Effect of suspension stability on bonding strength and electrochemical behavior of electrophoretically deposited HA–YSZ nanostructured composite coatings

In the present study, HA–YSZ nanostructured composites were deposited on Ti–6Al–4 V substrates by electrophoretic deposition of suspensions containing 0, 10, 20 and 40 wt% YSZ. The stability of each suspension was determined by applying response surface methodology, DLVO theory and zeta potential measurement for different YSZ contents and dispersant concentrations. The maximum zeta potential and electromobility of suspended particles was obtained for the suspension with 20 wt% YSZ. The electrophoretic deposition of HA–YSZ nanostructured composites was carried out at a constant voltage of 20 V for 120 s. The deposition kinetics was studied based on a mass-charge correlating approach under ranges of voltage (20–60 V), time (30–300 s) and wt% YSZ (0–40). The as–deposited and sintered HA–YSZ coatings were characterized by SEM, XRD, DSC–TG and FT–IR analyses. The micro-scratch behavior of coated samples indicated the highest critical contact pressures of crack initiation, P_c1 = 4.50 GPa, crack delamination, P_c2 = 5.14 GPa and fracture toughness, K_IC = 0.622 MPa m^1/2 for HA-20 wt% YSZ sample. The results of potentiodynamic polarization measurements showed that the implementation of 20 wt% YSZ could efficiently decrease the corrosion current density and corrosion rate of coated samples, while corrosion potential and linear polarization resistance were increased.     

Development of hydroxyapatite coatings on laser textured 316 LSS and Ti-6Al-4V and its electrochemical behavior in SBF solution for orthopedic applications

The current work focused on the development of hydroxyapatite (HAP) coating on laser textured metallic implants using electrophoretic deposition. HAP was synthesized by sol-gel technique and its phase purity and surface morphology were confirmed by FT-IR, XRD and SEM analysis. 316 L SS and Ti-6Al-4V metal implants were polished and the surface was modified using Nd-YAG laser operating at a pulse interval of 10 ns at various overlapping rate of 0%, 25% and 50%. The laser treated surface was characterized for its surface roughness using surface profilometry and surface morphology. The surface roughness of the metallic implants was increased by increase in the overlapping rate. The prepared HAP powder was electrophoretically deposited on bare and laser textured Ti-6Al-4V and 316 L stainless steel followed by vacuum sintering at 300 °C for 2 h. Scratch analysis results showed an improvement in adhesion strength for the HAP coatings on laser treated specimens than untreated metal. Corrosion efficiency of the coated samples was studied in SBF solution using EIS and potentiodynamic polarization studies. The result from the corrosion experiments proved increased corrosion resistance property of laser textured coated samples when compared to bare alloy due to higher adhesion of HAP coating on the metal surface.     

Corrosion resistance of poly p-phenylenediamine conducting polymer coated 316L SS bipolar plates for Proton Exchange Membrane Fuel Cells

The usage of conducting polymers as coating materials for bipolar plates to prevent corrosion is the recent trend in Proton Exchange Membrane Fuel Cell (PEMFC) technology. Paraphenylenediamine (pPD) monomer was electropolymerized to poly p-phenylenediamine (PpPD) over 316L SS. The characterization of PpPD, the conducting polymer coating, over 316L SS was done using attenuated total reflectance infra-red (ATR-IR) spectroscopy to confirm the formation of PpPD. The surface morphology and topography were studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The corrosion protection performance of the coating was evaluated using open circuit potential (OCP) measurement, electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization studies in PEMFC environment. EIS studies revealed that the charge transfer resistance for the coated substrates has increased by one order of magnitude than the bare substrate. Potentiodynamic polarization studies have registered lower corrosion current density by one order magnitude for the 0.06 M pPD coated substrate than the bare substrate and the polarization resistance values for the coated substrates have increased by two and a half time than the bare substrate. These results showed that PpPD coated substrates exhibited enhanced corrosion resistance in PEMFC environment.     

