耐蚀油套管管材的国内外研究现状

世界油气田中大约1/2含有H2S和CO2气体,针对CO2/H2S腐蚀所采取最安全的防护措施是使用耐蚀油套管材料。本文综述了国内外抗腐蚀油套管管材的研究现状,详细介绍了低碳钢、低合金钢、低碳3-5wt.%Cr钢、13Cr和超级13Cr不锈钢的冶金成分、组织结构及抗CO2/H2S腐蚀,特别是抗硫化物应力腐蚀开裂(SSC)的性能。指出了耐蚀油套管管材在CO2/H2S油气田应用的不足之处及在以后研发过程中有待解决的问题。     

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.     

Materials for flue gas desulfurization systems operating in Korea and their failures

Abstract

Most flue gas desulfurization (FGD) systems operating in Korea are wet systems which are exposed to aggressive chemical and mechanical environments. Many kinds of materials such as stainless steels, nickel-based alloys, fiberglass reinforced plastic (FRP), C276 or Ti clad steels, and non-metallic coatings/linings over carbon steel have been used for the FGD systems, with their ductwork and chimney exposed in the severe environments. The materials are required to survive during their design life, but some materials are not sufficiently resistant to the corrosive environments in the FGD systems, resulting in the failures of materials and hence increased maintenance costs. Especially, the non-metallic materials and stainless steels have been used extensively in early installations in order to reduce the initial material costs, but they frequently failed early in the severe corrosive environments. This paper presents some representative examples of failures that occurred at the wet FGD systems operating in Korea and their counter measures.     

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.     

Grain boundary engineering of titanium-stabilized 321 austenitic stainless steel

Grain boundary engineering (GBE) primarily aims to prevent the initiation and propagation of intergranular degradation along grain boundaries by frequent introduction of coincidence site lattice (CSL) boundaries into the grain boundary networks in materials. It has been reported that GBE is effective to prevent intergranular corrosion due to sensitization in unstabilized 304 and 316 austenitic stainless steels, but the effect of GBE on intergranular corrosion in stabilized austenitic stainless steels has not been clarified. In this study, a twin-induced GBE utilizing optimized thermomechanical processing with small pre-strain and subsequent annealing was applied to introduce very high frequencies of CSL boundaries into a titanium-stabilized 321 austenitic stainless steel. The resulting steel showed much higher resistance to intergranular corrosion after sensitization subsequent to carbon re-dissolution heat treatment during the ferric sulfate–sulfuric acid test than the as-received one. The high CSL frequency resulted in a very low percolation probability of random boundary networks in the over-threshold region and remarkable suppression of intergranular corrosion during GBE.     

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.     

Mechanical,electrochemical and magnetic behaviour of duplex stainless steel for biomedical applications

Mechanical, electrochemical and magnetic properties of duplex stainless steel were analysed to evaluate its use as biomaterial, comparing the results with those obtained for austenitic stainless steel. Yield and ultimate tensile strengths are almost twice in duplex stainless steel, being the values 870?MPa and 564?MPa, respectively. The electrochemical test revealed that this material has lower susceptibility to localised corrosion because of its greater passive range, 1?V from the open circuit potential, while the austenitic stainless steel exhibited a passive region of 0.370?V. Both steels behave as soft magnetic materials, however, duplex stainless steel has higher magnetic saturation and remanence, while austenitic stainless steel is more prone to heating when exposed to a magnetic field.     

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。     

Corrosion properties of S-phase layers formed on medical grade austenitic stainless steel

The corrosion properties of S-phase surface layers formed in AISI 316LVM (ASTM F138) and High-N (ASTM F1586) medical grade austenitic stainless steels by plasma surface alloying with nitrogen (at 430°C), carbon (at 500°C) and both carbon and nitrogen (at 430°C) has been investigated. The corrosion behaviour of the S-phase layers in Ringer’s solutions was evaluated using potentiodynamic and immersion corrosion tests. The corrosion damage was evaluated using microscopy, hardness testing, inductive coupled plasma mass spectroscopy and X-ray diffraction. The experimental results have demonstrated that low-temperature nitriding, carburising and carbonitriding can improve the localised corrosion resistance of both industrial and medical grade austenitic stainless steels as long as the threshold sensitisation temperature is not reached. Carburising at 500°C has proved to be the best hardening treatment with the least effect on the corrosion resistance of the parent alloy.     

