Polyelectrolyte/silver nanocomposite multilayer films as multifunctional thin film platforms for remote activated protein and drug delivery

We demonstrate a nanoparticle loading protocol to develop a transparent, multifunctional polyelectrolyte multilayer film for externally activated drug and protein delivery. The composite film was designed by alternate adsorption of poly(allylamine hydrochloride) (PAH) and dextran sulfate (DS) on a glass substrate followed by nanoparticle synthesis through a polyol reduction method. The films showed a uniform distribution of spherical silver nanoparticles with an average diameter of 50 +/- 20 nm, which increased to 80 +/- 20 nm when the AgNO3 concentration was increased from 25 to 50 mM. The porous and supramolecular structure of the polyelectrolyte multilayer film was used to immobilize ciprofloxacin hydrochloride (CH) and bovine serum albumin (BSA) within the polymeric network of the film. When exposed to external triggers such as ultrasonication and laser light the loaded films were ruptured and released the loaded BSA and CH. The release of CH is faster than that of BSA due to a higher diffusion rate. Circular dichroism measurements confirmed that there was no significant change in the conformation of released BSA in comparison with native BSA. The fabricated films showed significant antibacterial activity against the bacterial pathogen Staphylococcus aureus. Applications envisioned for such drug-loaded films include drug and vaccine delivery through the transdermal route, antimicrobial or anti-inflammatory coatings on implants and drug-releasing coatings for stents. (C) 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Small-scale mechanical testing of materials

Small-scale mechanical testing of materials has gained prominence in the last decade or so due to the continuous miniaturization of components and devices in everyday application. This review describes the various micro-fabrication processes associated with the preparation of miniaturized specimens, geometries of test specimens and the small scale testing techniques used to determine the mechanical behaviour of materials at the length scales of a few hundred micro-meters and below. This is followed by illustrative examples in a selected class of materials. The choice of the case studies is based on the relevance of the materials used in today's world: evaluation of mechanical properties of thermal barrier coatings (TBCs), applied for enhanced high temperature protection of advanced gas turbine engine components, is essential since its failure by fracture leads to the collapse of the engine system. Si-based substrates, though brittle, are indispensible for MEMS/NEMS applications. Biological specimens, whose response to mechanical loads is important to ascertain their role in diseases and to mimic their structure for attaining high fracture toughness and impact resistance. An insight into the mechanisms behind the observed size effects in metallic systems can be exploited to achieve excellent strength at the nano-scale. A future outlook of where all this is heading is also presented.

WEAR AND SLIDING-FRICTION CHARACTERISTICS OF STAINLESS STEEL SS316LN WITHOUT A COATING AND WITH A CrN COATING AT ELEVATED TEMPERATURES AND IN A VACUUM

Stainless steel of type AISI 316LN - one of the structural materials of fast neutron reactors - must have a long service life under conditions that subject it to different types of wear (galling, adhesion, fretting, and abrasion). Cobalt-based hard facings are generally avoided due to induced radioactivity. Nickel-based hard facings are strongly preferred instead. One alternative to both types of coatings is a hard-alloy coating of CrN. This article examines wear and friction characteristics during the sliding of uncoated steel SS316LN and the same steel with a CrN coating. In addition, a specially designed pin-on-disk tribometer is used to perform tests in a vacuum at temperatures of up to 1000 degrees C in order to study the effect of oxygen on the wear of these materials. The morphology of the wear surface and the structure of the subsurface were studied by scanning electron microscopy. The formation of an adhesion layer and the self-welding of mating parts are seen to take place in the microstructure at temperatures above 500 degrees C. It is also found that steel SS316LN undergoes shear strain during sliding wear. The friction coefficient depends on the oxygen content, load, and temperature, while the wear rate depends on the strain-hardening of the surface of the material being tested.

Fretting wear study of Cu-10 wt% TiB2 and Cu-10 wt% TiB2-10 wt% Pb composites

In developing materials with better tribological properties, it is always conceived that the addition of softer phase would result in better frictional behavior. In order to address this issue, we report here the results of fretting wear study on Cu-10 wt% TiB2 and Cu-10 wt% TiB2-10 wt% Pb composites, sintered using spark plasma sintering (SPS) technique. It was found out that the addition of softer phase i.e. 10 wt % Pb to Cu-10 wt% TiB2 composites has not resulted in the lowering of the coefficient of friction (COF). The combination of steady state COF (0.6) and wear rate (10(-3) mm(3)/N-m) was measured and such properties are even better than that obtained with TiB2 coatings reported in the literature. For Cu-10 wt% TiB2 sintered at different temperature, a lower wear resistance with increase in hardness is being measured. An attempt has been made to correlate the observed wear behavior with the surface and subsurface deformation. The formation of a wear-resistant delaminated tribolayer consisting of TiB2 particles and ultrafine oxide debris (Cu, Fe, Ti)(x)O-y was the reason assigned for the observed low wear rate of these composites. (C) 2013 Elsevier B.V. All rights reserved.

