quality epi-GaN films by involving controlled steps of nitridation. GaN epilayers were grown on m-plane (10-10) sapphire substrates using plasma assisted molecular beam epitaxy. The films grown on the nitridated surface resulted in a nonpolar (10-10) orientation while without nitridation caused a semipolar (11-22) orientation. Room temperature photoluminescence study showed that nonpolar GaN films have higher value of compressive strain as compared to semipolar GaN films, which was further confirmed by room temperature Raman spectroscopy. The room temperature UV photodetection of both films was investigated by measuring the I-V characteristics under UV light illumination. UV photodetectors fabricated on nonpolar GaN showed better characteristics, including higher external quantum efficiency, compared to photodetectors fabricated on semipolar GaN. X-ray rocking curves confirmed better crystallinity of semipolar as compared to nonpolar GaN which resulted in faster transit response of the device. (C) 2014 AIP Publishing LLC.

pentahexoctite: A new two-dimensional allotrope of carbon

The ability of carbon to exist in many forms across dimensions has spawned search in exploring newer allotropes consisting of either, different networks of polygons or rings. While research on various 3D phases of carbon has been extensive, 2D allotropes formed from stable rings are yet to be unearthed. Here, we report a new sp(2) hybridized two-dimensional allotrope consisting of continuous 5-6-8 rings of carbon atoms, named as ``pentahexoctite''. The absence of unstable modes in the phonon spectra ensures the stability of the planar sheet. Furthermore, this sheet has mechanical strength comparable to graphene. Electronically, the sheet is metallic with direction-dependent flat and dispersive bands at the Fermi level ensuring highly anisotropic transport properties. This sheet serves as a precursor for stable 1D nanotubes with chirality-dependent electronic and mechanical properties. With these unique properties, this sheet becomes another exciting addition to the family of robust novel 2D allotropes of carbon.

Thick PECVD Germanium films for MEMS Application

Plasma enhanced chemical vapour deposition (PECVD) of thick germanium (Ge) films (similar to 1 mu m) on silicon dioxide (SiO2) at low temperatures is described. A diborane pretreatment on SiO2 films is done to seed the Ge growth, followed by the deposition of thick Ge films using germane (GeH4) and argon (Ar). Further, the effect of hydrogen (H-2) dilution on the deposition rate is also investigated. The film thickness and morphology is characterized using SEM. Use of high RF power and substrate temperature show increased deposition rate. EDS analysis indicates that these films contain 97-98 atomic percentage of Ge. A recipe for anisotropic dry etching of the deposited Ge films with 10nm/ min etch rate is also suggested.

Effect of Anisotropy of Fibers on the Stress-Strain Response of Fiber-Reinforced Soil

Reinforcing soil with fibers is a useful method for improving the strength and settlement response of soil. The soil and fiber characteristics and their interaction are some of the major factors affecting the strength of reinforced soil. The fibers are usually randomly distributed in the soil, and their orientation has a significant effect on the behavior of the reinforced soil. In the paper, a study of the effect of anisotropic distribution of fibers on the stress-strain response is presented. Based on the concept of the modified Cam clay model, an analytical model was formulated for the fiber-reinforced soil, and the effect of fiber orientation on the stress-strain behavior of soil was studied in detail. The results show that, as the inclination of fibers with the horizontal plane increased, the contribution of fibers in improving the strength of fiber-reinforced soil decreased. The effect of fibers is maximum when they are in the direction of extension, and vice versa. (C) 2014 American Society of Civil Engineers.

Kinetics of dispersion of nanoparticles in thin polymer films at high temperature

We report the first detailed study of the kinetics of dispersion of nanoparticles in thin polymer films using temperature dependent in situ X-ray scattering measurements. We show a comparably enhanced dispersion at higher temperatures for systems which are otherwise phase segregated at room temperature. Detailed analysis of the time dependent X-ray reflectivity and diffuse scattering data allows us to explore the out-of-plane and in-plane mobility of the nanoparticles in the polymer films. While the out-of-plane motion is diffusive with a diffusion coefficient almost two orders of magnitude lower than that expected in bulk polymer, the in-plane one is found to be super-diffusive resulting in significantly larger in-plane displacement at similar time scales. We discuss the origin of the observed highly anisotropic motion of nanoparticles due to their slaved motion with respect to the anisotropic chain orientation and consequent diffusivity anisotropy of matrix chains. We also suggest strategies to utilize these observations to kinetically improve dispersion in otherwise thermodynamically segregated polymer nanocomposite films.

Low temperature giant magnetocaloric effect in multiferroic GdMnO3 single crystals

Magnetocaloric (MC) properties of GdMnO3 single crystals are investigated using magnetic and magneto-thermal measurements. GdMnO3 exhibits a giant MC effect (isothermal change in magnetic entropy (-Delta S-M) similar to 31 J (kg K)(-1) at 7 K and adiabatic change in temperature similar to 10 K at 19 K for magnetic field variation 0-80 kOe). Complex interactions between 3d and 4f magnetic sublattices influence MC properties. The rare-earth antiferromagnetic ordering induces an inverse MC effect (positive Delta S-M) along `a' and `c' axes whereas it's not seen along the `b' axis, revealing complex anisotropic magnetic ordering. The antiferromagnetic ordering possibly changes to ferromagnetic ordering at higher fields.

