超级马氏体不锈钢的等离子渗氮和氮碳共渗

超级马氏体不锈钢(SMSSs)是典型的新一代13%Cr马氏体钢,含碳量较低,并含镍和钼,故具有更好的可焊性和低温韧性。研究表明,不锈钢低温等离子渗氮或氮碳共渗可形成硬的表层从而提高耐磨性。本文对SMSS试样分别在400℃、450℃和500℃进行了等离子渗氮和氮碳共渗,并对处理后的SMSS试样分别采用光学显微镜、显微硬度、XRD和干磨损试验进行了表征。X射线衍射分析证明,氮化铬含量随着渗氮和氮碳共渗温度的升高而增加,也显示出铁和铬的碳化物含量随着处理温度的升高而增加。不同温度下处理后的试样均随着处理温度的升高,磨损体积减小、耐磨性提高。对经等离子处理和未处理的试样所观察到的主要磨损机制都是凿削磨损。     

Influence of oxygen in plasma nitriding

Abstract

The development of low temperature nitriding treatments to enhance wear resistance over the past 40 years is reviewed. The progress achieved is illustrated with evidence from extensive laboratory investigations and industrial trials on textile machine components and other parts. It is demonstrated that small additions of an oxidising component to gaseous nitrocarburising or plasma nitriding/nitrocarburising atmospheres have a beneficial effect on layer formation and on the wear properties of the treated components. The presence of oxygen increases layer formation rates and stabilises the ?-compound layer. The role of oxygen on surface activation is important for chromium containing steels but also on plain carbon or alloyed steels and to neutralise the passivating effect of finishing procedures. Applying a post-oxidation step after nitrocarburising can significantly increase the corrosion resistance of the surface but close control of gas composition and treatment parameters is necessary.     

Corrosion behavior of martensitic and precipitation hardening stainless steels treated by plasma nitriding

Plasma nitriding is a well established technology to improve wear and corrosion properties of austenitic stainless steels. Nevertheless, in the case of martensitic stainless steels, it continues being a problem mainly from the corrosion resistance viewpoint.In this work, three high chromium stainless steels (M340, N695 and Corrax) were hardened by ion nitriding at low temperature, intending to preserve their corrosion resistance.Corrosion behavior was evaluated by CuSO₄ spot, salt spray fog and potentiodynamic polarization in NaCl solution. Microstructure was analyzed by optical microscopy, SEM (EDS) and glancing angle X-ray diffraction. All the samples showed an acceptable corrosion resistance in experiments with CuSO₄, but in salt spray fog and electrochemical tests, only Corrax showed good behavior. The poor corrosion performance could be explained by chromium carbides formed in thermal treatment stage in martensitic steels and chromium nitrides formed during nitriding, even though the process was carried out at low temperature.     

High temperature wear and friction properties of duplex surface treated bearing steels

Duplex treatments by thermo reactive diffusion (TRD) chromizing and puls plasma nitriding were carried out on AISI 52100 and 8620 bearing steels. Tribological behaviors of TRD chromized and duplex treated bearing steels were investigated against Al₂O₃ ball in ball-on-disc system at room temperature and 500 °C. The samples were pack chromized in a furnace at temperature of 1000 °C for 5 h. After chromizing, the samples were puls plasma nitrided for 5 h at 500 °C. The coated steels were characterized using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), scratch and microhardness testing. Plasma nitriding of chromized steels increased the total thickness of the compound layer. The subsequent plasma nitriding increased the surface hardness to 2135 HK_0.025 due to the formation of CrN and Cr₂N. The surface hardness and scratch resistance of coating can be increased with duplex treatment of chromizing followed by plasma nitriding, resulting in high wear resistance. Tribological tests indicated that puls plasma nitriding process decreased the coefficient of friction values and wear rate of the chromized steels at room temperature and 500 °C. Also, examination of the worn surface of the samples showed that particularly at high temperature, the oxidized compact layer occurs and tribo-oxidation played an important role in oxidation behaviour of the steels after the duplex treatment.     

