Nickel-free austenitic stainless steels for medical applications

Abstract

The adverse effects of nickel ions being released into the human body have prompted the development of high-nitrogen nickel-free austenitic stainless steels for medical applications. Nitrogen not only replaces nickel for austenitic structure stability but also much improves steel properties. Here we review the harmful effects associated with nickel in medical stainless steels, the advantages of nitrogen in stainless steels, and emphatically, the development of high-nitrogen nickel-free stainless steels for medical applications. By combining the benefits of stable austenitic structure, high strength and good plasticity, better corrosion and wear resistances, and superior biocompatibility compared to the currently used 316L stainless steel, the newly developed high-nitrogen nickel-free stainless steel is a reliable substitute for the conventional medical stainless steels.     

低压等离子喷涂316L等轴晶涂层及其性能研究

为研究低压等离子喷涂等轴晶涂层组织性能和形成机理,采用大气等离子喷涂（APS）和低压等离子喷涂（LPPS）,分别制备了316L不锈钢涂层.利用金相显微镜,X射线衍射和显微硬度等方法,分析了2种涂层的金相组织、相结构、显微硬度和耐蚀性.结果表明：一定条件下制备的低压等离子喷涂SUS316L不锈钢涂层明显不同于传统大气等离...     

Correlation of processing route and heat treatment with the abrasive wear resistance of a plastic mold steel

The processing of polymers necessitates the use of corrosion and wear resistant tool materials being in direct contact with the feedstock material. Corrosion resistant cold work tool steels, the so called plastic mold steels, are successfully applied here, offering both a good wear and corrosion resistance. The lifetime of this tool depends on the applied heat treatment but also the processing route has a distinct effect on the resulting properties. In this work, different powder metallurgical routes like hot isostatic pressing, build‐up welding (plasma transfer arc (PTA)) and thermal spraying (high velocity oxy fuel (HVOF) and atmospheric plasma spraying (APS)) were applied to produce coatings on low‐alloyed construction steel. Coatings are compared in relation to the changes in microstructure and the feasibility of an adequate heat treatment. This paper discusses strategies to maximize wear resistance in dependence of heat treatment and the microstructural changes arising from the processing.     

Surface hardness improvement of plasma-sprayed AISI 316L stainless steel coating by low-temperature plasma carburizing

Low-temperature carburizing below 773 K of austenite stainless steel can produce expanded austenite, known as S-phase, where surface hardness is improved while corrosion resistance is retained. Plasma-sprayed austenitic AISI 316L stainless steel coatings were carburized at low temperatures to enhance wear resistance. Because the sprayed AISI 316L coatings include oxide layers synthesized in the air during the plasma spraying process, the oxide layers may restrict carbon diffusion. We found that the carbon content of the sprayed AISI 316L coatings by low-temperature carburizing was less than that of the AISI 316L steel plates; however, there was little difference in the thickness of the carburized layers. The Vickers hardness of the carburized AISI 316L spray coating was above 1000 HV and the amount of specific wear by dry sliding wear was improved by two orders of magnitude. We conclude that low-temperature plasma carburizing enabling the sprayed coatings to enhance the wear resistance to the level of carburized AISI 316L stainless steel plates. As for corrosion resistance in a 3.5 mass% NaCl solution, the carburized AISI 316L spray coating was slightly inferior to the as-sprayed AISI 316L coating.     

MHB4新型合金抗蚀性能研究

用中频感应炉熔炼了新型超低碳高合金奥氏体不锈钢ＭＨＢ４和３１６Ｌ不锈钢,研究了它们在不同介质中的抗腐蚀性能。结果表明,由于ＭＨＢ４增加了Ｃｒ、Ｎｉ、Ｍｏ的含量,并加入Ｗ,极大地提高了抵抗Ｃｌ＾－离子引起的点蚀能力,因此ＭＨＢ４的耐点蚀、耐缝隙腐蚀以及在合成海水中的抗蚀性均优于３１６Ｌ不锈钢。     