Fabrication of nanoporous sodium niobate coating on 316L SS for orthopaedics

Niobium oxide is known for its biocompatibility; however it lacks on bioactivity. Sodium is one of the essential elements required for the formation and maintenance of bone. In this present study, we focus on improving the bioactivity of niobium oxide by incorporating sodium ions and obtaining nanoporous morphology by adding polyethylene glycol. Sodium niobate was prepared using sol-gel method and dip coated on 316L SS. The coated sample was sintered at the optimised heating rate of 0.5 °C min⁻¹. The surface morphology, chemical composition, phase composition and porosity were analysed using scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), X-ray diffraction analysis (XRD) and porosimetry. The BET analysis and AFM studies showed that the coating exhibited pores with the average diameter of 97 and 101 nm. The Vicker's microhardness test showed that sodium niobate coating exhibits three fold higher microhardness compared to 316L SS. In vitro studies show that the coating exhibited good bioactivity. Electrochemical studies confirmed that the coating offers better corrosion resistance to the substrate at pH 5.2 and pH 7.4. The hemolysis percentage of the coating was found to be 1.54% and anticoagulation studies showed that coagulation time of sodium niobate coating was similar to that of the plasma. Better adhesion, proliferation and differentiation of MG-63 cells with significant cell spreading were observed in the coating.     

In-vitro electrochemical and bioactivity evaluation of SS316L reinforced hydroxyapatite functionally graded materials fabricated for biomedical implants

Three sets of FGMs of stainless steel 316L (SS) reinforced with micro-, nano- and mixed (1:1 mass ratio) hydroxyapatite (HA) were fabricated by powder metallurgy route. The concentration of the HA was varied from 0 to 20 wt% with the increment of 5 wt% in all sets to strengthen the discrete layers of FGMs. The sintered densities along the discrete layers of FGMs continually decreased as a function of HA content which enhanced the bioactivity of the FGMs towards the end with high content of HA. All FGMs experienced an excellent corrosion response in the 0.9% NaCl solution with high passivity. Heavy diffusion of chromium (Cr) form SS to HA made the matrix Cr deficient. The chromium depletion regions around the interface of SS and HA caused an active corrosion behavior of FGMs in 0.1 M HCl solution. FGMs with micro-sized HA demonstrated the better corrosion properties than that of other FGMs. After being immersed in the simulated body fluid (SBF) solution for 7 days, the apatite layer formed on the surface of FGMs with micro-sized HA had a mature spherical morphology and leaf like shape for the other two FGMs. The apatite morphology and gained weight results proved the highest bioactivity for micro-sized HA reinforced FGMs.     

Graphene oxide/hydroxyapatite composite coatings fabricated by electrophoretic nanotechnology for biological applications

Graphene oxide (GO) was firstly employed as nanoscale reinforcement fillers in hydroxyapatite (HA) coatings by a cathodic electrophoretic deposition process, and GO/HA coatings were fabricated on pure Ti substrate. The transmission electron microscopy observation and particle size analysis of the suspensions indicated that HA nanoparticles were uniformly decorated on GO sheets, forming a large GO/HA particle group. The addition of GO into HA coatings could reduce the surface cracks and increase the coating adhesion strength from 1.55 ± 0.39 MPa (pure HA) to 2.75 ± 0.38 MPa (2 wt.% GO/HA) and 3.3 ± 0.25 MPa (5 wt.% GO/HA), respectively. Potentiodynamic polarization and electrochemical impedance spectroscopy studies indicated that the GO/HA composite coatings exhibited higher corrosion resistance in comparison with pure HA coatings in simulated body fluid. In addition, superior (around 95% cell viability for 2 wt.% GO/HA) or comparable (80–90% cell viability for 5 wt.% GO/HA) in vitro biocompatibility were observed in comparison with HA coated and uncoated Ti substrate.     

The production of a corrosion resistant graphene reinforced composite coating on copper by electrophoretic deposition

We report the fabrication of a robust graphene reinforced composite coating with excellent corrosion resistance by aqueous cathodic electrophoretic deposition (EPD). At optimum EPD conditions, a coating thickness of around 40 nm is obtained at 10 V and deposition time of 30 s. The surface morphological characterization are carried out by scanning electron microscopy which clearly shows reduced graphene oxide (rGO) with sizes ranging from 1 to 2 μm uniformly coated on the copper sheet. The composite coating is shown to significantly increase the resistance of the metal to electrochemical degradation. Tafel analysis confirms that the corrosion rate exhibited by composite coating is an order of magnitude lower than that of bare copper. It is expected that this simple EPD technique for producing a graphene-reinforced composite coating can open a new avenue especially for marine engineering materials where resistance to salt water is of paramount importance.     