Micromechanisms of fracture and strengthening in free-standing Pt-aluminide bond coats under tensile loading

Free-standing Pt-aluminide (PtAl) bond coats exhibit a linear stress strain response under tensile loading and undergo brittle cleavage fracture at temperatures below the brittle-to-ductile transition temperature (BDTT). Above the BDTT, these coatings show yielding and fail in a ductile manner. In this paper, the various micromechanisms affecting the tensile fracture stress (FS) below the BDTT and yield strength (YS) above the BDTT in a PtAl bond coat have been ascertained and quantified at various temperatures. The micromechanisms have been identified by carrying out microtensile testing of stand-alone PtAl coating specimens containing different levels of Pt at temperatures between room temperature and 1100 degrees C and correlation of the corresponding fracture mechanisms with the deformation substructure in the coating. An important aspect of the influence of Pt on the tensile behavior, slip characteristics, FS/YS and BDTT in the PtAl coating has also been examined. The addition of Pt enhances the FS of the coating by Pt solid solution strengthening and imparts a concomitant increase in fracture toughness and yet causes a significant increase in the BDTT of the coating. Published by Elsevier Ltd. on behalf of Acta Materialia Inc.

Morphology and electrostatics play active role in neuronal differentiation processes on flexible conducting substrates

This commentary discusses and summarizes the key highlights of our recently reported work entitled ``Neuronal Differentiation of Embryonic Stem Cell Derived Neuronal Progenitors Can Be Regulated by Stretchable Conducting Polymers.'' The prospect of controlling the mechanical-rigidity and the surface conductance properties offers a unique combination for tailoring the growth and differentiation of neuronal cells. We emphasize the utility of transparent elastomeric substrates with coatings of electrically conducting polymer to realize the desired substrate-characteristics for cellular development processes. Our study showed that neuronal differentiation from ES cells is highly influenced by the specific substrates on which they are growing. Thus, our results provide a better strategy for regulated neuronal differentiation by using such functional conducting surfaces.

Cost-effective wear and oxidation resistant electrodeposited Ni-pumice coating

In the search for newer distributed phases that can be used in Ni-composite coatings, inexpensive and naturally available pumice has been identified as a potential candidate material. The composition of the pumice mineral as determined by Rietveld analysis shows the presence of corundum, quartz, mulllite, moganite and coesite phases. Pumice stone is crushed, ball-milled, dried and dispersed in a nickel sulfamate bath and Ni-pumice coatings are electrodeposited at different current densities and magnetic agitation speeds. Pumice particles are uniformly incorporated in the nickel matrix and Ni-pumice composite coatings with microhardness as high as 540 HK are obtained at the lowest applied current density. In the electrodeposited Ni-pumice coatings, the grain size of Ni increases with the applied current density. The overall intensity of texture development is slightly stronger for the Ni-pumice composite coating compared to plain Ni coating and the texture evolution is possibly not the strongest deciding factor for the enhanced properties of Ni-pumice coatings. The wear and oxidation resistances of Ni-pumice coating are commensurate with that of Ni-SiC coating electrodeposited under similar conditions. (C) 2014 Elsevier B.V. All rights reserved.

Crack stability in edge-notched clamped beam specimens: modeling and experiments

Stability of a fracture toughness testing geometry is important to determine the crack trajectory and R-curve behavior of the specimen. Few configurations provide for inherent geometric stability, especially when the specimen being tested is brittle. We propose a new geometrical construction called the single edge notched clamped bend specimen (SENCB), a modified form of three point bending, yielding stable cracking under load control. It is shown to be particularly suitable for small-scale structures which cannot be made free-standing, (e.g., thin films, coatings). The SENCB is elastically clamped at the two ends to its parent material. A notch is inserted at the bottom center and loaded in bending, to fracture. Numerical simulations are carried out through extended finite element method to derive the geometrical factor f(a/W) and for different beam dimensions. Experimental corroborations of the FEM results are carried out on both micro-scale and macro-scale brittle specimens. A plot of vs a/W, is shown to rise initially and fall off, beyond a critical a/W ratio. The difference between conventional SENB and SENCB is highlighted in terms of and FEM simulated stress contours across the beam cross-section. The `s of bulk NiAl and Si determined experimentally are shown to match closely with literature values. Crack stability and R-curve effect is demonstrated in a PtNiAl bond coat sample and compared with predicted crack trajectories from the simulations. The stability of SENCB is shown for a critical range of a/W ratios, proving that it can be used to get controlled crack growth even in brittle samples under load control.