Anodic plasma electrolytic nitrocarburising of VT22 titanium alloy in carbamide and ammonium chloride electrolyte

The structure of alpha- and beta-titanium alloy VT22, its microhardness, surface roughness, wear and corrosion resistance after anodic plasma electrolytic nitrocarburising in an electrolyte containing carbamide and ammonium chloride were investigated. An X-ray diffractometer and a scanning electron microscope were used to characterize the phase composition and structure of the modified surface. Tribological properties of the treated titanium alloy were evaluated using a ball-on-disc tribometer under lubricated testing conditions. The effect of processing temperature on corrosion resistance of the plasma electrolytic nitrocarburising samples was examined by means of potentiodynamic polarization in Ringer’s solution. It was shown that the anodic nitrocarburising provides saturation of the titanium alloy with oxygen, nitrogen and carbon and the formation of TiO₂ with a rutile structure and a nitrogen/carbon solid solution in titanium. The anodic plasma electrolytic nitrocarburising at all treatment temperatures diminishes the wear rate of the titanium alloy samples and the surface roughness. Friction coefficient of treated samples can be reduced by 4.7 times. The anodic nitrocarburising results in an enhanced corrosion resistance since the corrosion potential increases by an order of magnitude.     

Effect of nitrogen on microstructure and corrosion resistance of Cr15 super martensitic stainless steel

ABSTRACT

To investigate the influence of nitrogen on structure and corrosion resistance of Cr15 super martensitic stainless steels (SMSS), two types (N-free and N-0.12%) of specimens were quenched at 1050°C and tempered at different temperatures, and then, optical microscope, transmission electron microscopy, X-ray diffraction, potentiodynamic polarisation, immersion experiments and Kelvin Probe Force Microscope were used to characterize its microstructures and corrosion properties. The experimental results show that the microstructure in the N-free Cr15 super martensitic stainless steel is a biphasic tissue with alternating martensite and austenite distribution while quenched at 1050°C and tempered between 600 and 700°C. The nitrogen addition increases the content of austenite, and changes the austenite morphology significantly into the coarse block and strip distribution. What’s more, micro-galvanic corrosion is formed between austenite and martensite, which deteriorates the corrosion resistance of the SMSS.     

奥氏体不锈钢的低温离子氮碳共渗研究

利用低压等离子体辉光放电技术对AISI 316奥氏体不锈钢进行低温离子氮碳共渗硬化处理，处理是在不降低奥氏体不锈钢耐蚀性能的前提下进行的。处理后的奥氏体不锈钢属于一种无氮化铬或碳化铬析出的氮和碳的过饱和固溶体(S相结构)。这种渗入钢中的过饱和氮和碳元素引起奥氏体晶格发生畸变，使渗层的硬度和耐磨性都有较大幅度的提高。由于处理后的奥氏体不锈钢渗层内的最大含氮量和最大含碳量分别出现在不同的深度，因而使离子氮碳共渗处理后的奥氏体不锈钢既有离子渗氮处理的高硬度，又有离子渗碳处理后的高的渗层厚度和良好的硬度梯度等特点。     

Study of plasma nitriding and nitrocarburising of AISI 430F stainless steel for high hardness and corrosion resistance

ABSTRACT

In order to improve both the hardness and corrosion resistance properties of AISI 430F stainless steel, plasma nitriding (PN) and nitrocarburising processes were carried out at different temperatures ranging from 350 to 500°C for 4?h. After PN, the nitrided layer was found to be thicker compared to that obtained by plasma nitrocarburising process. There was an increase in microhardness values by a factor of six to seven compared to the plasma nitrided and nitrocarburised specimens respectively, treated at 500°C. The electrochemical corrosion behaviour of the plasma nitrided and nitrocarburised AISI 430F specimens show that the plasma nitrided and nitrocarburised specimens treated at 400°C for 4?h showed better corrosion resistance and higher surface hardness than the untreated AISI 430F stainless steel specimens. This is mainly attributed to the presence of nitrogen in the modified layer existing as a solid solution in the ferrite phase.

This paper is part of a supplementary issue from the 17th Asia-Pacific Corrosion Control Conference (APCCC-17).     

