Enhancement of Corrosion Resistance of Zinc Coatings Using Green Additives

In the present work, morphology, microstructure, and electrochemical behavior of Zn coatings containing non-toxic additives have been investigated. Zn coatings were electrodeposited over mild steel substrates using Zn sulphate baths containing four different organic additives: sodium gluconate, dextrose, dextrin, and saccharin. All these additives are ``green'' and can be derived from food contents. Morphological and structural characterization using electron microscopy, x-ray diffraction, and texture co-efficient analysis revealed an appreciable alteration in the morphology and texture of the deposit depending on the type of additive used in the Zn plating bath. All the Zn coatings, however, were nano-crystalline irrespective of the type of additive used. Polarization and electrochemical impedance spectroscopic analysis, used to investigate the effect of the change in microstructure and morphology on corrosion resistance behavior, illustrated an improved corrosion resistance for Zn deposits obtained from plating bath containing additives as compared to the pure Zn coatings.

Electromagnetic shielding materials and coatings derived from gelation of multiwall carbon nanotubes in an LCST mixture

Thermally induced demixing in an LCST mixture, polystyrene (PS)/polyvinyl methyl ether] (PVME), was used as a template to design materials with high electrical conductivity. This was facilitated by gelation of multiwall carbon nanotubes (MWNTs) in a given phase of the blends. The MWNTs were mixed in the miscible blends and the thermodynamic driven demixing further resulted in selective localization in the PVME phase of the blends. This was further confirmed by atomic force microscopy (AFM). The time dependent gelation of MWNTs at shallow quench depth, evaluated using isochronal temperature sweep by rheology, was studied by monitoring the melt electrical conductivity of the samples in situ by an LCR meter coupled to a rheometer. By varying the composition in the mixture, several intricate shapes like gaskets and also coatings capable of attenuating the EM radiation in the microwave frequency can be derived. For instance, the PVME rich mixtures can be molded in the form of a gasket, O-ring and other intricate shapes while the PS rich mixtures can be coated onto an insulating polymer to enhance the shielding effectiveness (SE) for EM radiation. The SE of the various materials was analyzed using a vector network analyzer in both the X-band (8.2 to 12 GHz) and the K-u-band (12 to 18 GHz) frequency. The improved SE upon gelation of MWNTs in the demixed blends is well evident by comparing the SE before and after demixing. A reflection loss of -35 dB was observed in the blends with 2 wt% MWNTs. Further, by coating a layer of ca. 0.15 mm of PS/PVME/MWNT, a SE of -15 dB at 18 GHz could be obtained.

Development, in vitro and in vivo characterization of zoledronic acid functionalized hydroxyapatite nanoparticle based formulation for treatment of osteoporosis in animal model

We investigated the potential of using novel zoledronic acid (ZOL)-hydroxyapatite (HA) nanoparticle based drug formulation in a rat model of postmenopausal osteoporosis. By a classical adsorption method, nanoparticles of HA loaded with ZOL (HNLZ) drug formulation with a size range of 100-130 nm were prepared. 56 female Wistar rats were ovariectomized (OVX) or sham-operated at 3 months of age. Twelve weeks post surgery, rats were randomized into seven groups and treated with various doses of HNLZ (100, 50 and 25 mu g/kg, intravenous single dose), ZOL (100 mu g/kg, intravenous single dose) and HA nanoparticle (100 mu g/kg, intravenous single dose). Untreated OVX and sham OVX served as controls. After three months treatment period, we evaluated the mechanical properties of the lumbar vertebra and femoral mid-shaft. Femurs were also tested for trabecular microarchitecture. Sensitive biochemical markers of bone formation and bone resorption in serum were also determined. With respect to improvement in the mechanical strength of the lumbar spine and the femoral mid-shaft, the therapy with HNLZ drug formulation was more effective than ZOL therapy in OVX rats. Moreover, HNLZ drug therapy preserved the trabecular microarchitecture better than ZOL therapy in OVX rats. Furthermore, the HNLZ drug formulation corrected increase in serum levels of bone-specific alkaline phosphatase, procollagen type I N-terminal propeptide, osteocalcin, tartrate-resistant acid phosphatase 5b and C-telopeptide of type 1 collagen better than ZOL therapy in OVX rats. The results strongly suggest that HNLZ novel drug formulation appears to be more effective approach for treating severe osteoporosis in humans. (C) 2014 Elsevier B.V. All rights reserved.