Steel and nickel alloys at high temperatures: Part D of ‘The requirements for and limitations of materials at high temperatures’

The range of steels considered includes corrosion resistant ferritic and austenitic steels and low alloy, martensitic 12% Cr and austenitic steels for higher strength applications. Nickel superalloys are discussed under the gas turbine applications for which they were largely developed. Nickel alloys for corrosion resistant applications are discussed and a short section on the refractory materials Mo, Nb, Tn and W is included.     

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.     

Fabrication and properties of Lotus-type porous nickel-free stainless steel for biomedical applications

Lotus-type porous Fe–25 wt.%Cr, Fe–23 wt.%Cr–2 wt.%Mo alloys and type AISI 446 stainless steel were fabricated by continuous zone melting technique in pressurized hydrogen and helium gas. The porosity of the samples varied in the range 44–48% and the mean pore size values obtained (145–374 μm) are in the biomedical field desired range. The fabricated Lotus-type porous nickel-free stainless steel was nitrided at high temperature up to the nitrogen concentration of 1.0 wt.% and this amount resulted to be sufficient for maintaining almost single-phase austenitic structure at room temperature. The combination of very small magnetic susceptibility, light weight, mechanical properties close to the human cortical bone, together with the known good enough corrosion resistance of high nitrogen nickel-free stainless steel, makes this Lotus-type porous Fe–Cr–N alloys very attractive for bone implant applications.     

Analysis of Magnetism in High Nitrogen Austenitic Stainless Steel and Its Elimination by High Temperature Gas Nitriding

Stable austenitic structure in medical stainless steels is basically required for surgical implantation. A weak magnetism was found in a high nitrogen nickel-free austenitic stainless steel for cardiovascular stent application. This magnetic behavior in high nitrogen stainless steel was investigated by optical microscopy, X-ray diffraction (XRD), electron probe microanalysis (EPMA) and superconducting quantum interference device (SQUID). The results showed that the magnetism came from the composition segregation of ferrite formation elements such as Cr and Mo in the steel and some δ-ferrites were locally formed during the pressurized electroslag remelting process. The magnetism of high nitrogen stainless steel could be eliminated by a proper high temperature gas nitriding (HTGN).     

Zum Verhalten rost‐ und säurebeständiger Stähle unter Komplexbeanspruchung. Teil 1 Passivität und Lochkorrosionsbeständigkeit

Some Aspects on Corrosion Fatique of Stainless Steels. Part 1 Passivity and Pitting Corrosion Susceptibility Iron‐Chromium‐Nickel alloys are of special interest for many applications because of their excellent resistance to corrosion. The nature and composition of passive films formed on stainless steels depend on the prevailing conditions, viz. steel‐composition, passivation potential, aging, pH, electrolyt composition and temperature. Passive films may be damaged by local breakdown. At least two mechanisms are possible for this localisation: mechanical breakdown by slip steps and electrochemical breakdown (for e.g. by the effects of chloride ions). Because of this, steels suffer a degradation of their fatique properties when exposed to an aqueous environment. Passivation of austenitic, ferritic‐austenitic and martensitic stainless steels has been studied in different solutions using electrochemical techniques. The results clarified that for two of the investigated alloys the prediction of fracture initiation based on pitting corrosion in chlorid containing solutions is possible. (To be continued.)     

Increasing the wear resistance of stainless steels

The wear resistance of martensitic, austenitic and duplex stainless steels is increased by carbon and nitrogen in solid solution and in addition by carbides and nitrides, which are formed during conventional ingot metallurgy or by powder metallurgical processing. High temperature and low temperature nitriding provide a hard surface zone. Characteristic alloys and applications are discussed, which try to optimize the resistance to wear and corrosion.     