Korrosion thermisch gespritzter Schichten auf der Basis von Aluminiumoxid

Corrosion of thermally sprayed coatings based on aluminium oxide In this paper, the results of corrosion investigations performed on thermally sprayed coatings with different compositions in the Al₂O₃‐TiO₂ system (Al₂O₃, Al₂O₃‐3 %TiO₂, Al₂O₃‐40 %TiO₂, Al₂TiO₅) are presented. The coatings were deposited on corrosion‐resistant stainless steel substrates using APS and HVOF processes. The coatings were characterized by means of optical microscopy and SEM of metallographically prepared cross sections as well as surfaces before and after corrosion testing. The changes in phase composition occurring during spraying were studied by X‐ray diffraction. The corrosion experiments were performed with 1 N solutions of NaOH and H₂SO₄ at room temperature, 60 °C, and 85 °C. In contrast to expectations, APS‐sprayed coatings were found to be more corrosion‐resistant than the denser HVOF‐sprayed coatings were.     

铸造双相不锈钢点腐蚀行为研究

采用化学浸泡腐蚀试验及微观组织和化学成分分析研究了5种铸造双相不锈钢在6%Fe Cl3溶液中的点腐蚀行为,并与316L奥氏体不锈钢进行了对比。结果表明,铸造双相不锈钢的抗点腐蚀性能均优于316L的,腐蚀速率和点腐蚀深度均小于316L奥氏体不锈钢的;双相不锈钢主要耐点蚀能力合金元素在奥氏体和铁素体相内分布不均匀,铬、钼更多地分配于铁素体相内,而镍、氮则更多地分配于奥氏体相内,铁素体相的耐点蚀指数PRE(Cr%+3.3Mo%+16N%)大于奥氏体相;双相不锈钢的耐点腐蚀性能与化学成分有关,随着PRE的增加,双相不锈钢的耐点腐蚀性能提高,铜元素在铁素体内析出的富铜相导致点蚀优先在铁素体内发生和发展。     

超音速火焰喷涂NiCr金属陶瓷涂层的高温硫腐蚀性能

超（超）临界机组锅炉管在硫含量较高的烟气环境中常遭受严重的高温硫酸盐及硫化腐蚀,成为锅炉安全的隐患。在2Crl3不锈钢表面利用超音速火焰喷涂（HVOF）制备了NiCr金属陶瓷涂层（1375VM和TPRI—A）,并用超音速电弧喷涂（SWAS）制备传统45CT涂层以作比较,研究了各涂层在700℃,H2—1％H2s环境中的硫...     

A review on nickel-free nitrogen containing austenitic stainless steels for biomedical applications

The field of biomaterials has become a vital area, as these materials can enhance the quality and longevity of human life. Metallic materials are often used as biomaterials to replace structural components of the human body. Stainless steels, cobalt–chromium alloys, commercially pure titanium and its alloys are typical metallic biomaterials that are being used for implant devices. Stainless steels have been widely used as biomaterials because of their very low cost as compared to other metallic materials, good mechanical and corrosion resistant properties and adequate biocompatibility. However, the adverse effects of nickel ions being released into the human body have promoted the development of “nickel-free nitrogen containing austenitic stainless steels” for medical applications. Nitrogen not only replaces nickel for austenitic structure stability but also much improves steel properties. Here we review the harmful effects associated with nickel and emphatically the advantages of nitrogen in stainless steel, as well as the development of nickel-free nitrogen containing stainless steels for medical applications. By combining the benefits of stable austenitic structure, high strength, better corrosion and wear resistance and superior biocompatibility in comparison to the currently used austenitic stainless steel (e.g. 316L), the newly developed nickel-free high nitrogen austenitic stainless steel is a reliable substitute for the conventionally used medical stainless steels.     