Hydroxyapatite-titanium bulk composites for bone tissue engineering applications

The research work on bulk hydroxyapatite (HA)-based composites are driven by the need to develop biomaterials with better mechanical properties without compromising its bioactivity and biocompatibility properties. Despite several years of research, the mechanical properties of the HA-based composites still need to be enhanced to match the properties of natural cortical bone. In this regard, the scope of this review on the HA-based bulk biomaterials is limited to the processing and the mechanical as well as biocompatibility properties for bone tissue engineering applications of a model system that is hydroxyapatite-titanium (HA-Ti) bulk composites. It will be discussed in this review how HA-Ti based bulk composites can be processed to have better fracture toughness and strength without compromising biocompatibility. The advantages of the functionally gradient materials to integrate the mechanical and biocompatibility properties is a promising approach in hard tissue engineering and has been emphasized here in reference to the limited literature reports. On the biomaterials fabrication aspect, the recent results are discussed to demonstrate that advanced manufacturing techniques, like spark plasma sintering can be adopted as a processing route to restrict the sintering reactions, while enhancing the mechanical properties. Various toughening mechanisms related to careful tailoring of microstructure are discussed. The in vitro cytocompatibilty, cell fate processes as well as in vivo biocompatibility results are also reviewed and the use of flow cytometry to quantify in vitro cell fate processes is being emphasized. (C) 2014 Wiley Periodicals, Inc.

Manipulating Crystallographic Texture of Sn Coatings by Optimization of Electrodeposition Process Conditions to Suppress Growth of Whiskers

The effects of two major electrodeposition process conditions, electrolyte bath temperature and current density, on the microstructure and crystallographic texture of pure tin coatings on brass and, ultimately, on the extent of whisker formation have been examined. The grain size of the deposited coatings increased with increasing electrolyte bath temperature and current density, which significantly affected the dominant texture: (211) or (420) was the dominant texture at low current densities whereas, depending on deposition temperature, (200) or (220) became the dominant texture at high current densities. After deposition, coatings were subjected to different environmental conditions, for example isothermal aging (room temperature, 50A degrees C, or 150A degrees C) for up to 90 days and thermal cycling between -25A degrees C and 85A degrees C for 100 cycles, and whisker growth was studied. The Sn coatings with low Miller index planes, for example (200) and (220), and with moderate aging temperature were more prone to whiskering than coating with high Miller index planes, for example (420), and high aging temperature. A processing route involving the optimum combination of current density and deposition temperature is proposed for suppressing whisker growth.

CHARACTERIZATION AND MICROHARDNESS OF ELECTRODEPOSITED Ni-W COATINGS OBTAINED FROM GLUCONATE BATH

Ni-W alloy coatings are electrodeposited with direct and pulse current using gluconate bath at pH5. Effects of direct current (DC) and pulse current (PC) on structural characteristics of the coatings have been investigated by energy dispersive X-ray spectroscopy (EDXS), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), differential scanning calorimetry (DSC) and X-ray photoelectron spectroscopy (XPS). EDXS shows that W contents are 13.3 and 12.6 at.% in DC and PC (10:40) Ni-W coatings, respectively. FESEM analysis exhibits the homogeneous coarse nodular morphology in DC plated deposits. DSC studies reveal that Ni-W coatings are thermally stable up to 400 degrees C. XPS studies demonstrate that DC plated coating has significant amount of Ni and W in elemental form along with their respective oxidized species. In contrast, mainly oxidized metals are present in the as-deposited coatings prepared with PC plating. The microhardness of pulse current (100:400) deposited Ni-W coating is about 750HK that is much higher than DC plated coating (635 HK). Heat treatment of the deposits carried out at different temperatures show a significant increase in microhardness which can be comparable with hard chromium coatings.

Conductivity Studies of Silver-, Potassium-, and Magnesium-Doped Hydroxyapatite

We report the electrical transport properties of silver-, potassium-, and magnesium-doped hydroxyapatites (HAs). While Ag+ or K+ doping to HA enhances the conductivity, Mg+2 doping lowers the conductivity when compared with undoped HA. The mechanism behind the observed differences in ionic conductivity has been discussed using the analysis of high-temperature frequency-dependent conductivity data, Cole-Cole plots of impedance data as well as on the basis of the frequency dependence of the imaginary part (M) of the complex electric modulus. The f(max) of modulus M decreased in silver- and potassium-doped samples in comparison with the undoped HA.

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.

