Layer-by-Layer Self-Assembled Metal-Ion- (Ag-, Co-, Ni-, and Pd-) Doped TiO2 Nanoparticles: Synthesis, Characterisation, and Visible Light Degradation of Rhodamine B

Metal-ion- (Ag, Co, Ni and Pd) doped titania nanocatalysts were successfully deposited on glass slides by layer-by-layer (LbL) self-assembly technique using a poly(styrene sulfonate sodium salt) (PSS) and poly(allylamine hydrochloride) (PAH) polyelectrolyte system. Solid diffuse reflectance (SDR) studies showed a linear increase in absorbance at 416 nm with increase in the number of m-TiO2 thin films. The LbL assembled thin films were tested for their photocatalytic activity through the degradation of Rhodamine B under visible-light illumination. From the scanning electron microscope (SEM), the thin films had a porous morphology and the atomic force microscope (AFM) studies showed ``rough'' surfaces. The porous and rough surface morphology resulted in high surface areas hence the high photocatalytic degradation (up to 97% over a 6.5 h irradiation period) using visible-light observed. Increasing the number of multilayers deposited on the glass slides resulted in increased film thickness and an increased rate of photodegradation due to increase in the availability of more nanocatalysts (more sites for photodegradation). The LbL assembled thin films had strong adhesion properties which made them highly stable thus displaying the same efficiencies after five (5) reusability cycles.

The effect of potential on electrodeposited CdSe thin films

Cadmium selenide (CdSe) thin films have been successfully prepared by the electrodeposition technique on indium doped tin oxide (ITO) substrates with aqueous solutions of cadmium sulphate and selenium dioxide. The deposited films were characterized with X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive analysis by X-rays (EDAX), photoluminescence (PL), UV spectrometry and electrical resistivity measurements. XRD analysis shows that the films are polycrystalline in nature with hexagonal crystalline structure. The various parameters such as crystallite size, micro strain, dislocation density and texture coefficients were evaluated. SEM study shows that the total substrate surface is well covered with uniformly distributed spherical shaped grains. Photoluminescence spectra of films were recorded to understand the emission properties of the films. The presence of direct transition with band gap energy 1.75 eV is established from optical studies. The electrical resistivity of the thin films is found to be 10(6) Omega cm and the results are discussed. (c) 2011 Elsevier Ltd. All rights reserved.

Structure and mechanical properties of Ti-C films deposited using combination of pulsed DC and normal DC magnetron co-sputtering

Titanium-carbon (Ti-C) thin films of different compositions were prepared by a combination of pulsed DC (for Ti target) and normal DC (for graphite target) magnetron co-sputtering on oxidized silicon and fused quartz substrates. At 33.7 at.% of C content, pure hcp Ti transforms into fcc-TiC with a preferential orientation of (2 2 0) along with (1 1 1) and (2 0 0). A clear transformation in the preferential orientation from (2 2 0) to (1 1 1) has been observed when the C content was increased to 56 at.%. At 62.5 at.% of C, TiC precipitates in an amorphous carbon matrix whereas further increase in C leads to X-ray amorphous films. The cross-sectional scanning electron microscope images reveal that the films with low carbon content consists of columnar grains, whereas, randomly oriented grains are in an amorphous carbon matrix at higher carbon content. A dramatic variation was observed in the mechanical properties such as hardness, H, from 30 to 1 GPa and in modulus, E, from 255 to 25 GPa with varying carbon content in the films. Resistance to plastic deformation parameter was observed as 0.417 for films containing 62.5 at.% of C. Nanoscratch test reveals that the films are highly scratch resistant with a coefficient of friction ranging from 0.15 to 0.04. (C) 2012 Elsevier B.V. All rights reserved.

Hygrothermal durability and failure modes of FRP for marine applications

This article deals with the durability of 2D woven mat carbon/polyester, glass/isopolyester, and gel-coated glass/isopolyester reinforced composites under hygrothermic conditions with regard to marine applications. The test coupons were exposed to 60 degrees C and 70 degrees C at 95% RH for a maximum duration of 100 h. The samples were periodically withdrawn and weighed for moisture absorption and tested for the degradation in the mechanical properties such as ultimate tensile strength, flexural strength, interlaminar shear strength, and Young's modulus and flexural modulus. Carbon/isopolyester-based specimens showed greater stability with respect to degradation in the mechanical properties than the glass/isopolyester/gel coat- and glass/isopolyester-based specimens. Glass/isopolyester exhibited the maximum moisture absorption, whereas the minimum moisture absorption was found in glass/isopolyester/gel coat. Diffusion coefficient (D) was found to be the highest for glass/isopolyester and the lowest for glass/isopolyester/gel coat, based on the Fick's law of diffusion. Diffusion coefficient increases with the increase in temperature for all the specimens. Microstructure study of fractured specimens was carried out using scanning electron microscope to compare matrix/fiber debonding and matrix-degradation of fiber-reinforced polymer composites.

