Cytotoxicity study of plasma-sprayed hydroxyapatite coating on high nitrogen austenitic stainless steels

Stainless steel has been frequently used for temporary implants but its use as permanent implants is restricted due to its low pitting corrosion resistance. Nitrogen additions to these steels improve both mechanical properties and corrosion resistance, particularly the pitting and crevice corrosion resistance. Many reports concerning allergic reactions caused by nickel led to the development of nickel free stainless steel; it has excellent mechanical properties and very high corrosion resistance. On the other hand, stainless steels are biologically tolerated and no chemical bonds are formed between the steel and the bone tissue. Hydroxyapatite coatings deposited on stainless steels improve osseointegration, due their capacity to form chemical bonds (bioactive fixation) with the bone tissue. In this work hydroxyapatite coatings were plasma-sprayed on three austenitic stainless steels: ASTM-F138, ASTM-F1586 and the nickel-free Böhler-P558. The coatings were analyzed by SEM and XDR. The cytotoxicity of the coatings/steels was studied using the neutral red uptake method by quantitative evaluation of cell viability. The three uncoated stainless steels and the hydroxyapatite coated Böhler-P558 did not have any toxic effect on the cell culture. The hydroxyapatite coated ASTM-F138 and ASTM-F1586 stainless steels presented cytotoxicity indexes (IC_50%) lower than 50% and high nickel contents in the extracts.     

Effect of TIG welding on corrosion behavior of 316L stainless steel

316L stainless steel (SS) is one of the most consumable materials in orthopedic implants. Certain types of orthopedic implants such as mono-bloc hip stems are often made of two elements welded together. In this study, effect of TIG welding on corrosion behavior of 316L stainless steel in physiological solution was investigated. In this method, filler metal wasn't used due to the small thickness of samples and it was welded to lap form. Corrosion behavior in physiological solution at 37 °C was investigated with potentiodynamic polarization curves. Microstructure of base metal (BM) and weld metal (WM) was studied with scanning electronic microscopy (SEM). The corrosion behavior of weld metal, base metal and couple (BM and WM together) was compared together. For detecting microstructure and phases in BM and WM, X-ray diffraction analysis was done. Finally, post-weld heat treatment (PWHT) was performed on as-welded samples. Results indicated that corrosion behavior of WM was better than the BM. This phenomenon was attributed to secondary phases that were present in the BM. Secondary phases in the weld metal are dissolved when the base metal is melting due to the welding process. Based on the results of electrochemical analysis, it was determined that the corrosion rate of a couple was more than of other parts. Heat affected zone (HAZ) is responsible for this phenomenon. The adjacent zones of the weld metal are classically less corrosion resistant, thereby being attacked preferentially when the steel is exposed to corrosive environments. PWHT decreased the corrosion rate of the couple.     

Pitting corrosion protection of low nickel stainless steel by electropolymerized conducting polymer coating in 0·5?M NaCl solution

Conducting polymers of polyaniline (PANi) and poly(o-phenylenediamine) (PoPD) were electropolymerized by cyclic voltammetric technique on low nickel stainless steel (LN SS) in H₂SO₄solution containing aniline and o-phenylenediamine monomers. The coatings were characterized by Fourier transform infrared spectroscopy, UV-visible and scanning electron microscopic techniques and the results are discussed. The corrosion protective properties of PANi and PoPD coatings on LN SS in 0·5 M NaCl were evaluated using potentiodynamic polarization and electrochemical impedance spectroscopic (EIS) techniques. The potentiodynamic polarization and electrochemical impedance spectroscopic results indicate that the PoPD coating inhibits the corrosion of LN SS in 0·5 M NaCl solution more effectively than PANi.     

Evaluation of hydroxyapatite coatings on borate passivated 316L SS in Ringer's solution

Surgical grade stainless steel (316L SS) is one of the widely used implant material in orthopedic surgeries. But often the release of metal ions is evidenced from the implants and subsequently a second surgery is required to remove the implant material. One way to control this release of metal ions is to coat the implant material with a biocompatible material like hydroxyapatite. In this paper we have reported a successful coating of hydroxyapatite over borate passivated 316L SS by a dip coating method. The coatings were characterized by electrochemical techniques such as potentiodynamic polarization, electrochemical impedance and cyclic voltammetry (CV). Also X-ray diffraction (XRD) and scanning electron microscopic (SEM) studies were performed to confirm the quality of the coatings. Results of accelerated leach out characteristics by inductively coupled plasma–atomic emission spectroscopy (ICP–AES) and the evaluation of shear strength are also presented to support the corrosion resistant nature of the coatings. The enhanced bio-resistivity of the as-formed HAP coatings on passivated 316L SS is attributed to the protective passive layer formed by borate buffer solution at selected potentials.     