Effect of Copper and Bronze Addition on Corrosion Resistance of Alloyed 316L Stainless Steel Cladded on Plain Carbon Steel by Powder Metallurgy

A sandwich structure with cladding alloyed 316L stainless steel on plain carbon steel was prepared by means of powder metallurgy (PM) processing. Electrolytic Cu and prealloyed bronze (95Cu wt pct, 5Sn wt pct) were added in different contents up to 15% into the surface cladded 316L layers and the effect of alloying concentrations on the corrosion resistance of the 316L cladding layers was studied. The corrosion performances of the cladding samples were studied by immersion tests and potentio-dynamic anodic polarization tests in H_2S0_4 and FeCl_3 solutions. Both 316L and alloyed 316L surface layers with 1.0 mm depth produced by PM cladding had an effect to improve corrosion resistance in H2SO4 and FeCI3 solutions. Small Cu and bronze addition (4%) had a positive effect in H_2SO_4 and FeCl3 solutions. 4% Cu alloyed 316L surface layer produced by PM cladding showed similar anodic polarization behaviour to the 316L cladding layer in H_2SO_4 and FeCl_3 solutions.     

几种电弧喷涂金属涂层在酸性土壤模拟液中的腐蚀行为

通过自然浸泡、动电位极化、电化学阻抗谱技术研究了电弧喷涂Zn、Zn15Al和316L不锈钢三种单层涂层和底层Zn或Zn15Al表层316L两种双层复合涂层喷涂试样在鹰潭酸性土壤模拟液中的腐蚀速率和腐蚀行为,以确定适合预应力高强混凝土管桩(PHC管桩)金属端头抗华南酸性土壤腐蚀的涂层体系.结果表明:Zn、Zn15Al、Zn-316L和Zn15Al-316L涂层均能明显抑制基体Q235钢的腐蚀;Zn和Zn15Al涂层表面的腐蚀产物膜致密且与涂层牢固结合,其耐蚀性指标随腐蚀时间延长而明显变好;腐蚀中后期Zn15Al涂层的耐蚀性指标稍优于Zn涂层;316L涂层的耐蚀性随腐蚀时间延长而急剧下降.     

Development of nitrogen-containing nickel-free austenitic stainless steels for metallic biomaterials—review

Metallic biomaterials—such as 316L stainless steel and cobalt-based alloys—have been used as biomaterials mainly because of their excellent mechanical and corrosion properties. However, the release of nickel trace elements—which cause toxicity—has prompted the development of nitrogen-containing nickel-free austenitic stainless steels. This paper reviews their development, traces the history of 316L stainless steel, and the improvement of properties by nitrogen addition. These steels are now available for production of implant devices such as bone plates and screws. Such production requires special techniques with nitrogen absorption treatment.     

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.     

Super austenitic stainless steels — a promising replacement for the currently used type 316L stainless steel as the construction material for flue-gas desulphurization plant

Potentiodynamic anodic cyclic polarization experiments on type 316L stainless steel and 6Mo super austenitic stainless steels were carried out in simulated flue-gas desulphurization (FGD) environment in order to assess the localized corrosion resistance. The pitting corrosion resistance was higher in the case of the super austenitic stainless steel containing 6Mo and a higher amount of nitrogen. The pit-protection potential of these alloys was more noble than the corrosion potential, indicating the higher repassivation tendency of actively growing pits in these alloys. The accelerated leaching study conducted for the above alloys showed that the super austenitic stainless steels have a little tendency for leaching of metal ions such as iron, chromium and nickel at different impressed potentials. This may be due to surface segregation of nitrogen as CrN, which would, in turn, enrich a chromium and molybdenum mixed oxide film and thus impedes the release of metal ions. The present study indicates that the 6Mo super austenitics can be adopted as a promising replacement for the currently used type 316L stainless steel as the construction material for FGD plants.     

高氮奥氏体不锈钢耐点蚀性能研究

目前产于高氮不锈钢的研究多集中于理论基础、制造工艺和力学性能等方面,有关耐蚀性方面的研究有限。通过循环极化、Mott-Schottky曲线以及电化学阻抗(EIS)等方法,研究了Cr23Mo1N奥氏体不锈钢(高氮钢,HNSS)和316L不锈钢在Cl-溶液中的耐点蚀性能。结果表明:与316L不锈钢相比,高氮钢具有更正的自腐蚀电位,更小的维钝电流密度。阻抗谱表明高氮钢的钝化膜比316L更加稳定,且电荷转移电阻更大。Mott-Schottky曲线表明高氮钢的点缺陷施主浓度比316L不锈钢低一个数量级,钝化膜的绝缘性更好。循环极化曲线表明高氮钢的点蚀敏感性更小,钝化膜的自修复能力更强,耐蚀性能更加优越。     