Solution Combustion Synthesis of Nanosized Copper Chromite and Its Use as a Burn Rate Modifier in Solid Propellants

Nano sized copper chromite, which is used as a burn rate accelerator for solid propellants, was synthesized by the solution combustion process using citric acid and glycine as fuel. Pure spinel phase copper chromite (CuCr2O4) was synthesized, and the effect of different ratios of Cu-Cr ions in the initial reactant and various calcination temperatures on the final properties of the material were examined. The reaction time for the synthesis with glycine was lower compared to that with citric acid. The synthesized samples from both fuel cycles were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), BET surface area analysis, and scanning electron microscope (SEM). Commercial copper chromite that is currently used in solid propellant formulation was also characterized by the same techniques. XRD analysis shows that the pure spinel phase compound is formed by calcination at 700 degrees C for glycine fuel cycle and between 750 and 800 degrees C for citric acid cycle. XPS results indicate the variation of the oxidation state of copper in the final compound with a change in the Cu-Cr mole ratio. SEM images confirm the formation of nano size spherical shape particles. The variation of BET surface area with calcination temperature was studied for the solution combusted catalyst. Burn rate evaluation of synthesized catalyst was carried out and compared with the commercial catalyst. The comparison between BET surface area and the burn rate depicts that surface area difference caused the variation in burn rate between samples. The reason behind the reduction in surface area and the required modifications in the process are also described.

Optical, electrochemical and morphological investigations of poly (3,4-propylenedioxythiophene)-sultone (PProDOT-S) thin films

In this paper, we have carried out thin film characterization of poly(3,4-propylenedioxythiophene)-sultone (PProDOT-S), a derivative of electrochromic poly(3,4-propylenedioxythiophene) (PProDOT). PProDOT-S was deposited onto transparent conducting oxide coated glass substrates by solution casting method. Single wavelength spectrophotometry is used to monitor the switching speed and contrast ratio at maximum wavelength (lambda (max)). The percentage transmittance at the lambda (max) of the neutral polymer is monitored as a function of time when the polymer film is repeatedly switched. This experiment gives a quantitative measure of the speed with which a film is able to switch between the two states i.e. the coloured and the bleached states. PProDOT-S films were switched at a voltage of 1 center dot 9 V with a switching speed of 2 s at lambda (max) of 565 nm and showed a contrast of similar to 37%. Cyclic voltammetry performed at different scan rates have shown the characteristic anodic and cathodic peaks. The structural investigations of PProDOT-S films by IR spectra were in good agreement with previously reported results. Raman spectra of PProDOT-S showed a strong Raman peak at 1509 cm (-aEuro parts per thousand 1) and a weak peak at 1410 cm (-aEuro parts per thousand 1) due to the C = C asymmetric and symmetric stretching vibrations of thiophene rings. The morphological investigations carried out by using scanning electron microscope (SEM) of polymer films have shown that these polymers are found to be arranged in dense packed clusters with non-uniform distribution having an average width and length of 95 nm and 160 nm, respectively.

Charge transport in functionalized multi-wall carbon nanotube-Nafion composite

The charge transport in sulfonated multi-wall carbon nanotube (sMWNT)-Nafion composite is reported. The scanning electron microscope images of the composite, at 1 and 10 wt % of sMWNT, show that the nanotubes are well dispersed in polymer matrix, with conductivity values of 0.005 and 3.2 S/cm, respectively; and the percolation threshold is nearly 0.42 wt. %. The exponent (∼0.25) of the temperature dependence of conductivity in both samples indicates Mott's variable range hopping (VRH) transport. The conductance in 1 wt. % sample increases by three orders of magnitude at high electric-fields, consistent with VRH model. The negative magnetoresistance in 10 wt. % sample is attributed to the forward interference scattering mechanism in VRH transport. The ac conductance in 1 wt. % sample is expressed by σ(ω)∝ωs, and the temperature dependence of s follows the correlated barrier hopping model.

Fracture processes of self compacting Concrete using image analysis

The mode I fracture toughness of concrete can be experimentally determined using three point bend beam in conjunction with digital image correlation (DIC). Three different geometrically similar sizes of beams are cast for this study. To study the influence of fly ash and silica fume on fracture toughness of SCC, three SCC mixes are prepared with and without mineral additions. The scanning electron microscope (SEM) images are taken on the fractured surface to add information on fracture process in SCC. From this study, it is concluded that the fracture toughness of SCC with mineral addition is higher when compared to those without mineral addition.