Corrosion of a stainless steel handrail

AISI 304 and 304L stainless steels are “workhores” grades of austenitic stainless steel frequently used in architectural applications, as well as in cookware, appliances, and numerous other applications where resistance to corrosion is required. This paper examines a corrosion failure (the appearance of rustlike stains on the surface) of a 304 stainless steel handrail that appears to have occurred as a result of contamination during the fabrication process.     

Corrosion behavior of candidate heat exchanger materials in oxidizing and reducing gases relevant to oxyfuel power plants

Abstract

In the present paper, the oxidation behavior of potentially suitable construction materials for heat exchanging components in coal fired power plants was studied in the temperature range 550–700 °C. The selected materials (low alloy steel 13CrMo44, martensitic steel P92, austenitic steel S304HCu and Ni-base alloy 617) were exposed in a simulated atmosphere typical for oxyfuel combustion and the results were compared with the behavior in a test gas simulating oxyfuel gas with addition of CO, thus simulating locally occurring reducing operating conditions which may happen due to incomplete combustion. The oxidation/corrosion behavior was studied by gravimetry in combination with a number of characterization methods such as optical microscopy, scanning electron microscopy with energy dispersive X-ray analysis (SEM/EDX) and glow discharge optical emission spectroscopy (GDOES). For the low alloy steel and P92 only minor differences in oxidation rates between the different environments were found. For S304HCu generally smaller corrosion rates were found in the reducing gas, whereas for alloy 617 the effect of gas composition depended on temperature. The obtained results are interpreted on the basis of thermodynamic considerations comparing equilibrium activities of the main species in the gas atmospheres with the thermodynamic stabilities of various possible corrosion products.     

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.     

新型不锈钢材料的耐高温氧化及耐高温KCl蒸汽腐蚀性能

为缓解生物质电厂锅炉烟气侧的高温碱性环境腐蚀,对我国自主研发的4种新型不锈钢材料采用高温挂片试验(包括高温氧化试验和高温KCl蒸汽腐蚀试验)检测并绘制腐蚀动力学曲线;采用扫描电镜(SEM)、能谱仪(EDS)对试验后试片的形貌、结构、元素含量进行了分析,比较了4种新型不锈钢材料、传统TP316材料和高铬材料的耐高温氧化及耐高温KCl蒸汽腐蚀性能。结果表明:4种新型材料均表现出较好的耐腐蚀性能,明显优于传统的TP316材料和以往试验的高铬材料,当前更适用于生物质电厂锅炉烟气侧的高温碱性环境。     

Structure and properties of ion-nitrided stainless steels

The structure and properties of ion-nitrided layers on several stainless steels, 410 martensitic stainless steel, 430 ferritic stainless steel and 321 austenitic stainless steel, has been studied under varying process conditions with microhardness-depth correlations, optical microscopy and transmission electron microscopy. The process variables studied include time (2 to 10 h) and temperature (400 to 600° C). The highest case depth values and hardness levels were observed in martensitic stainless steels. The lowest case depths were observed in austenitic stainless steel. In general, the behaviour of matensitic and ferritic stainless steels were similar. All three steels showed increasing case depths and decreasing surface hardnesses with increasing ion-nitriding temperatures and times. Nitriding depth was found to be parabolic with ion nitriding time in all three steels at all ion-nitriding temperatures investigated, the nitriding reaction being faster in martensitic stainless steel than the others. Electron microscopy showed that almost no structural difference arises in the core of ferritic and austenitic stainless steels whereas recrystallization of the martensitic structure was observed in the core of martensitic steel following ion nitriding. Electron microscopy results also showed that ion nitriding produces platelets or disc-shaped precipitates on {001} matrix planes, coherent with the matrix. These platelets showed a striated morphology which is thought to be the result of the elastic strain in the matrix.