奥氏体不锈钢耐磨和耐蚀复合改性

采用电子回旋共振(ECR)微波等离子体源离子渗氮技术对奥氏体不锈钢进行氮化处理,获得与等离子体浸没离子注入(PII)结果相似的高硬度、高耐磨性表面改性层。     

等离子体浸没离子注入改善45钢的摩擦学性能

采用灯丝放电和射频(RF)辉光放电等离子体浸没离子注入(PⅢ)工艺对45钢表面进行了氮离子注入强化处理。通过X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、显微硬度、针-盘磨损和电化学腐蚀试验等测试手段，分析比较了经灯丝放电PⅢ和RF辉光放电PⅢ改性后试样表面元素的浓度分布、显微硬度、摩擦磨损性能和耐腐蚀性能。结果表明：不同条件下的氮离子注入均能提高45钢表面的显微硬度、耐磨性和抗腐蚀性能；且RF辉光放电PⅢ处理后试样的显微硬度提高了76．8％，摩擦系数下降到0．3，与灯丝放电PⅢ处理后的试样相比，其表面强化效果更加明显。     

Wear and corrosion properties of plasma-based low-energy nitrogen ion implanted titanium

Plasma-based low-energy nitrogen ion implantation, including plasma source ion nitriding/carburizing and plasma source low-energy ion enhanced deposition, has emerged as a low-temperature surface engineering technique for metal and alloy. In this paper, the pure metal Ti samples have been modified by the plasma source ion nitriding process at a process temperature of 700 °C for a processing time of 4 h. The nitrided Ti surfaces were constructed of a continuous and dense Ti₂N compound layer about 2 μm thick and a 7-8 μm diffused layer. During tribological test on a ball on disk tribometer against the Si₃N₄ ceramic counterface, a low friction coefficient of about 0.3 and the faint wear volume were obtained for the nitrided Ti samples. The cyclic polarization curves of the nitrided Ti samples in 3.5% and 6.0% NaCl solutions showed that the improved pitting corrosion resistance with an increase of corrosion potential and a decrease of passive current, compared with that of the unnitrided Ti sample. The plasma source ion nitriding of the Ti samples provided the engineering surfaces for the functional applications with the combined improvement in wear and corrosion resistance.     

TC4合金表面全方位离子注入Ag的耐摩擦磨损和抗腐蚀性能

为改善TC4合金表面的耐磨性能和抗腐蚀性能,用等离子体浸没离子注入(PIII)技术在合金表面注入不同剂量的金属银.采用XRD、XPS、AES等方法分析改性层的元素浓度分布和化学组成,研究Ag离子注入后试样表面的耐摩擦磨损性能、抗腐蚀性能、纳米硬度和弹性模量.结果表明,表面改性层中主要存在Ag相,同时含有少量的TiAg;处理后注入剂量为1×10~(17) ions/cm~2试样的纳米硬度和弹性模量分别提高62.5%和54.5%;磨损面积减小57.6%;摩擦系数由基体合金的0.78下降到0.2.在3.5%NaCl溶液中的腐蚀电位升高,腐蚀电流密度明显减小,耐蚀性得到了显著改善.     

Plasma nitriding of plastic mold steel to increase wear- and corrosion properties

In this study, the wear- and corrosion resistance of the layers formed on the surface of a precipitation hardenable plastic mold steel (NAK55) by plasma nitriding were investigated. Plasma nitriding experiments were carried out at an industrial nitriding facility in an atmosphere of 25% N₂ + 75% H₂ at 475 °C, 500 °C, and 525 °C for 10 h. The microstructures of the nitrided layers were examined, and various phases present were determined by X-ray diffraction. Wear tests were carried out on a block-on-ring wear tester under unlubricated conditions. The corrosion behaviors were evaluated using anodic polarization tests in 3.5% NaCl solution.The findings had shown that plasma nitriding does not cause the core to soften by overaging. Nitriding and aging could be achieved simultaneously in the same treatment cycle. Plasma nitriding of NAK55 mold steel produced a nitrided layer consisted of a compound layer rich in ε-nitride and an adjacent nitrogen diffusion layer on the steel surface. Increasing the nitriding temperature could bring about increase in the thickness of the nitrided layer and the nitride volume fraction. Plasma nitriding improved not only surface hardness but also wear resistance. The anti-wear property of the steel was found to relate to the increase in the thickness of the diffusion layer. Corrosion study revealed that plasma nitriding significantly improved corrosion resistance in terms of corrosion potential and corrosion rate. Improvement in corrosion resistance was found to be directly related to the increase in the nitride volume fraction at the steel surface.     

In vitro corrosion behavior of TiN layer produced on orthopedic nickel-titanium shape memory alloy by nitrogen plasma immersion ion implantation using different frequencies

In the present work, the NiTi surface was modified by nitrogen plasma immersion ion implantation (PIII) in an effort to improve the corrosion resistance and mitigate nickel release from the materials. The implanted nitrogen depths and thicknesses of the surface TiN barrier layers were varied by changing the pulsing frequencies during PIII. In order to determine the optimal parameters including the pulsing frequencies, electrochemical tests including open circuit potential (OCP) measurements and potentiodynamic polarization tests were conducted on the untreated and N-implanted NiTi in simulated body fluids (SBF). Our results reveal that the nitride layer produced using a frequency of 50 Hz has the best stability under the OCP conditions and the TiN layer produced using 200 Hz has the highest potentiodynamic stability after immersion in SBF for a long time. The observation can be correlated to the temperature during PIII and the thickness of TiN layer. The TiN layer on the NiTi surface favors deposition of Ca-P composites thereby compensating for the instability of the TiN layer produced at a higher frequency.     

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.     