Failure analysis of the outside coating on the process roller

A failure case of the outside coating on the process roller is presented in this study. The coating consists of WC-Co, which is deposited on 45 steel by High Velocity Oxygen Fuel (HVOF) spraying. The spalling of coatings has been found in the middle of the roller. Rust was also observed on the coatings of the roller. The failure analysis of the coating was performed in terms of composition analysis, and microstructure observation etc. In addition, the effects of sandblasting post-treatments were compared on the residual sand on the interface between the coating and substrate. And the effect of substrate material is investigated on the corrosion of coatings. It was concluded that the sandblasting particles remained on the substrate surface have effects on the failure of the coating. The peeling-off coating on the roller is also related with the formation of iron oxides. Less sand can be remained on the substrate surface when air purging and brushing is used after the sand-blasting compared with only air purging or non-treatment is applied. The stainless steel shows excellent corrosion resistance than the low carbon steel when they are used as substrate for WC-Co coatings during the wet/dry cyclic corrosion tests.     

In vitro corrosion resistance of Lotus-type porous Ni-free stainless steels

The corrosion behavior of three kinds of austenitic high nitrogen Lotus-type porous Ni-free stainless steels was examined in acellular simulated body fluid solutions and compared with type AISI 316L stainless steel. The corrosion resistance was evaluated by electrochemical techniques, the analysis of released metal ions was performed by inductively coupled plasma mass spectrometry (ICP-MS) and the cytotoxicity was investigated in a culture of murine osteoblasts cells. Total immunity to localized corrosion in simulated body fluid (SBF) solutions was exhibited by Lotus-type porous Ni-free stainless steels, while Lotus-type porous AISI 316L showed very low pitting corrosion resistance evidenced by pitting corrosion at a very low breakdown potential. Additionally, Lotus-type porous Ni-free stainless steels showed a quite low metal ion release in SBF solutions. Furthermore, cell culture studies showed that the fabricated materials were non-cytotoxic to mouse osteoblasts cell line. On the basis of these results, it can be concluded that the investigated alloys are biocompatible and corrosion resistant and a promising material for biomedical applications.     

Compatibility of ferritic and duplex stainless steels as implant materials: in vitro corrosion performance

The pitting corrosion, crevice corrosion and accelerated leaching of iron, chromium and nickel of super-ferritic and duplex stainless steels, and for effective comparison the presently used 316L stainless steel, have been studied in an artificial physiological solution (Hank's solution) by the potentiodynamic anodic polarization method. The results of the above studies have shown the new super-ferritic stainless steel to be immune to pitting and crevice corrosion attack. The pitting and crevice corrosion resistances of duplex stainless steel were found to be superior to those of the commonly used type 316L stainless steel implant materials. The accelerated leaching study conducted for the above alloys showed very little tendency for the leaching of metal ions when compared with 316L stainless steel. Thus the present study indicated that super-ferritic and duplex stainless steels can be adopted as implant materials due to their higher pitting and crevice corrosion resistance.     

Microstructure and Mechanical Properties of Fe-based Amorphous Composite Coatings Reinforced by Stainless Steel Powders

In this study,a few Fe-based amorphous matrix composite coatings reinforced with various portions(4,8 and16 vol.%) of 31 6L stainless steel powders have been successfully produced through high velocity oxy-fuel(HVOF) spraying.The microstructure of the composite coatings was systematically characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM) and transmission electron microscopy(TEM).The main structure of composite coatings remained amorphous while 31 6L stainless steel splats were distributed homogeneously in the amorphous matrix and well connected with surrounding amorphous phase.Bonding strength of coatings to the substrate was determined by "pull-off" tensile tests.The results revealed that the31 6L stainless steel phase effectively improved the bonding strength of amorphous coatings,which is mainly contributed by the strong metallurgical bonding between stainless steel and amorphous splats.The addition of31 6L stainless steel also enhanced the ductility and fracture resistance of the coatings due to the ductile stainless steel phases,which can arrest crack propagation and increase energy dissipation.     

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).