Development of high performance electroless Ni-P-HNT composite coatings

Halloysite nanotubes (HNTs) of the dimension 50nm x 1-3 mu m (diameter x length) are utililized to fabricate the alloy composite by employing electroless/autocatalytic deposition technique. Electroless Ni-P-HNT binary alloy composite coatings are prepared successfully on low carbon steel. These nanotubes were made to get inserted/incorporated into nickel matrix and corresponding composites are examined for their electrochemical, mechanical and tribological performances and compared with that of plain Ni-P. The coatings were characterized using scanning electron microscopy (SEM) and Energy dispersive X-ray analysis (EDX) techniques to analyze surface nature and composition correspondingly. Small amount of incorporated HNTs made Ni-P deposits appreciable enhancement and betterment in corrosion resistance, hardness and friction resistance. This drastic improvement in the properties reflects the effect of addition of HNTs into Ni-P matrix leading to the development of high performance Ni-P-HNT composite coatings. (C) 2012 Elsevier B. V. All rights reserved.

Electrochemical capacitors: Technical challenges and prognosis for future markets

Electrochemical capacitors are potential devices that could help bringing about major advances in future energy storage. They are lightweight and their manufacture and disposal has no detrimental effects on the environment. A comprehensive description of fundamental science of electrochemical capacitors is presented. Similarities and differences between electrochemical capacitors and secondary batteries for electrical energy storage are highlighted and various types of electrochemical capacitors are discussed with special reference to lead-carbon hybrid ultracapacitors. Some envisaged applications of electrochemical capacitors are described along with the technical challenges and prognosis for future markets. (C) 2012 Published by Elsevier Ltd.

A Durable Graphitic-Carbon Support for Pt and Pt3Co Cathode Catalysts in Polymer Electrolyte Fuel Cells

The high efficiency of fuel-cell-powered electric vehicles makes them a potentially viable option for future transportation. Polymer Electrolyte Fuel Cells (PEFCs) are most promising among various fuel cells for electric traction due to their quick start-up and low-temperature operation. In recent years, the performance of PEFCs has reached the acceptable level both for automotive and stationary applications and efforts are now being expended in increasing their durability, which remains a major concern in their commercialization. To make PEFCs meet automotive targets an understanding of the factors affecting the stability of carbon support and platinum catalyst is critical. Alloying platinum (Pt) with first-row transition metals such as cobalt (Co) is reported to facilitate both higher degree of crystallinity and enhanced activity in relation to pristine Pt. But a major challenge for the application of Pt-transition metal alloys in PEFCs is to improve the stability of these binary catalysts. Dissolution of the non-precious metal in the acidic environment could alleviate the activity of the catalysts and hence cell performance. The use of graphitic carbon as cathode-catalyst support enhances the long-term stability of Pt and its alloys in relation to non-graphitic carbon as the former exhibits higher resistance to carbon corrosion in relation to the latter in PEFC cathodes during accelerated-stress test (AST). Changes in electrochemical surface area (ESA), cell performance and charge-transfer resistance are monitored during AST through cyclic voltammetry, cell polarization and impedance measurements, respectively. Studies on catalytic electrodes with X-ray diffraction, Raman spectroscopy and transmission electron microscopy reflect that graphitic carbon-support resists carbon corrosion and helps mitigating aggregation of Pt and Pt3Co catalyst particles. (C) 2012 The Electrochemical Society. DOI: 10.1149/2.051301jes] All rights reserved.

Electrochemical determination of thermodynamic properties of DyRhO3 and phase relations in the system Dy-Rh-O

Thermodynamic properties of Dysprosium rhodite (DyRhO3) are measured in the temperature range from 900 to 1,300 K using a solid-state electrochemical cell incorporating yttria-stabilized zirconia as the electrolyte. The standard Gibbs free energy of formation of DyRhO3 with O-type perovskite structure from its components binary oxides, Dysprosia with C-rare earth structure and beta-Rh2O3 with orthorhombic structure, can be represented by the equation: Delta G(f(OX))(O) (+/- 182)/J mol(-1) = -52710+3.821(T/K). By using the thermodynamic data for DyRhO3 from experiment and auxiliary data for other phases from the literature, the phase relations in the system Dy-Rh-O are computed. Thermodynamic data for intermetallic phases in the binary system Dy-Rh, required for constructing the chemical potential diagrams, are evaluated using calorimetric data available in the literature for three intermetallics and Miedema's model, consistent with the phase diagram. The results are presented in the form of Gibbs triangle, oxygen potential-composition diagram, and three-dimensional chemical potential diagram at 1,273 K. Temperature-composition diagrams at constant oxygen partial pressures are also developed. The decomposition temperature of DyRhO3 is 1,732 (+/- 2.5) K in pure oxygen and 1,624 (+/- 2.5) K and in air at standard pressure.