Improving the surface properties of A286 precipitation-hardening stainless steel by low-temperature plasma nitriding

Plasma nitriding over a wide range of treatment temperatures between 350 and 500 °C and time from 5 to 30 h on A286 austenitic precipitation-hardening stainless steels has been investigated. Systematic materials characterisation of the plasma surface alloyed A286 alloy was carried out in terms of microstructure observations, phase identification, chemical composition depth profiling, surface and cross-section microhardness measurements, electrochemical corrosion tests, dry sliding wear tests and corrosion-wear tests. Experimental results have shown that plasma nitriding can significantly improve the hardness and wear resistance of A286 stainless steels owing to the formation of nitrogen supersaturated S-phase; the surface layer characteristics (e.g. microstructure, case depth and hardness) of the plasma surface alloyed cases are highly process condition dependent and there are possibilities to provide considerable improvement in wear, corrosion and corrosion-wear resistance of A286 steel.     

The corrosion and corrosion-wear behaviour of plasma nitrided 17-4PH precipitation hardening stainless steel

Plasma surface nitriding of 17-4 PH martensitic precipitation hardening stainless steels was conducted at 350 °C, 420 °C and 500 °C for 10 h using a DC plasma nitriding unit, and the surface properties of the plasma surface engineered samples were systematically evaluated. Experimental results have shown that the surface properties of the plasma nitrided layers in terms of hardness, wear resistance, corrosion behaviour and corrosion-wear resistance are highly process condition dependent, and it is feasible to provide considerable improvement in wear, corrosion and corrosion-wear resistance of 17-4PH steel using optimised plasma treatment conditions. All three treatments can effectively improve the surface hardness and the sliding wear resistance under unlubricated conditions; high temperature (420 °C and 500 °C) treated materials revealed improved corrosion and corrosion-wear properties due to the formation of surface compound layers.     

离子渗氮对304L不锈钢组织及高温耐磨性能的影响

以焚烧炉用热电偶304L不锈钢套管为研究对象,开展了不同温度的离子渗氮试验研究。采用光学显微镜、扫描电镜、显微硬度计等分析了304L不锈钢离子渗氮前后的微观结构与力学性能,并研究了其在400 ℃的耐磨损性能。结果表明,304L不锈钢离子渗氮后,可形成硬度1300 HV以上的表面硬化层。随着渗氮温度的提高,表面硬度有所提升,同时硬化层厚度显著增加。离子渗氮可提高304L不锈钢的磨损性能及耐高温氧化性能。     

Investigations on the Corrosion Behaviour and Structural Characteristics of Low Temperature Nitrided and Carburised Austenitic Stainless Steel

The wear resistance of austenitic stainless steels can be improved by thermo-chemical surface treatment with nitrogen and carbon. However, it is possible that the corrosion resistance will be impaired by the precipitation of chromiumnitrid or -carbide. The present contribution deals with investigations of the corrosion behaviour and structural characteristics of a low temperature nitrided and carburised austenitic stainless steel.The material investigated was AISI 316L (X2CrNiMol7-12-2) austenitic stainless steel. A commercial plasma-nitriding unit (pulsed dc) was used for the nitriding and carburising process. Additional samples were treated by the gasoxinitriding process for a comparison between plasma- and gasoxinitriding. The nitrided and carburised layer of austenitic stainless steel consists of the nitrogen or carbon S-phase (expanded austenite), respectively. X-ray diffraction investigations show the typical shift of the peaks to lower angles, indicating expansion of the fcc lattice. Also the X-ray diffraction technique was employed to study the residual stresses in the nitrogen and carbon S-phase. The corrosion behaviour of surface engineered samples was investigated with electrochemical methods. Anodic potentiodynamic polarisation curves were recorded for testing the resistance against general corrosion (in H2SO4) and pitting corrosion (in NaCl).     

The Effect of Time and Temperature of Nitridation-Oxidation Process on Properties and Corrosion Resistance of AISI 316L Steel

In this research, AISI 316L austenitic stainless steel has been subjected to plasma nitriding and oxidation- nitridation heat treatment at several temperatures for different times. Plasma nitriding of the samples was performed in N₂/H₂ = 1/3 atmosphere at temperatures of 425, 450, and 475°C for 5 h. To study the effects of the combined nitridation-oxidation process on mechanical and physical properties, the samples have been exposed in O₂/H₂ = 1/5 oxidating atmosphere at 425, 450, and 500°C for 15, 30, and 60 min, respectively. The mechanical and physical properties of the samples were studied after nitridation-oxidation heat treatment. The microstructural properties were examined by optical microscopy and scanning electron microscopy; the phases were analyzed by X-ray diffraction. The wear behavior of the oxidized-nitrided samples was studied using pin-on-disk tribotesting. The hardness and depth of the nitrided layer were measured by a Vickers hardness tester. The corrosion resistance of both untreated and treated samples was tested by the Tafel polarization and potentiodynamic polarization in 3.5% NaCl solution at ambient temperature. The results indicate that the combined nitridation-oxidation heat treatment improves both the pitting corrosion and wear resistances of AISI 316L steel and further increases its hardness.     