Characterization of metallic piercings that caused adverse reactions during use

This investigation characterizes five surgical stainless steel piercings and one niobium piercing that caused adverse reactions during use, culminating with the removal of the jewelry. Chemical composition shows that none of the materials are in accordance with ISO (International Organization for Standardization) standards for surgical implant materials. Additionally, none of the stainless steel piercings passed the pitting-resistance criterion of ISO 5832-1, which implies that %Cr + 3.3 × %Mo >26. Under microscopic examination, most of the jewelry revealed the intense presence of linear irregularities on the surface. The lack of resistance to pitting corrosion associated with the poor surface finishing of the stainless steel jewelry may induce localized corrosion, promoting the release of cytotoxic metallic ions (such as Cr, Ni, and Mo) in the local tissue, which can promote several types of adverse effects in the human body, including allergic reactions. The adverse reaction to the niobium jewelry could not be directly associated with the liberation of niobium ions or the residual presence of cytotoxic elements such as Co, Ni, Mo, and Cr. The poor surface finish of the niobium jewelry seems to be the only variable of the material that may promote adverse reactions.     

Effects of chloride ions on electrochemical reaction of 316 stainless steel in mixtures of molten nitrate salts

Effects of chloride ion on decomposition of ternary nitrate and corrosion behaviors of 316 stainless steel (316 SS) were studied by electrochemical corrosion tests in molten salt. Chemical composition and morphology of the corrosion products were analyzed using x-ray diffraction and scanning electron microscopy equipped with energy disperse spectroscopy. Composition analysis for molten salt combined with morphology analyses of corrosion layer showed that presence of chlorine ions slowed down decomposition of ternary nitrate and increased corrosion rate of stainless steel markedly. The polarization curve obtained indicated that the corrosion current density increased from 3.02 mA ⋅ cm⁻² to 8.76 mA ⋅ cm⁻² with the addition of 10 % NaCl. Electrochemical impedance spectroscopy indicated a decrease in charge-transfer resistance of the double layer between 316 SS and ternary Nitrate containing 10 % NaCl, resulting in a decreased corrosion resistance of 316 SS.     

Corrosion protection of CrN/TiN multi-coating for bipolar plate of polymer electrolyte membrane fuel cell

The electrochemical corrosion cells will be generated from the possible pinholes of the promising CrN and TiN coatings in a PEMFC environment. To prevent the elution of possible pinholes, CrN/TiN multi-coatings on SS have been considered. This study examined the electrochemical behavior of three CrN/TiN coatings on 316L stainless steel deposited at different CrN/TiN thickness ratios by rf-magnetron sputtering as potential bipolar plate materials. Potentiodynamic tests of CrN/TiN-coated 316L stainless steel carried out in a 1 M H₂SO₄ + 2 ppm HF solution at 70 °C revealed a significantly lower corrosion current density than that of uncoated 316L SS, as well as a decrease in the corrosion current density with decreasing inner-layer CrN thickness. Electrochemical impedance spectroscopy also showed that the CrN/TiN-coated 316L SS sample had higher charge transfer resistance than the uncoated 316L SS sample, which increased with decreasing inner-layer CrN thickness. This was attributed to the crystalline-refined CrN/TiN(200).     

Mechanical properties and corrosion behaviour of developed high nitrogen high manganese stainless steels

Influence of composition, specifically manganese and nitrogen content, on the microstructure associated corrosion resistance property of newly developed stainless steel has been studied. The developed steels have been characterised for their microstructure, mechanical and electrochemical properties. The results indicate that the addition of manganese and nitrogen as a substitute for nickel favours the austenite microstructure, higher yield strength (>350 MPa), tensile strength (>700 MPa), elongation and superior Charpy V-notch impact toughness properties. The results obtained from electrochemical tests such as potentiodynamic polarisation and electrochemical impedance spectroscopy of manganese stainless steel show remarkable improvement (about 4 times) in corrosion resistance exhibiting passivity behaviour like that of commercial stainless steel (316L).     