Durability of Pt/C and Pt/MC-PEDOT catalysts under simulated start-stop cycles in polymer electrolyte fuel cells

A composite of mesoporous carbon (MC) with poly(3,4-ethylenedioxythiophene) (PEDOT) is studied as catalyst support for platinum nanoparticles. The durability of commercial Pt/carbon and Pt/MC-PEDOT as cathode catalyst is investigated by invoking air-fuel boundary at the anode side so as to foster carbon corrosion at the cathode side of a polymer electrolyte fuel cell (PEFC). Pt/MC-PEDOT shows higher resistance to carbon corrosion in relation to Pt/C. Electrochemical techniques such as cyclic voltammetry (CV) and impedance measurements are used to evaluate the extent of degradation in the catalyst layer. It is surmised that the resistance of MC-PEDOT as catalyst support toward electrochemical oxidation makes Pt/MC-PEDOT a suitable and stable cathode catalyst for PEFCs.

EQCM investigation of electrochemical deposition and stability of Co-Pi oxygen evolution catalyst of solar energy storage

Photoassisted electrolysis of water is considered as an effective way of storing solar energy in the form of hydrogen fuel. This overall reaction involves the oxidation of water to oxygen at the anode and the reduction of protons to hydrogen at the cathode. Cobalt-phosphate-based catalyst (Co-Pi) is a potentially useful material for oxygen evolution reaction. In the present study, electrochemical deposition of Co-Pi catalyst is carried out on Au-coated quartz crystal from 0.1 M phosphate buffer (pH 7) containing 0.5 mM Co2+ ion, along with the simultaneous measurement of mass changes at the electrode surface. Cyclic voltammograms and mass variations are recorded during the course of deposition. A current peak is observed at 0.92 V vs Ag/AgCl, 3 M KCl corresponding to oxidation of Co2+ ion. The mass of the electrode starts increasing at this potential, suggesting the deposition of a Co(III)-based insoluble product on the electrode surface. The stability of the catalyst is also studied at several potentials in both buffered and nonbuffered electrolyte by monitoring the real-time mass variations.

Probing hemoglobin confinement inside submicron silica tubes using synchrotron SAXS and electrochemical response

The configuration of hemoglobin in solution and confined inside silica nanotubes has been studied using synchrotron small angle X-ray scattering and electrochemical activity. Confinement inside submicron tubes of silica aid in preventing protein aggregation, which is vividly observed for unconfined protein in solution. The radius of gyration (R-g) and size polydispersity (p) of confined hemoglobin was found to be lower than that in solution. This was also recently demonstrated in case of confined hemoglobin inside layered polymer capsules. The confined hemoglobin displayed a higher thermal stability with Rg and p showing negligible changes in the temperature range 25-75 degrees C. The differences in configuration between the confined and unconfined protein were reflected in their electrochemical activity. Reversible electrochemical response (from cyclic voltammograms) obtained in case of the confined hemoglobin, in contrary to the observance of only a cathodic response for the unconfined protein, gave direct indication of the differences between the residences of the electroactive heme center in a different orientation compared to that in solution state. The confined Hb showed loss of reversibility only at higher temperatures. The electron transfer coefficient (alpha) and electron transfer rate constant (k(s)) were also different, providing additional evidence regarding structural differences between the unconfined and confined states of hemoglobin. Thus, absence of any adverse effects due to confinement of proteins inside the inorganic matrices such as silica nanotubes opens up new prospects for utilizing inorganic matrices as protein ``encapsulators'', as well as sensors at varying temperatures.