The wear and corrosion properties of stainless steel nitrided by low-pressure plasma-arc source ion nitriding at low temperatures

Low pressure plasma arc discharge-assisted nitriding of AISI 304 austenitic stainless steel is a process that produces surface layers with useful properties such as a high surface hardness of approximately 1500 Hv_0.1 and a high resistance to frictional wear and corrosion. The phase composition, the thickness, the microstructure and the surface topography of the nitrided layer, as well as its properties, depend essentially on the process parameters. Among them, the processing temperature is the most important factor for forming a hard layer with good wear and corrosion resistance. Nitriding austenitic stainless steel at approximately 420°C for 70 min can produce a thin layer of 7–8 μm with very high hardness and good corrosion resistance on the surface. The microstructure was studied by optical microscopy and both glancing angle and conventional Bragg–Brentano (θ–2θ) symmetric geometry X-ray diffraction (XRD). The formation of expanded austenite was observed. Measurements of the wear depths indicated that the wear resistance of austenitic stainless steel can be improved greatly by nitriding at approximately 420°C using low-pressure plasma-arc source ion nitriding.     

Improvement of corrosion and wear resistances of AISI 420 martensitic stainless steel using plasma nitriding at low temperature

The influence of low temperature plasma nitriding on the wear and corrosion resistance of AISI 420 martensitic stainless steel was investigated. Plasma nitriding experiments were carried out with DC-pulsed plasma in 25% N₂ + 75% H₂ atmosphere at 350 °C, 450 °C and 550 °C for 15 h. The composition, microstructure and hardness of the nitrided samples were examined. The wear resistances of plasma nitrided samples were determined with a ball-on-disc wear tester. The corrosion behaviors of plasma nitrided AISI420 stainless steel were evaluated using anodic polarization tests and salt fog spray tests in the simulated industrial environment.The results show that plasma nitriding produces a relatively thick nitrided layer consisting of a compound layer and an adjacent nitrogen diffusion layer on the AISI 420 stainless steel surface. Plasma nitriding not only increases the surface hardness but also improves the wear resistance of the martensitic stainless steel. Furthermore, the anti-wear property of the steel nitrided at 350 °C is much more excellent than that at 550 °C. In addition, the corrosion resistance of AISI420 martensitic stainless steel is considerably improved by 350 °C low temperature plasma nitriding. The improved corrosion resistance is considered to be related to the combined effect of the solid solution of Cr and the high chemical stable phases of ?-Fe₃N and α_N formed on the martensitic stainless steel surface during 350 °C low temperature plasma nitriding. However, plasma nitriding carried out at 450 °C or 550 °C reduces the corrosion resistance of samples, because of the formation of CrN and leading to the depletion of Cr in the solid solution phase of the nitrided layer.     

Surface nanocrystallization by surface mechanical attrition treatment and its effect on structure and properties of plasma nitrided AISI 321 stainless steel

A plastic deformation surface layer with nanocrystalline grains was produced on AISI 321 austenitic stainless steel by means of surface mechanical attrition treatment (SMAT). Low-temperature nitriding of SMAT and un-SMAT AISI 321 stainless steel was carried out in pulsed-DC glow discharge. The effect of SMAT pretreatment on the microstructure and properties of the stainless steel were investigated using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Vickers hardness tester and UMT-2MT tribometer. The results show that the plasma nitriding of AISI 321 steel can be enhanced considerably by means of SMAT process before nitriding, and a much thicker nitrogen diffusion layer with higher hardness was obtained for the SMAT samples when compared with un-SMAT samples. In addition, the wear resistance and load capacity of the nitrided layers on the SMAT samples was much higher than that of the un-SMAT samples due to the thicker S phase case and the gradient nitrogen diffusion layer.     