Enhancement of corrosion protection of mild steel by chitosan/ZnO nanoparticle composite membranes

The development of active corrosion protection systems for metallic substrates is an issue of prime importance for many industrial applications. Nanostructured chitosan/ZnO nanoparticle films were coated on mild steel by sol–gel process, dip coating technique. Sol–gel protective coatings have shown excellent chemical stability, oxidation control and enhanced corrosion resistance for metal substrates. Further, the sol–gel method is an environmentally friendly technique of surface protection which has traditionally been used for increasing corrosion resistance of metals. Films so formed were characterized by UV–vis absorption spectroscopy (UV–vis), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive X-ray fluorescence spectrometry (EDX). Corrosion protection behavior of these coated mild steel substrates in 0.1 N HCl solutions was evaluated by potentiodynamic polarisation studies (Tafel), linear polarisation studies (LPR), electrochemical impedance spectroscopy studies (EIS).     

Enhancement of antimicrobial and long-term biostability of the zinc-incorporated hydroxyapatite coated 316L stainless steel implant for biomedical application

Antimicrobial hydroxyapatite (HAp) nanoparticles with different concentrations (0, 3, and 6 mol%) of zinc were prepared by the ultrasonication process. The prepared nanoparticles and chitosan (CTS) composite were coated on 316L stainless steel implant by spin coating technique. The powder samples were characterised by particle size analyser, X-ray fluorescence, and X-ray diffraction studies. The morphology of the coating was investigated by scanning electron microscopy. The diameter of the particle size decreased with increase in the concentration of zinc in HAp structure. The structure of the coated implant was found to be uniform without any cracks and pores. Antimicrobial activity of the composites against Bacillus subtilis, Staphylococcus aureus, Klebsiella pneumonia, Salmonella typhi and Pseudomonas aeruginosa was analysed. The results showed that the increase in the concentration of zinc enhances the antimicrobial properties of 316L stainless steel implant. The stability of the implant in physiological environment was characterised by electrochemical impedance spectroscopy and polarisation analysis. The higher concentration of the ZnHAp/CTS composite shows higher corrosion resistance than that of the HAp/CTS-coated implant. This study shows that the coating provides corrosion resistance to the stainless steel substrate in simulated body fluid (SBF). The in vitro bioactivity study of the coated samples immersed in SBF solution confirms the formation of bone-like apatite layer on the surface of the implant. Thus, highly biocompatible ZnHAp/CTS-coated materials could be very useful in the long-term stability of the biomedical applications.     

The role of titania on the microstructure,biocorrosion and mechanical properties of Mg/HA-based nanocomposites for potential application in bone repair

Bone defects are very challenging in orthopedic practice. The ideal bone grafts should provide mechanical support and enhance the bone healing. Biodegradable magnesium (Mg)–based alloys demonstrate good biocompatibility and osteoconductive properties, which are promising biomaterials for bone substitutes. However, the high rate of their biodegradation in human body environment is still challenging. For this scope, synthesis Mg-based composites with bioceramic additives such as HA and titania (TiO₂) is a routine to solve this problem. The aim of this study was to evaluate the effect of addition TiO₂ nanopowders on the corrosion behavior and mechanical properties of Mg/HA-based nanocomposites fabricated using a milling-pressing-sintering technique for medical applications. The microstructure of Mg/HA/TiO₂ nanocomposites, in vitro degradation and biological properties including in vitro cytocompatibility were investigated. The corrosion resistance of Mg/HA-based nanocomposites was significantly improved by addition 15 wt% of TiO₂ and decrease HA amount to 5 wt% this was inferred from the lower corrosion current; 4.8 µA/cm² versus 285.3 µA/cm² for the Mg/27.5 wt%HA, the higher corrosion potential; −1255.7 versus −1487.3 mV_SCE, the larger polarization resistance; 11.86 versus 0.25 kΩ cm² and the significantly lower corrosion rate; 0.1 versus 4.28 mm/yr. Compressive failure strain significantly increased from 1.7% in Mg/27.5HA to 8.1% in Mg/5HA/15TiO₂ (wt%). The Mg/5HA/15TiO₂ (wt%) nanocomposite possessed high corrosion resistance, cytocompatibility and mechanical properties and can be considered as a promising material for implant applications.     