Employing denaturation for rapid electrochemical detection of myoglobin using TiO2 nanotubes

An alternative antibody-free strategy for the rapid electrochemical detection of cardiac myoglobin has been demonstrated here using hydrothermally synthesized TiO2 nanotubes (Ti-NT). The denaturant induced unfolding of myoglobin led to easy access of the deeply buried electroactive heme center and thus the efficient reversible electron transfer from protein to electrode surface. The sensing performance of the Ti-NT modified electrodes were compared vis a vis commercially available titania and GCEs. The tubular morphology of the Ti-NT led to facile transfer of electrons to the electrode surface, which eventually provided a linear current response (obtained from cyclic voltammetry) over a wide range of Mb concentration. The sensitivity of the Ti-NT based sensor was remarkable and was equal to 18 mu A mg(-1) ml (detection limit = 50 nM). This coupled with the rapid analysis time of a few tens of minutes (compared to a few days for ELISA) demonstrates its potential usefulness for the early detection of acute myocardial infarction (AMI).

Hardening and corrosion behaviour of copper added SUS 304H austenitic steels subjected to thermal cycling

This research was aimed at determining optimum Cu content for the alloy design of SUS 30411 austenitic steels having enhanced heat and corrosion resistance. Samples of the steel containing 1, 3, and 5 wt.% Cu were subjected to repeated heating and cooling to a temperature of 760 degrees C and to a maximum of 15 cycles. Hardness measurement and the corrosion behaviour in 1M NaCl solution were evaluated. The hardness increases with an increase in the number of heating cycles for the three compositions. The hardening response to the thermal cycles is however higher for the 1 wt.% Cu composition and decreases with an increase in the Cu wt.%. The SUS 30411 steel containing 3 wt.% Cu exhibited the least susceptibility to corrosion in the 1M NaCl solution irrespective of the number of heating cycles. The SUS 30411 steel containing 1 wt.% Cu was found to exhibit the highest susceptibility to corrosion for all heating cycles compared.

Carbonaceous nickel oxide nano-composites: as electrode materials in electrochemical capacitor applications

Carbonaceous nickel oxide powder samples have been synthesized from an adducted nickel beta-ketoester complex used as a ``single source precursor'' through a solution-based microwave-assisted chemical route. Comprehensive analysis of the resulting powder material has been carried out using various characterization techniques. These analysis reveal that, depending on the solvent used, either NiO/C or Ni/NiO/C composites are formed, wherein Ni and/or NiO nanocrystals are enveloped in amorphous carbon. As the components emerge from the same molecular source, the composites are homogeneous on a fine scale, making them promising electrode materials for supercapacitors. Electrochemical capacitive behavior of these oxide composites is studied in a three-electrode configuration. With a specific capacitance of 113 F g(-1), Ni/NiO/C is superior to NiO/C as capacitor electrode material, in 0.1 M Na2SO4 electrolyte. This is confirmed by impedance measurements, which show that charge-transfer resistance and equivalent series resistance are lower in Ni/NiO/C than in NiO/C, presumably because of the presence of metallic nickel in the former. The cyclic voltammograms are nearly rectangular and the electrodes display excellent cyclability in different electrolytes: Na2SO4, KOH and Ca(NO3)(2)center dot 4H(2)O. Specific capacitance as high as 143 F g(-1), is measured in Ca(NO3)(2)center dot 4H(2)O electrolyte.

Li3MRuO5 (M = Co, Ni), new lithium-rich layered oxides related to LiCoO2: promising electrochemical performance for possible application as cathode materials in lithium ion batteries

We describe the synthesis and crystal structure of Li3MRuO5 (M = Co and Ni), new rock salt related oxides. Both the oxides crystallize in the layered LiCoO2 (alpha-NaFeO2) structure, as revealed by powder XRD data. Magnetic susceptibility data suggest that the oxidation states of transition metals are Li3Co3+(ls)Ru4+(ls) O-5 (ls = low spin) for the M = Co compound and Li3Ni2+Ru5+O5 for the M = Ni compound. Electrochemical investigations of lithium deintercalation-intercalation behaviour reveal that both Co and Ni phases exhibit attractive specific capacities of ca. 200 mA h g(-1) at an average voltage of 4 V that has been interpreted as due to the oxidation of Co3+ and Ru4+ in Li3CoRuO5 and Ni2+ to Ni4+ in the case of Li3NiRuO5. Thus, a different role of Ru ions is played in the isostructural oxides. Finally, in both cases evidence of irreversible behaviour above 4.2 V is observed and interpreted as formation of high valent ions or alternatively oxidation of oxide ions.

