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.

AZ91C magnesium alloy modified by Cd

In the present work, the effect of Cd on the microstructure, mechanical properties and general corrosion behaviour of AZ91C alloys was investigated. Addition of Cd was found not to be efficient in modifying/refining the microstructure or beta-phase. A morphology change in beta-phase from fine continuous precipitates to discontinuous beta-phase upon the addition of Cd was observed. A marginal increment in mechanical properties was observed. General corrosion behaviour was followed with weight loss measurements, potentiostatic polarisation studies and surface studies in 3.5% sodium chloride solution and 3.5% sodium chloride with 2% potassium dichromate solution. Cd addition deteriorated the corrosion behaviour of AZ91C. This behaviour was attributed to the formation of chunks of beta-phase upon the addition of Cd. AZ91C with refined beta-phase distribution, performed rather better in the NaCl solutions. (C) 2013 Elsevier Ltd. All rights reserved.

Early osseointegration of a strontium containing glass ceramic in a rabbit model

The most important property of a bone cement or a bone substitute in load bearing orthopaedic implants is good integration with host bone with reduced bone resorption and increased bone regeneration at the implant interface. Long term implantation of metal-based joint replacements often results in corrosion and particle release, initiating chronic inflammation leading onto osteoporosis of host bone. An alternative solution is the coating of metal implants with hydroxyapatite (HA) or bioglass or the use of bulk bioglass or HA-based composites. In the above perspective, the present study reports the in vivo biocompatibility and bone healing of the strontium (Sr)-stabilized bulk glass ceramics with the nominal composition of 4.5SiO(2)-3Al(2)O(3)-1.5P(2)O(5)-3SrO-2SrF(2) during short term implantation of up to 12 weeks in rabbit animal model. The progression of healing and bone regeneration was qualitatively and quantitatively assessed using fluorescence microscopy, histological analysis and micro-computed tomography. The overall assessment of the present study establishes that the investigated glass ceramic is biocompatible in vivo with regards to local effects after short term implantation in rabbit animal model. Excellent healing was observed, which is comparable to that seen in response to a commercially available implant of HA-based bioglass alone. (C) 2013 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.

On Using Nanoporous Alumina Films as Tribological Coating

Anodization of aluminum alloys is a common surface treatment procedure employed for the protection against corrosion. A thin amorphous layer of alumina is formed on the surface of alloy, which seals the alloy surface from the surrounding. This alumina layer being harder than the base aluminum alloy can be useful as a tribological coating. But since this alumina layer is randomly formed with disordered voids and pores, predicting the mechanical properties is difficult. Specific anodizing conditions can be used to form highly ordered anodic nanoporous alumina films 1] on the aluminum alloy surface. These nanoporous alumina layer can be effectively used as a tribological coating, because of the highly ordered controllable geometry and the empty pores which can be used as reservoirs for lubricant.

Effect of TiN particulate reinforcement on corrosive behaviour of aluminium 6061 composites in chloride medium

In the present investigation, the corrosive behaviour of Al 6061-TiN particulate composites prepared by liquid metallurgy has been studied in chloride medium using electroanalytical techniques such as Tafel, cyclic polarization and electrochemical impedance spectroscopy (EIS). Surface morphology of the sample electrodes was examined using scanning electron micrography and energy dispersive X-ray methods. X-ray diffraction technique was used to confirm inclusion of TiN particulates in the matrix alloy and identify the alloying elements and intermetallic compounds in the Al 6061 composites. Polarization studies indicate an increase in the corrosion resistance in composites compared to the matrix alloy. EIS study reveals that the polarization resistance (R (p)) increases with increase in TiN content in composites, thus confirming improved corrosion resistance in composites. The observed decrease in corrosion rate in the case of composites is due to decoupling between TiN particles and Al 6061 alloy. It is understood that after the initiation of corrosion, interfacial corrosion products may have decoupled the conducting ceramic TiN from Al 6061 matrix alloy thus eliminating the galvanic effect between them.