Investigation of the tribological and biomechanical properties of CrAlTiN and CrN/NbN coatings on SST 304

This study examines the influence of thin layer coatings of CrAlTiN and CrN/NbN, deposited via physical vapor, on the biocompatibility, mechanical, tribological, and corrosion properties of stainless steel 304. The microstructure and morphology of the thin CrAlTiN and CrN/NbN layers were characterized by scanning electron microscopy (SEM), EDX, and X-ray diffraction. The pin on disc wear test was performed on bare and metal-nitride coated SST 304 under a 15 N load at 60 rpm and showed that the wear rates of the thin CrAlTiN and CrN/NbN film coatings were lower than the bare substrate wear ratio. The coefficients of friction (COFs) attained were 0.64, 0.5, and 0.55 for the bare substrate, CrN/NbN coating, and CrAlTiN coating, respectively. Nano indentation tests were also performed on CrAlTiN-coated and CrN/NbN-coated SST 304. The nanohardnesses and Young's moduli of the coated substrates were 28 GPa and 390 GPa (CrN/NbN-coated) and 33 GPa and 450 GPa (CrA1TiN-coated), respectively. For comparison, the nanohardness and Young's modulus of the uncoated substrate were 4.8 GPa and 185 GPa, respectively. Corrosion tests were conducted, and the behaviors of the bare and metal nitride-deposited substrates were studied in CaCl₂ for seven days. The corrosion Tafel test results showed that the metal-nitride coatings offer proper corrosion resistance and can protect the substrate against penetration of CaCl₂ electrolyte. The CrN/NbN-coated substrates showed better corrosion resistance compared to the CrAlTiN-coated ones. In evaluating the biocompatibility of the CrAlTiN and CrN/NbN coatings, the human cell line MDA-MB-231 was found to attach and proliferate well on the surfaces of the two coatings.     

Electrochemical investigation of chromium nanocarbide coated Ti–6Al–4V and Co–Cr–Mo alloy substrates

This study investigated the electrochemical behavior of chromium nano-carbide cermet coating applied on Ti–6Al–4V and Co–Cr–Mo alloys for potential application as wear and corrosion resistant bearing surfaces. The cermet coating consisted of a highly heterogeneous combination of carbides embedded in a metal matrix. The main factors studied were the effect of substrate (Ti–6Al–4V vs. Co–Cr–Mo), solution conditions (physiological vs. 1 M H₂O₂ of pH 2), time of immersion (1 vs. 24 h) and post coating treatments (passivation and gamma sterilization). The coatings were produced with high velocity oxygen fuel (HVOF) thermal spray technique at atmospheric conditions to a thickness of 250 μm then ground and polished to a finished thickness of 100 μm and gamma sterilized. Native Ti–6Al–4V and Co–Cr–Mo alloys were used as controls. The corrosion behavior was evaluated using potentiodynamic polarization, mechanical abrasion and electrochemical impedance spectroscopy under physiologically representative test solution conditions (phosphate buffered saline, pH 7.4, 37 °C) as well as harsh corrosion environments (pH ～ 2, 1 M H₂O₂, T = 65 °C). Severe environmental conditions were used to assess how susceptible coatings are to conditions that derive from possible crevice-like environments, and the presence of inflammatory species like H₂O₂. SEM analysis was performed on the coating surface and cross-section. The results show that the corrosion current values of the coatings (0.4–4 μA/cm²) were in a range similar to Co–Cr–Mo alloy. The heterogeneous microstructure of the coating influenced the corrosion performance. It was observed that the coating impedances for all groups decreased significantly in aggressive environments compared with neutral and also dropped over exposure time. The low frequency impedances of coatings were lower than controls. Among the coated samples, passivated nanocarbide coating on Co–Cr–Mo alloy displayed the least corrosion resistance. However, all the coated materials demonstrated higher corrosion resistance to mechanical abrasion compared to the native alloys.     