Inductively coupled reactive ion etching studies on sputtered yttria stabilized zirconia thin films in SF6, Cl-2, and BCl3 chemistries

Downscaling of yttria stabilized zirconia (YSZ) based electrochemical devices and gate oxide layers requires successful pattern transfer on YSZ thin films. Among a number of techniques available to transfer patterns to a material, reactive ion etching has the capability to offer high resolution, easily controllable, tunable anisotropic/isotropic pattern transfer for batch processing. This work reports inductively coupled reactive ion etching studies on sputtered YSZ thin films in fluorine and chlorine based plasmas and their etch chemistry analyses using x-ray photoelectron spectroscopy. Etching in SF6 plasma gives an etch rate of 7 nm/min chiefly through physical etching process. For same process parameters, in Cl-2 and BCl3 plasmas, YSZ etch rate is 17 nm/min and 45 nm/min, respectively. Increased etch rate in BCl3 plasma is attributed to its oxygen scavenging property synergetic with other chemical and physical etch pathways. BCl3 etched YSZ films show residue-free and smooth surface. The surface atomic concentration ratio of Zr/Y in BCl3 etched films is closer to as-annealed YSZ thin films. On the other hand, Cl-2 etched films show surface yttrium enrichment. Selectivity ratio of YSZ over silicon (Si), silicon dioxide (SiO2) and silicon nitride (Si3N4) are 1:2.7, 1:1, and 1:0.75, respectively, in BCl3 plasma. YSZ etch rate increases to 53 nm/min when nonoxygen supplying carrier wafer like Si3N4 is used. (C) 2015 American Vacuum Society.

CROSS-SECTIONAL ANALYSIS OF PRE-TWISTED THICK BEAMS USING VARIATIONAL ASYMPTOTIC METHOD

An asymptotically-exact methodology is presented for obtaining the cross-sectional stiffness matrix of a pre-twisted moderately-thick beam having rectangular cross sections and made of transversely isotropic materials. The anisotropic beam is modeled from 3-D elasticity, without any further assumptions. The beam is allowed to have large displacements and rotations, but small strain is assumed. The strain energy of the beam is computed making use of the constitutive law and the kinematical relations derived with the inclusion of geometrical nonlinearities and initial twist. Large displacements and rotations are allowed, but small strain is assumed. The Variational Asymptotic Method is used to minimize the energy functional, thereby reducing the cross section to a point on the reference line with appropriate properties, yielding a 1-D constitutive law. In this method as applied herein, the 2-D cross-sectional analysis is performed asymptotically by taking advantage of a material small parameter and two geometric small parameters. 3-D strain components are derived using kinematics and arranged as orders of the small parameters. Warping functions are obtained by the minimization of strain energy subject to certain set of constraints that renders the 1-D strain measures well-defined. Closed-form expressions are derived for the 3-D non-linear warping and stress fields. The model is capable of predicting interlaminar and transverse shear stresses accurately up to first order.

Mapping the intriguing transient morphologies and the demixing behavior in PS/PVME blends in the presence of rod-like nanoparticles

The demixing behavior, transient morphologies and mechanism of phase separation in PS/PVME blends were greatly altered in the presence of a very low concentration of rod-like particles (multiwall carbon nanotubes, MWNTs). This phenomenon is due to the specific interaction of one of the phases (PVME) with the anisotropic MWNTs, which creates a heterogeneous environment in the blend. This specific interaction alters the chain dynamics in the interfacial region as against the bulk. A comprehensive analysis using isochronal temperature sweep was performed to understand the demixing temperature in the blends. The evolution of phase morphology as a function of time and temperature was assessed by polarizing optical microscopy (POM), atomic force microscopy (AFM) and scanning electron microscopy (SEM). The addition of MWNTs increased the rheological demixing temperature and the spinodal temperature in almost all the compositions. The intriguing transient morphologies were mapped, which varied from nucleation and growth to coalescence-induced viscoelastic phase separation (C-VPS) in PVME-rich blends, to spinodal decomposition in the near-critical compositions, to transient gel-induced VPS (T-VPS) in the PS-rich compositions. Mapping of the morphology development displayed two types of fracture mechanisms: ductile fracture for near-critical compositions and brittle fracture for off-critical composition. The change in the phase separation mechanism in the presence of MWNTs was due to the variation in dynamic asymmetry brought about by these anisotropic particles. All these observations were correlated by POM, SEM and AFM studies. The length of the cooperatively rearranging region (CRR), as evaluated using modulated differential scanning calorimetry (MDSC) measurements, was found to be composition-independent. The observed variation of effective glass transition of PVME (low T-g component) on blending with PS (high Tg component) and by the addition of MWNTs accounts for the dynamic heterogeneity introduced by MWNTs in the system.