Autocatalytic duplex Ni-P/Ni-W-P coatings on AZ31B magnesium alloy

Autocatalytic duplex Ni-P/Ni-W-P coatings were deposited on AZ31B magnesium alloy using stabilizer free nickel carbonate bath. Some of the coated specimens were passivated in chromate solution with and without heat treatment. Plain Ni-P coatings were also prepared for comparison. Coatings were characterized for their surface morphology, composition and corrosion resistance. Energy dispersive analysis of X-ray (EDX) showed that the phosphorous content in the Ni-P coating is 6 wt.% and for Ni-W-P it reduced to 3 wt.% due to the codeposition of tungsten in the Ni-P coating. Marginal increase in P and W contents was observed on passivated coupons along with Cr (0.18 wt.%) and O (2.8 wt.%) contents. Field emission scanning electron microscopy (FESEM) examination of these coating surfaces exhibited the nodular morphology. Chromate passivated surfaces showed the presence of uniformly distributed bright Ni particles along with nodules. Potenfiodynamic polarization and electrochemical impedance spectroscopy (EIS) studies were carried out in deaerated 0.15 M NaCI solution to find out the corrosion resistance of the coatings. Among the coatings developed, duplex-heat treated-passivated (duplex-HIP) coatings showed lower corrosion current density (i(corr)) and higher polarization resistance (R-p) indicating the improved corrosion resistance. The charge transfer resistance (R-ct) value obtained for the duplex-HIP was about 170 times higher compared to that for Ni P coating. (c) 2013 Elsevier B.V. All rights reserved.

Conformal Cytocompatible Ferrite Coatings Facilitate the Realization of a Nanovoyager in Human Blood

Controlled motion of artificial nanomotors in biological environments, such as blood, can lead to fascinating biomedical applications, ranging from targeted drug delivery to microsurgery and many more. In spite of the various strategies used in fabricating and actuating nanomotors, practical issues related to fuel requirement, corrosion, and liquid viscosity have limited the motion of nanomotors to model systems such as water, serum, or biofluids diluted with toxic chemical fuels, such as hydrogen peroxide. As we demonstrate here, integrating conformal ferrite coatings with magnetic nanohelices offer a promising combination of functionalities for having controlled motion in practical biological fluids, such as chemical stability, cytocompatibility, and the generated thrust. These coatings were found to be stable in various biofluids, including human blood, even after overnight incubation, and did not have significant influence on the propulsion efficiency of the magnetically driven nanohelices, thereby facilitating the first successful ``voyage'' of artificial nanomotors in human blood. The motion of the ``nanovoyager'' was found to show interesting stick-slip dynamics, an effect originating in the colloidal jamming of blood cells in the plasma. The system of magnetic ``nanovoyagers'' was found to be cytocompatible with C2C12 mouse myoblast cells, as confirmed using MTT assay and fluorescence microscopy observations of cell morphology. Taken together, the results presented in this work establish the suitability of the ``nanovoyager'' with conformal ferrite coatings toward biomedical applications.

Pristine and graphitized-MWCNTs as durable cathode-catalyst supports for PEFCs

Long-term deterioration in the performance of PEFCs is attributed largely to reduction in active area of the platinum catalyst at cathode, usually caused by carbon-support corrosion. Multi-walled carbon-nanotubes (MWCNTs) as cathode-catalyst support are found to enhance long-term stability of platinum catalyst (Pt) in relation to non-graphitic carbon. In addition, highly graphitic MWCNTs (G-MWCNTs) are found to be electrochemically more stable than pristine MWCNTs. This is because graphitic-carbon-supported-Pt (Pt/MWCNTs) cathodes exhibit higher resistance to carbon corrosion in-relation to non-graphitic-carbon-supported-Pt (Pt/C) cathodes in PEFCs during accelerated stress-test (AST) as evidenced by chronoamperometry and carbon dioxide studies. The corresponding change in electrochemical surface area (ESA), cell performance, and charge-transfer resistance are monitored through cyclic voltammetry, cell polarization, and impedance measurements, respectively. The extent of crystallinity, namely amorphous or graphitic nature of the three supports, is examined by Raman spectroscopy. X-ray diffraction and transmission electron microscopy studies both prior and after AST suggest lesser deformation in catalyst layer and catalyst particles for Pt/G-MWCNTs and Pt/MWCNTs cathodes in relation to Pt/C cathodes, reflecting that graphitic carbon-support resists carbon corrosion and helps mitigating aggregation of Pt particles. It is also found that with increasing degree of graphitization, the electrochemical stability for MWCNTs increases due to the lesser surface defects.

Biodegradable Mg and Mg based alloys for biomedical implants

Mg and its alloys become natural biomaterials as the elemental Mg is found in the human body in abundance and their mechanical properties being akin to the natural bone as well as due to their inherent bioabsorbable/bioresorbable property. This paper discusses the development of new Mg alloys and their corrosion characteristics in detail. The latest advancements in coating of Mg alloys to control their degradation rate are also reviewed along with the future challenges that need to be addressed.