Effect of wettability and surface roughness on ice-adhesion strength of hydrophilic, hydrophobic and superhydrophobic surfaces

The anti-icing properties of hydrophilic, hydrophobic and superhydrophobic surfaces/coatings were evaluated using a custom-built apparatus based on zero-degree cone test method. The ice-adhesion reduction factor (ARF) of these coatings has been evaluated using bare aluminium alloy as a reference. The wettability of the surfaces was evaluated by measuring water contact angle (WCA) and sliding angle. It was found that the ice-adhesion strength (tau) on silicone based hydrophobic surfaces was similar to 43 times lower than compared to bare polished aluminium alloy indicating excellent anti-icing property of these coatings. Superhydrophobic coatings displayed poor anti-icing property in spite of their high water repellence. Field Emission Scanning Electron Microscope reveal that Silicone based hydrophobic coatings exhibited smooth surface whereas the superhydrophobic coatings had a rough surface consisting of microscale bumps and protrusions superimposed with nanospheres. Both surface roughness and surface energy play a major role on the ice-adhesion strength of the coatings. The 3D surface roughness profiles of the coatings also indicated the same trend of roughness. An attempt is made to correlate the observed ice-adhesion strength of different surfaces with their wettability and surface roughness. (C) 2014 Elsevier B.V. All rights reserved.

Biocompatible and Antibacterial SnO2 Nanowire Films Synthesized by E-Beam Evaporation Method

In this work, the biocompatibility and antibacterial activities of novel SnO2 nanowire coatings prepared by electron-beam (E-Beam) evaporation process at low temperatures were studied. The nanowire coatings were characterized by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), and X-ray diffraction (XRD) methods. The results of in vitro cytotoxicity and cell proliferation assays suggested that the SnO2 nanowire coatings were nontoxic and promoted the proliferation of C2C12 and L929 cells (> 90% viability). Cellular activities, cell adhesion, and lactate dehydrogenase activities were consistent with the superior biocompatibility of the nanowire materials. Notably, the nanowire coating showed potent antibacterial activity against six different bacterial strains. The antibacterial activity of the SnO2 material was attributed to the photocatalytic nature of SnO2. The antibacterial activity and biocompatibility of the newly developed SnO2 nanowire coatings may enable their use as coating materials for biomedical implants.

Quantification of the Particle Size and Stability of Graphene Oxide in a Variety of Solvents

The exceptional solution processing potential of graphene oxide (GO) is always one of its main advantages over graphene in terms of its industrial relevance in coatings, electronics, and energy storage. However, the presence of a variety of functional groups on the basal plane and edges of GO makes understanding suspension behavior in aqueous and organic solvents, a major challenge. Acoustic spectroscopy can also measure zeta potential to provide unique insight into flocculating, meta-stable, and stable suspensions of GO in deionized water and a variety of organic solvents (including ethanol, ethylene glycol, and mineral oil). As expected, a match between solvent polarity and the polar functional groups on the GO surface favors stable colloidal suspensions accompanied by a smaller aggregate size tending toward disperse individual flakes of GO. This work is significant since it describes the characteristics of GO in solution and its ability to act as a precursor for graphene-based materials.