Tribological response of soft materials sliding against hard surface textures at various numbers of cycles

In the present investigation, various kinds of textures were attained on the steel surfaces. Roughness of the textures was varied using different grits of emery papers or polishing powders. Pins made of pure Al, Al-4Mg alloy and pure Mg were then slid against prepared steel plate surfaces at various numbers of cycles using an inclined pin-on-plate sliding tester. Tests were conducted at a sliding velocity of 2mms(-1) in ambient conditions under both dry and lubricated conditions. Normal loads were increased up to 110N during the tests. The morphologies of the worn surfaces of the pins and the formation of transfer layer on the counter surfaces were observed using a scanning electron microscope. Surface roughness parameters of the plate were measured using an optical profilometer. In the experiments, it was observed that the coefficient of friction and formation of a transfer layer (under dry and lubricated conditions) only depended on surface texture during the first few sliding cycles. The steady-state variation in the coefficient of friction under both dry and lubrication conditions was attributed to the self-organisation of texture of the surfaces at the interface during sliding. Copyright (C) 2012 John Wiley & Sons, Ltd.

Effect of Annealing Temperature in Al 1145 Alloy Sheets on Formability, Void Coalescence, and Texture Analysis

This paper deals with a combined forming and fracture limit diagram and void coalescence analysis for the aluminum alloy Al 1145 alloy sheets of 1.8 mm thickness, annealed at four different temperatures, namely 200, 250, 300, and 350 A degrees C. At different annealing temperatures these sheets were examined for their effects on microstructure, tensile properties, formability, void coalescence, and texture. Scanning electron microscope (SEM) images taken from the fractured surfaces were examined. The tensile properties and formability of sheet metals were correlated with fractography features and void analysis. The variation of formability parameters, normal anisotropy of sheet metals, and void coalescence parameters were compared with texture analysis.

Role of electrolyte chemistry on electronic and in vitro electrochemical properties of micro-arc oxidized titania films on Cp Ti

The primary objective of the present work was to study the electronic and in vitro electrochemical properties of micro-arc oxidized titania films on Cp Ti, fabricated independently in various electrolyte solutions consisting of anions such as phosphate (PO43-), borate (B4O72-), citrate (C6H5O73-) and silicate (SiO32-). Further the role of anions on the structural, morphological and compositional properties of the fabricated films was studied. All the titania films were developed by micro-arc oxidation (MAO) technique for a fixed treatment time of 8 min under constant current mode. The surface morphology, elemental distribution, composition and structural characteristics of the films were assessed by scanning electron microscope (SEM) equipped with energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) techniques. The thermodynamic and kinetic corrosion properties of the films were studied under simulated body fluid (SBF) conditions (pH 7.4 and 37 degrees C) by conducting chronopotentiometric and potentiodynamic polarization tests. Electrochemical impedance spectroscopy (EIS) coupled with equivalent circuit modelling was carried out to analyse the frequency response and Mott-Schottky analysis was performed to study the semiconducting (electronic) properties of the films. Salt spray fog accelerated corrosion test was conducted for 168h as per ASTM B117 standard to corroborate the corrosion and semiconducting properties of the samples based on the visual examination. The XRD results showed that the transformation from the metastable anatase phase to the thermodynamically stable rutile phase and the crystalline growth of the respective phases were strongly influenced by the addition of anions. The SEM-EDS results demonstrated that the phosphorous (P) content in the films varied from 2.4 at% to 5.0 at% indicating that the amount of P in the films could be modified by adding an appropriate electrolyte additive. The electrochemical corrosion test results showed that the film fabricated in citrate (C6H5O73-) containing electrolyte is thermodynamically and kinetically more stable compared to that of all the others. The results of the Mott-Schottky analysis indicated that all the fabricated films showed an n-type semiconducting behaviour and the film developed in citrate (C6H5O73-) containing electrolyte exhibited the lowest donor concentration and the most negative flat band potential that contributed to its highest corrosion resistance in SBF solution. The results of the salt spray accelerated corrosion tests were in agreement with those obtained from the electrochemical and Mott-Schottky analysis.