Optimisation of an asymmetric polymerase chain reaction assay for the amplification of single-stranded DNA from Wuchereria bancrofti for electrochemical detection

Single-stranded DNA (ssDNA) is a prerequisite for electrochemical sensor-based detection of parasite DNA and other diagnostic applications. To achieve this detection, an asymmetric polymerase chain reaction method was optimised. This method facilitates amplification of ssDNA from the human lymphatic filarial parasite Wuchereria bancrofti. This procedure produced ssDNA fragments of 188 bp in a single step when primer pairs (forward and reverse) were used at a 100:1 molar ratio in the presence of double-stranded template DNA. The ssDNA thus produced was suitable for immobilisation as probe onto the surface of an Indium tin oxide electrode and hybridisation in a system for sequence-specific electrochemical detection of W. bancrofti. The hybridisation of the ssDNA probe and target ssDNA led to considerable decreases in both the anodic and the cathodic currents of the system's redox couple compared with the unhybridised DNA and could be detected via cyclic voltammetry. This method is reproducible and avoids many of the difficulties encountered by conventional methods of filarial parasite DNA detection; thus, it has potential in xenomonitoring.

Effect of Texture and Grain Size on Bio-Corrosion Response of Ultrafine-Grained Titanium

The bio-corrosion response of ultrafine-grained commercially pure titanium processed by different routes of equal-channel angular pressing has been studied in simulated body fluid. The results indicate that the samples processed through route B-c that involved rotation of the workpiece by 90 deg in the same sense between each pass exhibited higher corrosion resistance compared to the ones processed by other routes of equal-channel angular pressing, as well as the coarse-grained sample. For a similar grain size, the higher corrosion resistance of the samples exhibiting off-basal texture compared to shear texture indicates the major role of texture in corrosion behavior. It is postulated that an optimum combination of microstructure and crystallographic texture can lead to high strength and excellent corrosion resistance.

Synthesis, characterisation and application of an exfoliated graphite-diamond composite electrode in the electrochemical degradation of trichloroethylene

A composite electrode made up of exfoliated graphite (EG) and diamond was prepared for the electrochemical oxidation of trichloroethylene (TCE). The SEM images of the EG-diamond material showed that diamond powders were dispersed on the surface of EG materials. The N-2 adsorption-desorption isotherm of EG-diamond material resulted in a poor adsorption capability due to the insertion of diamond powders into the porous matrix of EG. Raman spectroscopy revealed the presence of characteristic sp(3) bands of diamond confirming good interaction of diamond with EG. Electrochemical characterisation of EG-diamond in 0.1 M Na2SO4 resulted in an enhanced working potential window. The EG-diamond electrode was employed for the electrochemical oxidation of trichloroethylene (0.2 mM) in a Na2SO4 supporting electrolyte. The EG-diamond, in comparison to the pristine EG electrode, exhibited a higher removal efficiency of 94% (EG was 57%) and faster degradation kinetics of 25.3 x 10(-3) min(-1) showing pseudo first order kinetic behaviour. Under the optimised conditions, 73% total organic content (TOC) removal was achieved after 4 h of electrolysis. The degradation of TCE was also monitored with gas chromatography-mass spectrometry. Dichloroacetic acid (DCAA) was identified as a major intermediate product during the electrochemical oxidation of TCE. The electrochemical degradation of TCE at the EG-diamond electrode represents a cost effective method due to the ease of preparation of EG-diamond composite material without the necessity of diamond activation which is normally achieved through doping.

Morphology and electrochemical performance of graphene nanosheet array for Li-ion thin film battery

Highly branched and porous graphene nanosheet synthesized over different substrates as anode for Lithium ion thin film battery. These films synthesized by microwave plasma enhanced chemical vapor deposition at temperature 700 degrees C. Scanning electron microscopy and X-ray photo electron spectroscopy are used to characterize the film surface. It is found that the graphene sheets possess a curled and flower like morphology. Electrochemical performances were evaluated in swezelock type cells versus metallic lithium. A reversible capacity of 520 mAh/g, 450 mAh/g and 637 mAh/g was obtained after 50 cycles when current rate at 23 mu A cm(2) for CuGNS, NiGNS and PtGNS electrodes, respectively. Electrochemical properties of thin film anode were measured at different current rate and gave better cycle life and rate capability. These results indicate that the prepared high quality graphene sheets possess excellent electrochemical performances for lithium storage. (C) 2013 Elsevier Ltd. All rights reserved.