Investigation of the corrosion protection behavior of natural montmorillonite clay/bitumen nanocomposite coatings

The influence of clay particles on the corrosion properties of bituminous coating was studied. Different percentages of natural montmorillonite clay (Cloisite Na⁺) were added to emulsified bitumen in water to make 2 wt.%, 3 wt.% and 4 wt.% of clay/bitumen nanocomposite coatings. The coatings were applied on steel 37. Optical microscopy and transmission electron microscopy (TEM) were employed to study the structure of nanocomposite. To investigate the anti-corrosion properties of the coated panels, electrochemical impedance spectroscopy (EIS) was used. The findings indicated that the addition of clay nanolayers improved corrosion resistance of the coatings. Moreover, increasing clay loading up to 4 wt.%, increased the corrosion resistance.     

Molten salt corrosion of high density graphite and partially stabilized zirconia coated high density graphite in molten LiCl–KCl salt

Corrosion studies were performed on uncoated high density graphite and plasma sprayed partially stabilized zirconia (PSZ) coated high density graphite with NiCrAlY bond coat in molten LiCl–KCl eutectic salt at 600 °C for periods of 250 h, 1000 h and 2000 h under inert argon atmosphere. High density graphite showed weight loss while PSZ coated high density graphite showed weight gain. There is no significant attack and degradation of top PSZ coating in molten salt, however microcracks were observed at the bond coat-substrate interface after 2000 h of exposure. PSZ coated high density graphite exhibited excellent corrosion resistance in molten LiCl–KCl salt due to chemical stability and absence of phase transformation as confirmed from scanning electron microscopy, X-ray diffraction and laser Raman studies, however adhesion of the coating has to be improved.     

Efficiency investigations of electrochemical realkalisation treatment applied to carbonated reinforced concrete — Part 1: Sacrificial anode process

The aim of this study was to assess the efficiency of a realkalisation treatment using sacrificial anodes applied to reinforced concrete degraded by carbonation. Analytical determinations (acid/base indicators, quantitative pH, alkaline profiles, SEM and micro-Raman) together with electrochemical characterizations (rest potential, impedance, linear polarisation resistance and corrosion current densities) were performed on artificially carbonated slabs, before and after treatment (mainly 15 days, 11 weeks, 6 and 12 months). The treatment efficiency was demonstrated by an increase of pH and by an alkaline ion penetration in the concrete cover. Rest potential and corrosion current densities indicated a slight decrease of the rebar corrosion activity. Complementary Raman spectroscopy showed a change in the oxide species and SEM observations indicated that the cement matrix remained almost unchanged.     

Evaluation of 316 L porous stainless steel for SOFC support

Solid oxide fuel cells (SOFCs) supported on porous steel substrates are recently gaining much attention, because fabrication cost of SOFC might be significantly reduced. In this paper high temperature properties of porous stainless steel 316 L for application in SOFCs are evaluated. The 316 L was investigated using thermogravimetric analysis, XRD analysis and electrical measurements of scales formed on steel surface. The YSZ ceramic electrolyte was deposited on the 316 L and interaction of formed interlayer was evaluated. The results show that the 316 L is applicable only for SOFCs operated below 500 °C.     

The corrosion resistance of electroless deposited nano-crystalline Ni–P alloys

Coatings of Ni–P alloys are increasingly used for their shiny appearance, the high degree of hardness and very good corrosion resistance. Electroless coatings are preferred in industry compared to the electroplated ones because they adhere well to different materials and form a homogeneous coating even on complicated geometries. Electroless Ni–P alloys produced as a coating on technical iron in a commercial autocatalytic hypophosphite-type plating bath were studied, with regard to their corrosion behaviour upon immersion in near neutral sulphate and chloride electrolytes. The anodic polarization curves of the alloys showed a current plateau at potentials E < +0.2 V SCE confirming their high corrosion resistance. The dynamic cathodic polarization curves in deaerated solutions showed a Tafel behaviour with a slope of ca. ?0.4 V, indicating inhibition of oxygen reduction on “as received” and on mechanically polished surfaces. Corrosion rates of ca. 0.5–0.7 μA/cm² were found during prolonged immersion in near neutral solutions open to air. Potentiostatic polarization at selected potentials in the range of the current plateau (?0.1 V SCE, +0.1 V SCE) showed a steady decrease of the current density following a power law with exponent ?0.5, thus a diffusion controlled process. These results show that the suppression of the anodic dissolution and the low corrosion rates of Ni–P alloys cannot be associated with the oxide-film passivity. Despite this fact, black spots identified as localized corrosion appeared on mechanically polished and “as plated” electroless Ni–P deposits after prolonged potentiostatic polarization at potentials in the range of dissolution suppression.     

