Structural and mechanical properties of room temperature sputter deposited CrN coatings

Chromium nitride (CrN) thin films were deposited at room temperature on silicon and glass substrates using DC reactive magnetron sputtering in Ar + N-2 plasma. Structure and mechanical properties of these films were examined by using XRD, FESEM and nanoindentation techniques. XRD studies revealed that films are of mixed phase at lower nitrogen partial pressure (P-N2) and single phase at higher (P-N2). Microscopy results show that the films were composed of non-equiaxed columns with nanocrystallite morphology. The hardness and elastic modulus of the films increase with increasing nitrogen partial pressure (P-N2). A maximum hardness of similar to 29 GPa and elastic modulus of 341 GPa were obtained, which make these films useful for several potential applications. (C) 2012 Elsevier Ltd. All rights reserved.

Effect of Metal Ions (Ag, Co, Ni, and Pd) on the Visible Light Degradation of Rhodamine B by Carbon-Covered Alumina-Supported TiO2 in Aqueous Solutions

Metal-ion (Ag, Co, Ni, and Pd) doped TiO2 nanocatalysts were successfully embedded on carbon-covered alumina supports. The CCA-embedded catalysts were crystalline and had a high surface area compared to the free metal-ion doped titania nanocatalysts while they still retained the anatase phase of the core TiO2. These catalysts were photocatalytically active under solar light irradiation. Rhodamine B was used as a model pollutant and the reactivity followed a pseudo-first-order reaction kinetics. The reaction rate of the CCA-supported catalysts was Pd > Ag > Co > Ni. Among the ratios of the CCA:catalyst used, it was found that the 1:1 ratio had the fastest reaction rate, followed by the 1:2 ratio, while the 2:1 ratio exhibited the lowest reaction rate. The CCA/metal-ion doped titania were found to have photocatalytic activities comparable with those of CCA-supported titania.

A Comparison of mechanical and tribological behavior of nanostructured and conventional WC-12Co detonation-sprayed coatings

In the present study, WC-12Co coatings were deposited by detonation-spraying technique using conventional and nanostructured WC-12Co feedstock at four different oxy/fuel ratios (OF ratio). The coatings exhibited the presence of phases like W2C and W due to the decarburization of the WC phase, and the proportions of these phases were higher in the nano WC-12Co coatings compared with conventional WC-12Co coatings. Coating hardness and fracture toughness were measured. The tribological performance of coatings was examined under dry sand rubber wheel abrasion wear, and solid particle erosion wear conditions. The mechanical and wear properties of coatings were influenced by degree of decarburization and more so in the case of nanostructured WC-Co coatings. The results indicate that the extent of decarburization has a substantial influence on the elastic modulus of the coating which in turn is related to the extent of intersplat cracking of the coating.

Electronic energy transfer between long-range resonance states of 3-mercaptopropionic acid capped CdTe quantum dots in aqueous media

We demonstrate electronic energy transfer between resonance states of 2 and 2.8 nm CdTe quantum dots in aqueous media using steady-state photoluminescence spectroscopy without using any external linker molecule. With increasing concentration of larger dots, there is subsequent quenching of luminescence in smaller dots accompanied by the enhancement of luminescence in larger dots. Our experimental evidence suggests that there is long-range resonance energy transfer among electronic excitations, specifically from the electronically confined states of the smaller dots to the higher excited states of the larger dots.

Chemical unfolding of chicken villin headpiece in aqueous dimethyl sulfoxide solution: cosolvent concentration dependence, pathway, and microscopic mechanism

Unfolding of a protein often proceeds through partial unfolded intermediate states (PUIS). PUIS have been detected in several experimental and simulation studies. However, complete analyses of transitions between different PUIS and the unfolding trajectory are sparse. To understand such dynamical processes, we study chemical unfolding of a small protein, chicken villin head piece (HP-36), in aqueous dimethyl sulfoxide (DMSO) solution. We carry out molecular dynamics simulations at various solution compositions under ambient conditions. In each concentration, the initial step of unfolding involves separation of two adjacent native contacts, between phenyl alanine residues (11-18 and 7-18). This first step induces, under appropriate conditions, subsequent separation among other hydrophobic contacts, signifying a high degree of cooperativity in the unfolding process. The observed sequence of structural changes in HP-36 on increasing DMSO concentration and the observed sequence of PUIS, are in approximate agreement with earlier simulation results (in pure water) and experimental observations on unfolding of HP-36. Peculiar to water-DMSO mixture, an intervening structural transformation (around 15% of DMSO) in the binary mixture solvent retards the progression of unfolding as composition is increased. This is reflected in a remarkable nonmonotonic composition dependence of RMSD, radius of gyration and the fraction of native contacts. At 30% mole fraction of DMSO, we find the extended randomly coiled structure of the unfolded protein. The molecular mechanism of DMSO induced unfolding process is attributed to the initial preferential solvation of the hydrophobic side chain atoms through the methyl groups of DMSO, followed by the hydrogen bonding of the oxygen atom of DMSO to the exposed backbone NH groups of HP-36.