Single-step synthesis of internally functionalizable hyperbranched polyethers

Radical catalyzed thiol-ene reaction has become a useful alternative to the Huisgen-type azide-yne click reaction as it helps expand the variability in reaction conditions as well as the range of clickable entities. In this study, the direct generation of a hyperbranched polyether (HBPE) having decyl units at the periphery and a pendant allyl group on every repeat unit of the polymer backbone is described; the allyl groups serve as a reactive handle for postpolymerization modifications and permits the generation of a variety of internally functionalized HBPEs. In this design, the AB(2) monomer carries two decylbenzyl ether units (B-functionality), an aliphatic OH (A-functionality) and a pendant allyl group within the spacer segment; polymerization of the monomer readily occurs at 150 degrees C via melt transetherification process by continuous removal of 1-decanol under reduced pressure. The resulting HBPE has a hydrophobic periphery due to the presence of numerous decyl chains, while the allyl groups that remain unaffected during the melt polymerization provides an opportunity to install a variety of functional groups within the interior; thiol-ene click reaction with two different thiols, namely 3-mercaptopropionic acid and mercaptosuccinic acid, generated interesting amphiphilic structures. Preliminary field emission scanning electron microscope (FESEM) and Atomic Force Microscopy (AFM) imaging studies reveal the formation of fairly uniform spherical aggregates in water with sizes ranging from 200 to 400 nm; this suggests that these amphiphilic HBPs is able to reconfigure to generate jellyfish-like conformations that subsequently aggregate in an alkaline medium. The internal allyl functional groups were also used to generate intramolecularly core-crosslinked HBPEs, by the use of dithiol crosslinkers; gel permeation chromatography traces provided clear evidence for reduction in the size after crosslinking. In summary, we have developed a simple route to prepare core-clickable HBPEs and have demonstrated the quantitative reaction of the allyl groups present within the interior of the polymers; such HB polymeric systems that carry numerous functional groups within the core could have interesting applications in analyte sequestration and possibly sensing, especially from organic media. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4125-4135

Deformation-induced grain growth and twinning in nanocrystalline palladium thin films

The microstructure and mechanical properties of nanocrystalline Pd films prepared by magnetron sputtering have been investigated as a function of strain. The films were deposited onto polyimide substrates and tested in tensile mode. In order to follow the deformation processes in the material, several samples were strained to defined straining states, up to a maximum engineering strain of 10%, and prepared for post-mortem analysis. The nanocrystalline structure was investigated by quantitative automated crystal orientation mapping (ACOM) in a transmission electron microscope (TEM), identifying grain growth and twinning/detwinning resulting from dislocation activity as two of the mechanisms contributing to the macroscopic deformation. Depending on the initial twin density, the samples behaved differently. For low initial twin densities, an increasing twin density was found during straining. On the other hand, starting from a higher twin density, the twins were depleted with increasing strain. The findings from ACOM-TEM were confirmed by results from molecular dynamics (MD) simulations and from conventional and in-situ synchrotron X-ray diffraction (CXRD, SXRD) experiments.

Magneto acoustical emission in nanocrystalline Mn-Zn ferrites

Mn0.4Zn0.6Fe2O4 powders were prepared by microwave hydrothermal method. The powders were characterized by X-ray diffraction, transmission electron microscope. The powders were sintered at different temperatures 400, 500, 600, 700, 800 and 900 degrees C/30 min using microwave sintering method. The grain size was estimated by scanning electron microscope. The room temperature dielectric and magnetic properties were studied in the frequency range (100 kHz-1.8 GHz). The magnetization properties were measured upto 1.5 T. The acoustic emission has been measured along the hysteresis loops from 80 K to Curie temperature. It is found that the magneto-acoustic emission (MAE) activity along hysteresis loop is proportional to the hysteresis losses during the same loop. This law has been verified on series of polycrystalline ferrites and found that the law is valid whatever the composition, the grain size and temperature. It is also found that the domain wall creation/or annihilation processes are the origin of the MAE. (C) 2013 Published by Elsevier Ltd.

Nonlinear optical second harmonic generation in ZnS quantum dots and observation on optical properties of ZnS/PMMA nanocomposites

ZnS quantum dots (QDs) of different sizes are synthesized by a simple chemical co-precipitation method at room temperature, by varying pH value of the reaction mixture. Samples are characterized by an X-ray diffractometer, transmission electron microscope, energy-dispersive X-ray analysis, etc. Linear optical properties, including UV-visible absorption and photoluminescence emission characteristics, of as-prepared QDs are measured. Size dependent nonlinear optical property, such as second harmonic generation (SHG) of 1064 nm Nd:YAG laser fundamental radiation in the synthesized ZnS QDs, is reported for the first time, to the best of our knowledge, by using the standard Kurtz-Perry powder method. In not to study the possibility of the synthesized ZnS QDs in different device applications ZnS/PMMA (polymethylmethacrylate) nanocomposites are also synthesized. The presence of weak chemical interaction between the polymer matrix and ZnS QDs is confirmed by Fourier transform infrared spectroscopy. Thermal properties of the nanocomposites are studied by differential scanning calorimetry and thermo-gravimetric analysis techniques, which show that the composites are stable up to similar to 300 degrees C temperature. (C) 2013 Elsevier B.V. All rights reserved.