Structural analysis and corrosion studies on an ISO 5832-9 biomedical alloy with TiO2 sol–gel layers

The aim of this study was to demonstrate the relationship between the structural and corrosion properties of an ISO 5832-9 biomedical alloy modified with titanium dioxide (TiO₂) layers. These layers were obtained via the sol–gel method by acid-catalyzed hydrolysis of titanium isopropoxide in isopropanol solution. To obtain TiO₂ layers with different structural properties, the coated samples were annealed at temperatures of 200, 300, 400, 450, 500, 600 and 800 °C for 2 h. For all the prepared samples, accelerated corrosion measurements were performed in Tyrode’s physiological solution using electrochemical methods. The most important corrosion parameters were determined: corrosion potential, polarization resistance, corrosion rate, breakdown and repassivation potentials. Corrosion damage was analyzed using scanning electron microscopy. Structural analysis was carried out for selected TiO₂ coatings annealed at 200, 400, 600 and 800 °C. In addition, the morphology, chemical composition, crystallinity, thickness and density of the deposited TiO₂ layers were determined using suitable electron and X-ray measurement methods. It was shown that the structure and character of interactions between substrate and deposited TiO₂ layers depended on annealing temperature. All the obtained TiO₂ coatings exhibit anticorrosion properties, but these properties are related to the crystalline structure and character of substrate–layer interaction. From the point of view of corrosion, the best TiO₂ sol–gel coatings for stainless steel intended for biomedical applications seem to be those obtained at 400 °C.     

Novel fluorapatite/niobium composite coating for metallic human body implants

This study's aim was to design and prepare a novel composite coating in order to improve the biocompatibility of the metallic implants. AISI 316L stainless steel (SS) was used as a substrate and a filler-matrix fluorapatite/niobium (FA/Nb) composite coating was performed on the substrate by using plasma-spray technique. XRD and SEM analyses were utilized to characterize the coatings. Electrochemical polarization tests were carried out in two types of physiological solutions in order to evaluate the corrosion behavior of the coated specimens as an indication of biocompatibility. The results indicated that the corrosion current density of the FA/Nb coated samples was much lower than the obtained values for the FA coated SS substrates. Obviously, the novel FA/Nb composite coating could improve the corrosion resistance and the biocompatibility of the SS implants.     

Enhanced localized and uniform corrosion resistances of bulk nanocrystalline 304 stainless steel in high-concentration hydrochloric acid solutions at room temperature

The localized and uniform corrosion resistances of bulk nanocrystalline 304 stainless steel (NC-304SS) produced by severe rolling technique, and its conventional polycrystalline 304 stainless steel (CC-304SS) counterpart, were investigated in high-concentration hydrochloric acid solutions at room temperature. NC-304SS can scarcely suffer from localized corrosion in 4 mol/L and 5 mol/L HCl solutions during 5-day immersion tests, and in 1–3 mol/L HCl solutions during thirty-five-day immersion tests. The corrosion rate of NC-304SS was also less than that of CC-304SS during these immersion tests. The improved localized and uniform corrosion resistances of NC-304SS were explained in terms of the adsorption and chemical activity of Cl^? on NC-304SS and CC-304SS characterized by X-ray photoelectron spectroscopy, and the valence electron configurations of NC-304SS and CC-304SS were characterized by ultra-violet photoelectron spectroscopy rather than conventional electrochemical results.     

Preparation and characterization of as-extruded Mg–Sn alloys for orthopedic applications

In this study, as-extruded Mg–Sn alloys with various Sn content were prepared and characterized for orthopedic applications. The results of microstructure observations and X-ray diffraction analysis showed that as-extruded Mg–Sn alloys were composed of α-Mg and Mg₂Sn phases, and the content of Mg₂Sn phase increased with increasing Sn content. The microstructure of as-extruded Mg–Sn alloy with 1 wt.% Sn was equiaxed grain, while the one with a higher Sn content was inhomogeneous microstructure and the grain size of the long elongated grains decreased with increasing Sn content. Tensile test revealed that the yield strength and ultimate tensile strength of as-extruded Mg–Sn alloys increased while the elongation decreased with increasing Sn content. Immersion and electrochemical tests indicated that the microstructure of as-extruded Mg–Sn alloys affected their corrosion properties, and the increase of Mg₂Sn phase resulted from the increase of the Sn content led to a higher corrosion rate. The cytotoxicity test showed that as-extruded Mg–1Sn and Mg–3Sn alloys met the requirement of cell toxicity for orthopedic applications. Our analyses showed that as-extruded Mg–1Sn and Mg–3Sn alloys were promising to be used as biodegradable orthopedic implants.     