Characterization and microhardness of Co-W coatings electrodeposited at different pH using gluconate bath: a comparative study

Electrodeposition of Co-W alloy coatings has been carried out with DC and PC using gluconate bath at different pH. These coatings are characterized for their structure, morphology and chemical composition by X-ray diffraction, field emission scanning electron microscopy, differential scanning calorimetry and X-ray photoelectron spectroscopy (XPS). Alloy coatings plated at pH8 are crystalline, whereas coatings electrodeposited at pH5 are nanocrystalline in nature. XPS studies have demonstrated that as-deposited alloy plated at pH8 with DC contain only Co2+ and W6+ species, whereas that alloy plated at pH5 has significant amount of Co-0 and W-0 along with Co2+ and W6+ species. Again, Co2+ and W6+ are main species in all as-deposited PC plated alloys in both pH. Co-0 concentration increases upon successive sputtering of all alloy coatings. In contrast, mainly W6+ species is detected in the following layers of all alloys plated with PC. Alloys plated at pH5 show higher microhardness compared to their pH8 counterparts.

Surfactant free, non-aqueous method, for the deposition of ZnO nanoparticle thin films on Si(100) substrate with tunable ultraviolet (UV) emission

We report, strong ultraviolet (UV) emission from ZnO nanoparticle thin film obtained by a green synthesis, where the film is formed by the microwave irradiation of the alcohol solution of the precursor. The deposition is carried out in non-aqueous medium without the use of any surfactant, and the film formation is quick (5 min). The film is uniform comprising of mono-disperse nanoparticles having a narrow size distribution (15-22 nm), and that cover over an entire area (625 mm(2)) of the substrate. The growth rate is comparatively high (30-70 nm/min). It is possible to tune the morphology of the films and the UV emission by varying the process parameters. The growth mechanism is discussed precisely and schematic of the growth process is provided.

Yield stress, thixotropy and shear banding in a dilute aqueous suspension of few layer graphene oxide platelets

We demonstrate a rigidity percolation transition and the onset of yield stress in a dilute aqueous dispersion of graphene oxide platelets (aspect ratio similar to 5000) above a critical volume fraction of 3.75 x 10(-4) with a percolation exponent of 2.4 +/- 0.1. The viscoelastic moduli of the gel at rest measured as a function of time indicate the absence of structural evolution of the 3D percolated network of disks. However a shear-induced aging giving rise to a compact jammed state and shear rejuvenation indicating a homogenous flow is observed when a steady shear stress (sigma) is imposed in creep experiments. We construct a shear diagram (sigma vs. volume fraction phi) and the critical stress above which shear rejuvenation occurs is identified as the yield stress sigma(y) of the gel. The minimum steady state shear rate (gamma) over dot(m) obtained from creep experiments agrees well with the end of the plateau region in a controlled shear rate flow curve, indicating a shear localization below (gamma) over dot(m). A steady state shear banding in the plateau region of the flow curve observed in particle velocimetry measurements in a Couette geometry confirms that the dilute suspensions of GO platelets form a thixotropic yield stress fluid.

Low temperature and rapid deposition of ZnO nanorods on Si(100) substrate with tunable optical emissions

This research article describes the large scale fabrication of ZnO nanorods of various shapes on Si(100) substrate, by using metalorganic precursor of Zn in solutions with microwave as the source of energy. This is a low temperature, environmental friendly and rapid thin film deposition process, where ZnO nanorods (1-3 mu m length) were grown only in 1-5 min of microwave irradiation. All as-synthesized nanorods are of single crystalline grown along the < 0001 > crystallographic direction. The coated nanorods were found to be highly dense having a thickness of similar to 1-3 mu m over the entire area 20 mm x 20 mm of the substrate. The ZnO thin film comprising of nanorods exhibits good adhesion with the substrate. A possible mechanism for the initial nucleation and growth of ZnO is discussed. A cross over from a strong visible light emission to an enhanced UV emission is observed, when the nature of the surfactants are varied from polymeric to ionic and nonionic. The position of the chromaticity coordinates in yellow region of the color space gives an impression of white light generation from these coatings by exciting with a blue laser.

Resonance raman detection and estimation in the aqueous phase using water dispersible cyclodextrin: reduced-graphene oxide sheets

Resonance Raman spectroscopy is a powerful analytical tool for detecting and identifying analytes, but the associated strong fluorescence background severely limits the use of the technique. Here, we show that by attaching beta-cyclodextrin (beta-CD) cavities to reduced graphene-oxide (rGO) sheets we obtain a water dispersible material (beta-CD: rGO) that combines the hydrophobicity associated with rGO with that of the cyclodextrin cavities and provides a versatile platform for resonance Raman detection. Planar aromatic and dye molecules that adsorb on the rGO domains and nonplanar molecules included within the tethered beta-CD cavities have their fluorescence effectively quenched. We show that it is possible using the water dispersible beta-CD: rGO sheets to record the resonance Raman spectra of adsorbed and included organic chromophores directly in aqueous media without having to extract or deposit on a substrate. This is significant, as it allows us to identify and estimate organic analytes present in water by resonance Raman spectroscopy.