Effect of electrical parameters on morphology and in-vitro corrosion resistance of plasma electrolytic oxidized films formed on zirconium

The objective of the present work is to study the effect of electrical process Parameters (duty cycle and frequency) on morphological, structural, and in-vitro corrosion characteristics of oxide films formed on zirconium by plasma electrolytic oxidation in an electrolyte system consisting of 5 g/L of trisodium orthophosphate. The oxide films fabricated on zirconium by systematically varying the duty cycle and frequency are characterized for its phase composition, surface morphology, chemical composition, roughness, wettability, surface energy, scratch resistance, corrosion resistance, apatite forming ability and osteoblast cell adhesion. X-ray diffraction pattern of all the oxide films showed the predominance of m-ZrO2 phase. Dense and uniform films with thickness varying from 9 to 15 mu m and roughness in the range of 0.62 to 1.03 mu m are formed. Porosity of oxide films is found to be increased with an increase infrequency. The water contact angle results demonstrated that the oxide films exhibited similar hydrophilicity to zirconium substrate. All oxide films showed improved corrosion resistance, as indicated by far lower corrosion current density and passive corrosion potential compared to the zirconium substrate in simulated body fluid environment, and among the four different combinations of duty cycle and frequency employed in the present study, the oxide film formed at 95% duty cycle and 50 Hz frequency (HDLF film) showed superior pitting corrosion resistance, which can be attributed to its pore free morpholOgy. Scratch test results showed that the HDLF oxide film adhered firmly to the substrate by developing a notable scratch resistance at 19.5 +/- 1.2.N. Besides the best corrosion resistance and scratch retistance, the HDLF film also showed good apatite forming ability and osteo sarcoma cell adhesion on its surface. The HDLF oxide film on zirconium with superior surface characteristics is believed to be useful for various types of implants in the dental and orthopedic fields. (C) 2015 Elsevier B.V. All rights reserved.

Electrochemical behavior of Sn-graphene composite coating

The electrochemical properties of pure Sn and Sn-graphene composite coating have been determined and compared. Coatings were electrodeposited on mild steel substrates. Graphene was synthesized by the electrochemical exfoliation process using SO42- ion as the intercalating agent. Morphological and structural characterization results revealed a clear effect of graphene on altering the texture, grain size and morphology of the coating. Corrosion behavior was analyzed through potentiodynamic polarization and electrochemical impedance spectroscopic methods. A significant improvement in the corrosion resistance in terms of reduction in corrosion current and corrosion rate and increase in polarization resistance was noted in case of Sn coating containing graphene.

RF plasma enhanced MOCVD of yttria stabilized zirconia thin films using octanedionate precursors and their characterization

Yttria stabilized zirconia thin films have been deposited by RF plasma enhanced MOCVD technique on silicon substrates at substrate temperature of 400 degrees C. Plasma of precursor vapors of (2,7,7-trimethyl-3,5-octanedionate) yttrium (known as Y(tod)(3)), (2,7,7-trimethyl-3,5-octanedionate) zirconium (known as Zr(tod)(4)), oxygen and argon gases is used for deposition. To the best of our knowledge, plasma assisted MOCVD of YSZ films using octanediaonate precursors have not been reported in the literature so far. The deposited films have been characterized by GIXRD, FTIR, XPS, FESEM, AFM, XANES, EXAFS, EDAX and spectroscopic ellipsometry. Thickness of the films has been measured by stylus profilometer while tribological property measurement has been done to study mechanical behavior of the coatings. Characterization by different techniques indicates that properties of the films are dependent on the yttria content as well as on the structure of the films. (C) 2015 Elsevier B.V. All rights reserved.

Effect of substrates and surfactants over the evolution of crystallographic texture of nanostructured ZnO thin films deposited through microwave irradiation

In spite of intense research on ZnO over the past decade, the detailed investigation about the crystallographic texture of as obtained ZnO thin films/coatings, and its deviation with growth surface is scarce. We report a systematic study about the orientation distribution of nanostructured ZnO thin films fabricated by microwave irradiation with the variation of substrates and surfactants. The nanostructured films comprising of ZnO nanorods are grown on semiconductor substrates such as Si(100), Ge(100)], conducting substrates (ITO-coated glass, Cr coated Si), and polymer coated Si (PMMA/Si) to examine the respective development of crystallographic texture. The ZnO deposited on semiconductor substrates yieldsmixed texture, whereas c-axis oriented ZnO nanostructured films are obtained by conducting substrate, and PMMA coated Si substrates. Among all the surfactants, nanostructured film produced by using the lower molecular weight of polymeric surfactants (polyvinylpyrrolidone) shows a stronger (0002) texture, and that can be tuned to (10 - 10) by increasing the molecular weight of the surfactant. The strongest basal pole is achieved for the ZnO deposited on PMMA coated Si as substrate, and cetyl-trimethyl ammonium bromide as cationic surfactant. The texture analysis is carried out by X-ray pole figure analysis using the Schultz reflection method. (C) 2015 Elsevier B.V. All rights reserved.