Corrosion behaviour of single (Ti) and duplex (Ti–TiO2) coating on 304L stainless steel in nitric acid medium

Sputter deposited single titanium (Ti) layer, and duplex Ti–TiO₂ coating on austenitic type 304L stainless steel (SS) was prepared, and the corrosion performance was evaluated in nitric acid medium using surface morphological and electrochemical techniques. Morphological analysis using atomic force microscope of the duplex Ti–TiO₂ coated surface showed minimization of structural heterogeneities as compared to single Ti layer coating. The electrochemical corrosion results revealed that, titanium coated 304L SS showed moderate to marginal improvement in corrosion resistance in 1 M, and 8 M nitric acid, respectively. Duplex Ti–TiO₂ coated 304L SS specimens showed improved corrosion resistance as compared to Ti coating from dilute (1 M) to concentrated medium (8 M). The percentage of protection efficiency for base material increases significantly for duplex Ti–TiO₂ coating as compared to single Ti layer coating. The oxidizing ability of nitric acid on both the coatings as well as factors responsible for improvement in protection efficiency are discussed and highlighted in this paper.     

医用316L不锈钢表面改性的研究进展

316L不锈钢作为生物医用材料在近20年内被广泛应用在矫形外科植入物、牙种植体和冠状动脉支架等领域。分析了目前医用316L不锈钢在临床应用中存在的主要问题,指出生物相容性、耐腐蚀性和耐磨损性有待提高和表面改性是改善上述问题的有效途径。综述了医用316L不锈钢表面改性的各种途径及研究成果,并展望了316L不锈钢表面改性的研究趋势。     

Synthesis and characterisation of nanostructured hardystonite coating on stainless steel for biomedical application

Here, nanostructured hardystonite bioceramic (Ca₂ ZnSi₂ O₇) was synthesised from tetraethyl orthosilicate, zinc nitrate hexahydrate, and calcium nitrate tetrahydrate via sol–gel method, dried at 60–120°C, and finally calcinated at 1300°C. X‐ray diffraction (XRD) analysis confirmed the formation of hardystonite bioceramic. Afterwards, electrophoretic method was utilised to coat the hardystonite ceramic on 316L stainless steel (SS). Methanol solution was used as suspension solvent. The best deposition procedure was carried out by electrophoretic device in the voltage of 50 V for 5 min. XRD analysis was employed for phase characterisation and scanning electron microscopy was utilised for microstructural and morphological characterisations of the coatings. Chemical composition of the coating was evaluated by energy‐dispersive X‐ray spectroscopy. The hardystonite coating improved the corrosion resistance of the substrate, so the corrosion current density in the coated samples was less than the uncoated ones (nine times). In order to assess the bioactivity of the coating, simulated body fluid was used. The main results of the coated sample bioactivity demonstrated that the nanostructured hardystonite coating could amend the in vitro SS bioactivity. Therefore, SS coated with nanostructured hardystonite may be a promising candidate to be applied as bioactive hard tissue implants.Inspec keywords: bioceramics, stainless steel, X‐ray diffraction, corrosion protective coatings, X‐ray chemical analysis, sol‐gel processing, calcium compounds, current density, nanofabrication, zinc compounds, scanning electron microscopy, corrosion resistance, calcination, crystal microstructure, nanostructured materials, prosthetics, nanomedicine, electrophoretic coatings, electrophoretic coating techniquesOther keywords: X‐ray diffraction analysis, electrophoretic method, XRD analysis, phase characterisation, microstructural characterisations, morphological characterisations, energy‐dispersive X‐ray spectroscopy, coated sample bioactivity, nanostructured hardystonite coating, zinc nitrate hexahydrate, sol–gel method, 316L stainless steel, tetraethyl orthosilicate, calcium nitrate tetrahydrate, suspension solvent, deposition procedure, scanning electron microscopy, chemical composition, corrosion resistance, corrosion current density, bioactive hard tissue implants, temperature 1300.0 degC, voltage 50.0 V, time 5.0 min, temperature 60 degC to 120 degC, Ca₂ ZnSi₂ O₇      