12 V / kilo-Farad Range Lead-Carbon Hybrid Ultracapacitors and Their Envisaged Applications

12 V / kilo-Farad (kF) range substrate-integrated lead-carbon hybrid ultracapacitors (HUCs) wherein the conventional positive plates of lead-acid batteries are replaced with substrate-integrated PbO2 positive plates and the negative plates are replaced with carbon-coated graphitic electrodes, providing totally non-faradaic and corrosion-free electrodes, are developed and performance tested. Constant-current discharge data at varying load-currents, constant-power discharge data at varying power values, and the capacitance data at different temperature for a 12 V / kF range substrate-integrated lead-carbon HUC are described along with its resistance, leakage current, self-discharge and cycle-life characteristics.

The importance of crystallographic texture in the use of titanium as an orthopedic biomaterial

Crystallographic texture is perceived to play an important role in controlling material properties. However, the influence of texture in modulating the properties of biomedical materials has not been well investigated. In this work, commercially pure titanium (cp-Ti) was processed through six different routes to generate a variety of textures. The effect of texture on mechanical properties, corrosion behavior, cell proliferation and osteogenesis was characterized for potential use in orthopedic applications. The presence of closely packed, low-energy crystallographic planes at the material surface was influenced by the volume fraction of the components in the overall texture, thereby influencing surface energy and corrosion behavior. Texture modulated osteoblast proliferation through variations in surface water wettability. It also affected mineralization by possibly influencing the coherency between the substrate and calcium phosphate deposits. This study demonstrates that crystallographic texture can be an important tool in improving the properties of biomaterials to achieve the enhanced performance of biomedical implants.

The control of crystallographic texture in the use of magnesium as a resorbable biomaterial

Magnesium and its alloys are an emerging class of resorbable materials for orthopedic and cardiovascular applications. The typical strategy underlying the development of these materials involves the control of material processing routes and the addition of alloying elements. Crystallographic texture is known to control bulk mechanical as well as surface properties. However, its role in determining the properties of magnesium for implant materials has not been well studied. In this work, an extruded rod of pure magnesium was cut in multiple directions to generate samples with different textures. It was found that texture significantly affected the strength and ductility of magnesium. Corrosion rates in Hank's solution decreased with the increased presence of low energy basal planes at the surface. In vitro cell studies revealed that changes in texture did not induce cytotoxicity. Thus, the control of texture in magnesium based implants could be used to tailor the mechanical properties and the resorption rates without compromising cytocompatibility. This study elucidates the importance of texture in the use of magnesium as a resorbable biomaterial.

Zinc oxide based photocatalysis: tailoring surface-bulk structure and related interfacial charge carrier dynamics for better environmental applications

As an alternative to the gold standard TiO2 photocatalyst, the use of zinc oxide (ZnO) as a robust candidate for wastewater treatment is widespread due to its similarity in charge carrier dynamics upon bandgap excitation and the generation of reactive oxygen species in aqueous suspensions with TiO2. However, the large bandgap of ZnO, the massive charge carrier recombination, and the photoinduced corrosion-dissolution at extreme pH conditions, together with the formation of inert Zn(OH)(2) during photocatalytic reactions act as barriers for its extensive applicability. To this end, research has been intensified to improve the performance of ZnO by tailoring its surface-bulk structure and by altering its photogenerated charge transfer pathways with an intention to inhibit the surface-bulk charge carrier recombination. For the first time, the several strategies, such as tailoring the intrinsic defects, surface modification with organic compounds, doping with foreign ions, noble metal deposition, heterostructuring with other semiconductors and modification with carbon nanostructures, which have been successfully employed to improve the photoactivity and stability of ZnO are critically reviewed. Such modifications enhance the charge separation and facilitate the generation of reactive oxygenated free radicals, and also the interaction with the pollutant molecules. The synthetic route to obtain hierarchical nanostructured morphologies and study their impact on the photocatalytic performance is explained by considering the morphological influence and the defect-rich chemistry of ZnO. Finally, the crystal facet engineering of polar and non-polar facets and their relevance in photocatalysis is outlined. It is with this intention that the present review directs the further design, tailoring and tuning of the physico-chemical and optoelectronic properties of ZnO for better applications, ranging from photocatalysis to photovoltaics.

Electrochemical behavior of Zn-graphene composite coatings

A Zn-graphene composite coating was electrodeposited on mild steel. The graphene was synthesized by electrochemical exfoliation of graphite. Electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction techniques were used to characterize the coatings. Compared to a pure Zn coating, the Zn-graphene coating exhibited reduced grain size, reduced surface defects, hillock structures over the coating surface and an altered texture. The corrosion behavior of the coatings was examined by Tafel 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 the case of the Zn coating containing graphene.