Structural and Magnetic Phase Transformations of Hydroxyapatite-Magnetite Composites under Inert and Ambient Sintering Atmospheres

The present work reports the impact of sintering conditions on the phase stability in hydroxyapatite (HA) magnetite (Fe3O4) bulk composites, which were densified using either pressureless sintering in air or by rapid densification via hot pressing in inert atmosphere. In particular, the phase abundances, structural and magnetic properties of the (1-x)HA-xFe(3)O(4) (x = 5, 10, 20, and 40 wt %) composites were quantified by corroborating results obtained from Rietveld refinement of the X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Mossbauer spectroscopy. Post heat treatment phase analysis revealed a major retention of Fe3O4 in argon atmosphere, while it was partially/completely oxidized to hematite (alpha-Fe2O3) in air. Mossbauer results suggest the high-temperature diffusion of Fe3+ into hydroxyapatite lattice, leading to the formation of Fe-doped HA. A preferential occupancy of Fe3+ at the Ca(1) and Ca(2) sites under hot-pressing and conventional sintering conditions, respectively, was observed. The lattice expansion in HA from Rietveld analysis correlated well with the amounts of Fe-doped HA determined from the Mossbauer spectra. Furthermore, hydroxyapatite in the monoliths and composites was delineated to exist in the monoclinic (P2(1)/b) structure as against the widely reported hexagonal (P6(3)/m) crystal lattice. The compositional similarity of iron doping in hydroxyapatite to that of tooth enamel and bone presents HA-Fe3O4 composites as potential orthopedic and dental implant materials.

Synthesis and electrochemical behaviour of NiFeCr nanoparticle coatings

NiFeCr nanoparticles with a Ni-rich composition were synthesized using a wet chemical synthesis technique. As-synthesized nanoparticles were crystalline with an average size of 6.8 +/- 2.5 nm. For electrochemical analysis, as-synthesized nanoparticles were mixed with epoxy and coated over a mild steel substrate. Electrochemical measurements exhibited a very high polarization resistance and very low corrosion current for the nanoparticle-epoxy coated sample illustrating high resistance of the NiFeCr nanoparticle-epoxy coating towards highly corrosive media.

Damage mechanisms in stainless steel and chromium carbide coatings under controlled environment fretting conditions

Fretting is of a serious concern in many industrial components, specifically, in nuclear industry for the safe and reliable operation of various component and/or system. Under fretting condition small amplitude oscillations induce surface degradation in the form of surface cracks and/or surface wear. Comprehensive experimental studies have been carried out simulating different fretting regimes under ambient and vacuum (10(-9) MPa) conditions and, temperature up to 400 degrees C. Studies have been carried out with stainless steel spheres on stainless steel flats, and stainless steel spheres against chromium carbide, with 25% nickel chrome binder coatings. Mechanical responses are correlated with the damage observed. It has been observed that adhesion plays a vital role in material degradation process, and its effectiveness depends on mechanical variables such as normal load, interfacial tangential displacement, characteristics of the contacting bodies and most importantly on the environment conditions. Material degradation mechanism for ductile materials involved severe plastic deformation, which results in the initiation or nucleation of cracks. Ratcheting has been observed as the governing damage mode for crack nucleation under cyclic tangential loading condition. Further, propagation of the cracks has been observed under fatigue and their orientation has been observed to be governed by the contact conditions prevailing at the contact interface. Coated surfaces show damage in the form of brittle fracture and spalling of the coatings. Existence of stick slip has been observed under high normal load and low displacement amplitude. It has also been observed that adhesion at the contact interface and instantaneous cohesive strength of the contacting bodies dictates the occurrence of material transfer. The paper discusses the mechanics and mechanisms involved in fretting damage under controlled environment conditions. (C) 2015 Elsevier B.V. All rights reserved.

Ag-doped hydroxyapatite as efficient adsorbent for removal of Congo red dye from aqueous solution: Synthesis, kinetic and equilibrium adsorption isotherm analysis