Evaluation of microwave assisted grafted sago starch as controlled release polymeric carrier

In the present investigation an attempt has been made to develop a new co-polymeric material for controlled release tablet formulations. The acrylamide grafting was successfully performed on the backbone of sago starch. The modified starch was tested for acute toxicity and drug-excipient compatibility study. The grafted material was used in making of controlled release tablets of lamivudine. The formulations were evaluated for physical characteristics such as hardness, friability, %drug content and weight variations. The in vitro release study showed that the optimized formulation exhibited highest correlation (R) value in case of Higuchi model and the release mechanism of the optimized formulation predominantly exhibited combination of diffusion and erosion process. There was a significant difference in the pharmacokinetic parameters (T-max, C-max, AUC, V-d, T-1/2 and MDT) of the optimized formulation as compared to the marketed conventional tablet Lamivir (R) was observed. The pharmacokinetics parameters were showed controlled pattern and better bioavailability. The optimized formulation exhibited good stability and release profile at the accelerated stability conditions. (c) 2013 Elsevier B.V. All rights reserved.

Laser receptive polyelectrolyte thin films doped with biosynthesized silver nanoparticles for antibacterial coatings and drug delivery applications

We report a simple method to fabricate multifunctional polyelectrolyte thin films to load and deliver the therapeutic drugs. The multilayer thin films were assembled by the electrostatic adsorption of poly (allylamine hydrochloride) (PAH) and dextran sulfate (DS). The silver nanoparticles (Ag NPs) biosynthesized from novel Hybanthus enneaspermus leaf extract as the reducing agent were successfully incorporated into the film. The biosynthesized Ag NPs showed excellent antimicrobial activity against the range of enteropathogens, which could be significantly enhanced when used with commercial antibiotics. The assembled silver nano composite multilayer films showed rupture and deformation when they are exposed to laser. The Ag NPs act as an energy absorption center, locally heat up the film and rupture it under laser treatment. The antibacterial drug, moxifloxacin hydrochloride (MH) was successfully loaded into the multilayer films. The total amount of MH release observed was about 63% which increased to 85% when subjected to laser light exposure. Thus, the polyelectrolyte thin film reported in our study has significant potential in the field of remote activated drug delivery, antibacterial coatings and wound dressings. (C) 2013 Elsevier B.V. All rights reserved.

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.

Morphological and electrochemical characterization of electrodeposited Zn-Ag nanoparticle composite coatings

Silver nanoparticles with an average size of 23 nm were chemically synthesized and used to fabricate Zn-Ag composite coatings. The Zn-Ag composite coatings were generated by electrodeposition method using a simple sulfate plating bath dispersed with 0.5, land 1.5 g/l of Ag nanoparticles. Scanning electron microscopy, X-ray diffraction and texture co-efficient calculations revealed that Ag nanoparticles appreciably influenced the morphology, micro-structure and texture of the deposit. It was also noticed that agglomerates of Ag nanopartides, in the case of high bath load conditions, produced defects and dislocations on the deposit surface. Ag nanoparticles altered the corrosion resistance property of Zn-Ag composite coatings as observed from Tafel polarization, electrochemical impedance analysis and an immersion test. Reduction in corrosion rate with increased charge transfer resistance was observed for Zn-Ag composite coatings when compared to a pure Zn coating. However, the particle concentration in the plating bath and their agglomeration state directly influenced the surface morphology and the subsequent corrosion behavior of the deposits. (C) 2013 Elsevier Inc. All rights reserved.

Stability of fluctuating and transient aggregates of amphiphilic solutes in aqueous binary mixtures: Studies of dimethylsulfoxide, ethanol, and tert-butyl alcohol

In aqueous binary mixtures, amphiphilic solutes such as dimethylsulfoxide (DMSO), ethanol, tertbutyl alcohol (TBA), etc., are known to form aggregates (or large clusters) at small to intermediate solute concentrations. These aggregates are transient in nature. Although the system remains homogeneous on macroscopic length and time scales, the microheterogeneous aggregation may profoundly affect the properties of the mixture in several distinct ways, particularly if the survival times of the aggregates are longer than density relaxation times of the binary liquid. Here we propose a theoretical scheme to quantify the lifetime and thus the stability of these microheterogeneous clusters, and apply the scheme to calculate the same for water-ethanol, water-DMSO, and water-TBA mixtures. We show that the lifetime of these clusters can range from less than a picosecond (ps) for ethanol clusters to few tens of ps for DMSO and TBA clusters. This helps explaining the absence of a strong composition dependent anomaly in water-ethanol mixtures but the presence of the same in water-DMSO and water-TBA mixtures. (C) 2013 AIP Publishing LLC.