Growth of carbon nanotube arrays using nanosphere lithography and their application in field emission devices

The present study investigates the patterned growth of carbon nanotubes (CNTs) by microwave plasma assisted chemical vapor deposition (MPCVD) and their field emission (FE) properties. The nanosphere monolayers were used as a mask for deposition of ultrathin (~ 3 nm) cobalt (Co) layer by DC sputtering. Periodic arrays of Co catalyst islands were obtained after the removal of spheres. Microscopic and Raman spectroscopic studies revealed the patterned growth of multiwall CNTs on catalyst islands. The CNTs length was around 10 µm and diameter was of 40–60 nm. The field emission properties were also compared with I–V characteristics of the un-patterned CNTs grown under the same conditions. The onset fields for un-patterned and patterned samples were nearly the same, 0.64 V/µm and 0.67 V/µm, respectively for a 10 µA current.     

Polyaniline/polyacrylate core–shell composites: Preparation,morphology and anticorrosive properties

Polyaniline/partially phosphorylated poly(vinyl alcohol)/polyacrylate nanoparticles ((PAn/P-PVA)_x/PAc_y) were synthesized by encapsulation of varying amounts of PAn/P-PVA nanoparticles (x = 0.3, 0.5 or 0.7 g) with PAc (y = 4, 6 or 8 g acrylate monomers) via emulsifier-free emulsion polymerization. A monomer conversion level of 93.9% was achieved for the synthesis of the (PAn/P-PVA)_0.5/PAc₄ nanoparticles. X-ray diffraction analysis revealed that PAc was intercalated between the PAn/P-PVA layers, whilst transmission electron microscopy analysis of the different nanoparticles revealed they were spherical PAn/P-PVA agglomerates coated with PAc. Thermogravimetric analysis revealed that the thermal stability of the (PAn/P-PVA)/PAc nanoparticles decreased with increasing amounts of PAc. Cyclic voltammetry based analysis of the different (PAn/P-PVA)/PAc nanoparticles coated onto carbon fiber electrodes revealed that the PAn/P-PVA nanoparticles were encapsulated sufficiently by the non-conductive PAc and that the peak current decreased with increasing amounts of acrylate. With respect to the corrosion resistance in 1.0 M sulfuric acid, steel coated with the (PAn/P-PVA)_0.7/PAc₈ nanocomposite showed the best corrosion resistance (11.4%), but for the nanocomposites at each PAn/P-PVA loading level, the anticorrosive properties increased with increasing PAc levels, presumably due to the increasing tortuosity of the diffusion pathway through the coating for any corrosion agents.     

Corrosion behavior of TiC–SiC composite ceramics in molten FLiNaK salt

Immersion corrosion tests of TiC_0.8, TiC, TiC–20 vol% SiC, TiC–40 vol% SiC and SiC have been performed in molten FLiNaK salt at 800 °C for 25–200 h under argon cover gas. All of these five samples showed small mass loss and relatively good corrosion resistance in molten FLiNaK salt. The corrosion patterns of TiC_0.8, TiC, TiC–20 vol% SiC and TiC–40 vol% SiC were inter-granular corrosion, which were attributed to the depletion of Ti along the grain boundaries. SiC exhibited a general corrosion process in which a carbon-rich layer formed on the surface, resulting from the depletion of Si. The carbon-rich layer protected SiC against further corrosion, hence lowering the corrosion rate. The corrosion results of TiC–20% SiC and TiC–40% SiC revealed the corrosion resistance of TiC could be improved by adding SiC. And the contribution of SiC to better corrosion resistance has been elucidated.