Effect of alpha prime due to 475 °C aging on fracture behavior and corrosion resistance of DIN 1.4575 and MA 956 high performance ferritic stainless steels

The 475 °C embrittlement in stainless steels is a well-known phenomenon associated to alpha prime (α′) formed by precipitation or spinodal decomposition. Many doubts still remain on the mechanism of α′ formation and its consequence on deformation and fracture mechanisms and corrosion resistance. In this investigation, the fracture behavior and corrosion resistance of two high performance ferritic stainless steels were investigated: a superferritic DIN 1.4575 and MA 956 superalloy were evaluated. Samples of both stainless steels (SS) were aged at 475 °C for periods varying from 1 to 1,080 h. Their fracture surfaces were observed using scanning electron microscopy (SEM) and the cleavage planes were determined by electron backscattering diffraction (EBSD). Some samples were tested for corrosion resistance using electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization. Brittle and ductile fractures were observed in both ferritic stainless steels after aging at 475 °C. For aging periods longer than 500 h, the ductile fracture regions completely disappeared. The cleavage plane in the DIN 1.4575 samples aged at 475 °C for 1,080 h was mainly {110}, however the {102}, {314}, and {131} families of planes were also detected. The pitting corrosion resistance decreased with aging at 475 °C. The effect of alpha prime on the corrosion resistance was more significant in the DIN 1.4575 SS comparatively to the Incoloy MA 956.     

Laser-treated austenitic steel and nickel alloy for human implants

The recent research in biocompatible materials has been useful in replacing and supporting the fractured natural human bones/joints. Under some condition, negative reaction like release of ions from the bare metal toward the human body fluid leads to corrosion. In this proposed research paper, the biocompatibility of the laser surface-modified austenitic stainless steel (SS316L) and nickel-based superalloy (Inconel 718) was studied. The investigation on laser-modified surfaces is evaluated through electrochemical polarization analysis using simulated body fluid (SBF). The samples subjected to electrochemical polarization analysis were characterized by optical image analysis, SEM, EDS, and XRD analysis. It was inferred that laser surface-modified materials provided enhanced corrosion resistance and bare nickel alloy is more susceptible to corrosion by SBF.     

Improved electrochemical performance of nitrocarburised stainless steel by hydrogenated amorphous carbon thin films for bone tissue engineering

In this study, hydrogenated amorphous carbon thin films, structurally similar to diamond‐like carbon (DLC), were deposited on the surface of untreated and plasma nitrocarburised (Nitrocarburizing‐treated) stainless steel medical implants using a plasma‐enhanced chemical vapour deposition method. The deposited DLC thin films on the nitrocarburising‐treated implants (CN+DLC) exhibited an appropriate adhesion to the substrates. The results clearly indicated that the applied DLC thin films showed excellent pitting and corrosion resistance with no considerable damage on the surface in comparison with the other samples. The CN+DLC thin films could be considered as an efficient approach for improving the biocompatibility and chemical inertness of metallic implants.Inspec keywords: tissue engineering, bone, biomedical materials, electrochemistry, amorphous state, carbon, hydrogen, thin films, plasma CVD, adhesion, corrosion resistance, surface hardeningOther keywords: electrochemical performance, plasma nitrocarburised stainless steel medical implants, hydrogenated amorphous carbon thin films, bone tissue engineering, plasma‐enhanced chemical vapour deposition method, adhesion, corrosion resistance, biocompatibility, chemical inertness, metallic implants, C:H     

Nickel-free Stainless Steel for Medical Applications

BIOSS4 steel is essentially a nickel-free austenitic stainless steel developed by the Institute of Metal Research, Chinese Academy of Sciences, in response to nickel allergy problems associated with nickel-containing stainless steels that are widely used in medical applications. The high nitrogen content of this steel effectively maintains the austenitic stability and also contributes to the high levels of corrosion resistance and strength. BIOSS4 steel possesses a good combination of high strength and toughness, better corrosion resistance, and better blood compatibility, in comparison with the medical 316L stainless steel. Potential applications of BIOSS4 steel can include medical implantation material and orthodontic or orthopedic devices, as well as jewelries and other decorations.