Improvement of Mechanical Properties of Martensitic Stainless Steel by Plasma Nitriding at Low Temperature

A series of experiments were carried out to study the influence of low temperature plasma nitriding on the mechanical properties of AISI 420 martensitic stainless steel. Plasma nitriding experiments were carried out for 15 h at 350℃ by means of DC- pulsed plasma in 25%N2＋ 75%H2 atmosphere. The microstructure, phase composition, and residual stresses profiles of the nitrided layers were determined by optical microscopy and X-ray diffraction. The microhardness profiles of the nitridied surfaces were also studied. The fatigue life, sliding wear, and erosion wear loss of the untreated specimens and plasma nitriding specimens were determined on the basis of a rotating bending fatigue tester, a ball-on-disc wear tester, and a solid particle erosion tester. The results show that the 350℃ nitrided surface is dominated by c-Fe3N and ON, which is supersaturated nitrogen solid solution. They have high hardness and chemical stabilities. So the low temperature plasma nitriding not only increases the surface hardness values but also improves the wear and erosion resistance. In addition, the fatigue limit of AISI 420 steel can also be improved by plasma nitriding at 350℃ because plasma nitriding produces residual compressive stress inside the modified layer.     

奥氏体不锈钢耐蚀渗氮工艺的研究

对AISI 321和AISI 304不锈钢进行了低温离子渗氮,其表面获得了均匀的渗氮层即白亮层。与未经渗氮的钢相比,经离子渗氮的钢表面硬度和耐磨性显著提高,而耐蚀性也并不降低;与经传统的盐浴氮碳共渗的钢相比,经离子渗氮的钢的耐磨性和耐蚀性也均有所提高。对经低温离子渗氮的AISI 321纲渗层进行了XRD分析,发现试样的谱峰明显向低角度偏移。     

Effect of heating post-treatment on nitrided stainless steel

Although plasma nitriding has been applied successfully to increase the hardness of austenitic stainless steels, the process cycles are long due to the low nitrogen diffusion rate for these steels. An alternative to reduce the nitriding time is to perform a heating treatment after nitriding to prolong the diffusion process. In this work we investigate the properties of plasma nitrided AISI 316 stainless steel after heating post-treatments. The samples were nitrided at 823 K during 3 h. After nitriding, heating post-treatments were performed in a vacuum furnace. The influence of the heating time, ranging from 1 up to 16 h, and heating temperatures, varying from 732 up to 873 K, on the surface properties was investigated. The samples were characterized using microhardness testing, scanning electron microscopy and X-ray diffraction. The nitriding treatment results in a compound layer 44 μm thick with a hardness of 1434 HV_0.1, consisting predominantly of γ'-[Fe₄N] and CrN phases. As expected, an increase of the compound layer thickness and a decrease of the surface hardness with heating time were observed. However, the microhardness profiles show that beneath the surface the layer hardness increases for long treatment times. New phases as Fe₃O₄ and FeCr₂O₄ appear and grow with increasing heating time.     

450℃渗氮AISI 316L不锈钢中膨胀奥氏体的分解

奥氏体不锈钢等离子渗氮时会形成膨胀奥氏体(γN),其强度、韧性和耐蚀性均高于传统的氮化物层。然而,膨胀奥氏体在热力学上是亚稳的,其性能会因其发生分解而降低。本文对AISI 316L不锈钢进行了等离子渗氮,工艺为450℃×5 h,压力500 Pa。对渗氮后试样采用XRD、OM和TEM等进行了显微组织表征。试验结果证明了面心立方膨胀奥氏体的存在,其晶格常数比未经渗氮奥氏体增加多达9.5%。薄片试样的TEM分析表明,N层中有细小的氮化物形成,并且发现一些区域呈奇特的层片状形貌,与碳钢中的珠光体团很相似。选区电子衍射(SAED)分析表明,这些区域由膨胀奥氏体局部分解产生的体心立方铁素体和立方晶系氮化铬组成。在所研究试样中的某些区域,发现有非晶态膨胀奥氏体。N的分解与膨胀奥氏体层局部区域中铁素体稳定元素(Cr,Mo)的显微偏析和奥氏体稳定元素(Ni)的贫化有关。