In the present study a versatile and efficient adsorbent with high adsorption capacity for adsorption of Congo red dye in aqueous solution at ambient temperature without adjusting any pH is presented over the Ag modified calcium hydroxyapatite (CaHAp). CaHAp and Ag-doped CaHAp materials were synthesized using facile aqueous precipitation method. The physico-chemical properties of the materials were determined by powder X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, Transmission electron microscopy (TEM), UV-Visible spectroscopy, N-2 physisorption and acidity was determined by n-butylamine titration and pyridine adsorption methods. XRD analysis confirmed all adsorbents exhibit hexagonal CaHAp structure with P6(3)/m space group. TEM analysis confirms the rod like morphology of the adsorbents and the average length of the rods were in the range of 40-45 nm. Pyridine adsorption results indicate increase in number of Lewis acid sites with Ag doping in CaHAp. Adsorption capacity of CaHAp was found increased with Ag content in the adsorbents. Ag (10): CaHAp adsorbent showed superior adsorption performance among all the adsorbents for various concentrations of Congo red (CR) dye in aqueous solutions. The amount of CR dye adsorbed on Ag (10): CaHAp was found to be 49.89-267.81 mg g(-1) for 50-300 ppm in aqueous solution. A good correlation between adsorption capacity and acidity of the adsorbents was observed. The adsorption kinetic data of adsorbents fitted well with pseudo second-order kinetic model with correlation coefficients ranged from 0.998 to 0.999. The equilibrium adsorption data was found to best fit to the Langmuir adsorption isotherm model. (C) 2015 Elsevier Inc. All rights reserved.

Twinning induced enhancement of fracture toughness in ultrafine grained Hydroxyapatite-Calcium Titanate composites

Despite being highly bioactive and biocompatible, the limitations of monolithic hydroxyapatite (HA) include extremely low fracture toughness, poor electrical conductivity. While addressing these issues, the present study demonstrates how CaTiO3 (CT) addition to HA can be utilized to obtain a combination of long crack fracture toughness (1.7 MPa m(1/2) SEVNB technique) and flexural strength of 98-155 MPa (3-point bending) and a moderate tensile strength (diametral compression) of 17-36 MPa. The enhancement in fracture resistance in spark plasma sintered HA-CT composites has been explained in reference to the observed twin morphology. TEM reveals the presence of twins in CT grains due to 1800 rotation about 101]. The measured properties along with our earlier reports on biocompatibility and electrical properties make HA-CT suitable for bone tissue engineering applications. When compared with other competing HA-based biocomposites, HA-CT composites are found to have a better combination of properties useful for medium load bearing implant applications. (C) 2015 Elsevier Ltd. All rights reserved.

Epoxy composites containing cobalt(II)-porphine anchored multiwalled carbon nanotubes as thin electromagnetic interference shields, adhesives and coatings

Herein a facile strategy has been adopted to design epoxy based adhesive/coating materials that can shield electromagnetic radiation. Multiwalled carbon nanotubes (MWNTs) were non-covalently modified with an ionic liquid and 5,10,15,20-tetrakis(4-methoxyphenyl)-21H,23H-porphine cobalt(II) (Co-TPP). The dispersion state of modified MWNTs in the composites was assessed using a scanning electron microscope. The electrical conductivity of the composites was improved with the addition of IL and Co-TPP. The shielding effectiveness was studied as a function of thickness and intriguingly, composites with as thin as 0.5 mm thickness were observed to reflect 497% of the incoming radiation. Carbon fibre reinforced polymer substrates were used to demonstrate the adhesive properties of the designed epoxy composites. Although, the shielding effectiveness of epoxy/MWNT composites with or without IL and Co-TPP is nearly the same for 0.5 mm thick samples, the lap shear test under tensile loading revealed an extraordinary adhesive bond strength for the epoxy/IL-MWNT/Co-TPP composites in contrast to neat epoxy. For instance, the lap shear strength of epoxy/IL-MWNT/Co-TPP composites was enhanced by 100% as compared to neat epoxy. Furthermore, the composites were thermally stable for practical utility in electronic applications as inferred from thermogravimetric analysis.

Anti-corrosive and anti-microbial properties of nanocrystalline Ni-Ag coatings

Anti-corrosive and anti-bacterial properties of electrodeposited nanocrystalline Ni-Ag coatings are illustrated. Pure Ni, Ni-7 at.% Ag, & Ni-14 at.% Ag coatings were electrodeposited on Cu substrate. Coating consisted of Ni-rich and Ag-rich solid solution phases. With increase in the Ag content, the corrosion resistance of the Ni-Ag coating initially increased and then decreased. The initial increase was due to the Ni-Ag solid solution. The subsequent decrease was due to the increased galvanic coupling between the Ag-rich and Ni-rich phases. For all Ag contents, the corrosion resistance of the Ni-Ag coating was higher than the pure Ni coating. Exposure to Sulphate Reducing Bacteria (SRB) revealed that the extent of bio-fouling decreased with increase in the Ag content. After 2 month exposure to SRB, the Ni-Ag coatings demonstrated less loss in corrosion resistance (58% for Ni-7 at.% Ag and 20% for Ni-14 at.% Ag) when compared pure Ni coating (115%). (C) 2016 Elsevier B.V. All rights reserved.