Corrosion resistance properties of glow-discharge nitrided AISI 316L austenitic stainless steel in NaCl solutions

Glow-discharge nitriding treatments can modify the hardness and the corrosion resistance properties of austenitic stainless steels. The modified layer characteristics mainly depend on the treatment temperature. In the present paper the results relative to glow-discharge nitriding treatments carried out on AISI 316L austenitic stainless steel samples at temperatures ranging from 673 to 773 K are reported. Treated and untreated samples were characterized by means of microstructural and morphological analysis, surface microhardness measurements and corrosion tests in NaCl solutions. The electrochemical characterization was carried out by means of linear polarizations, free corrosion potential-time curves and prolonged crevice corrosion tests. Nitriding treatments performed at higher temperatures (>723 K) can largely increase the surface hardness of AISI 316L stainless steel samples, but decrease the corrosion resistance properties due to the CrN precipitation. Nevertheless nitriding treatments performed at lower temperatures (?723 K) avoid a large CrN precipitation and allow to produce modified layers essentially composed by a nitrogen super-saturated austenitic metastable phase (S-phase) that shows high hardness and very high pitting and crevice corrosion resistance; at the same polarization potentials the anodic current density values are reduced up to three orders of magnitude in comparison with untreated samples and no crevice corrosion event can be detected after 60 days of immersion in 10% NaCl solution at 328 K.     

纯钛离子氮化层在人工唾液中的耐蚀性

用浸泡法和电化学法研究了纯钛（TA2）基体材料及其离子氮化层在人工唾液中的腐蚀行为。浸泡法研究表明,试样随着浸泡时间的延长而增重,而离子氮化层增重明显减缓,其腐蚀速率远小于TA2基材;电化学法研究表明,离子氮化层的自腐蚀电位较TA2基材提高,而腐蚀电流密度和腐蚀速度减小。由失重法和电化学法得出一致结论,离子氮化处理提高了TA2在人工唾液中的耐蚀性。     

Tribology and cyclic oxidation behavior of plasma nitrided valve steel

In this study, the tribology and cyclic oxidation behavior of plasma nitrided DIN 1.4871 austenitic valve steel were investigated. For this purpose plasma nitriding treatments were carried out in nitrogen and hydrogen with ratio N₂/H₂: 1/3 at 10 Torr pressure. Nitriding cycles of 400, 450, 500 and 550 °C for 7 h were selected. To remove oxide layer and to enhance diffusion, an effective sputter cleaning procedure was applied in argon and hydrogen gases. The pin-on-disc sliding wear experiments were performed at a load of 6 N and sliding velocity of 0.1 m/s in normal atmosphere under dry condition. Cyclic oxidation tests used to evaluate the oxidation characteristics of the samples consisted of 50 cycles each 30 min at 750 °C. The structure and properties of the samples were examined by optical and scanning electron microscopy (SEM), microhardness measurements and X-ray diffraction. The results indicated plasma nitriding at all temperatures increased the wear resistance of valve steel when sliding against bearing steel. The 550 °C nitrided layer, with CrN, Fe₄N and Fe_2-3N on the surface, was most effective in improving wear resistance. In the case of cyclic oxidation, the results showed that oxidation resistance depends strongly on nitriding temperature. Nitriding at 450 °C produced a layer of predominantly “S” phase which was more effective in improving the oxidation resistance of valve steel.     

Corrosion properties of active screen plasma nitrided 316 austenitic stainless steel

AISI 316 austenitic stainless steel has been plasma nitrided using the active screen plasma nitriding (ASPN) technique. Corrosion properties of the untreated and AS plasma nitrided 316 steel have been evaluated using various techniques, including qualitative evaluation after etching in 50%HCl + 25%HNO₃ + 25%H₂O, weight loss measurement after immersion in 10% HCl, and anodic polarisation tests in 3.5% NaCl solution. The results showed that the untreated 316 stainless steel suffered severe localised pitting and crevice corrosion under the testing conditions. AS plasma nitriding at low temperature (420 °C) produced a single phase nitrided layer of nitrogen expanded austenite (S-phase), which considerably improved the corrosion properties of the 316 austenitic stainless steel. In contrast, AS plasma nitriding at a high temperature (500 °C) resulted in chromium nitride precipitation so that the bulk of the nitrided case had very poor corrosion resistance. However, a thin deposition layer on top of the nitrided case, which seems to be unique to AS plasma nitriding, could have alleviated the corrosion attack of the higher temperature nitrided 316 steel.     

The microstructure and properties of 17-4PH martensitic precipitation hardening stainless steel modified by plasma nitrocarburizing

17-4PH martensitic precipitation hardening stainless steel was plasma nitrocarburized at 430 °C and 460 °C for 8 h. The nitrocarburized layers were characterized by optical microscope, scanning electron microscope, X-ray diffractometer, microhardness tests, pin-on-disc tribometer and the anodic polarization method in a 3.5% NaCl solution. The results show that the microstructure of plasma nitrocarburized layer is characterized by a compound layer with no evident diffusion zone. The phases in the 430 °C treated layer are mainly of γ′-Fe₄N, nitrogen and carbon expanded martensite (α′_N), and some incipient CrN phases. When the temperature increases up to 460 °C, there is no evidence of α′_N phase. The processes of bulk precipitation hardening and surface treatment by plasma nitrocarburizing can be successfully combined in a single-step process on this steel. The hardness of modified layer can reach up to 1186HV, which is 3 times higher than that of untreated steel. The wear and corrosion resistance of the specimens can be apparently improved by plasma nitrocarburizing. The 460 °C/8 h treated specimen has the best wear and corrosion resistance in the present test conditions.     

Influence of Plasma Nitriding on the Microstructure, Wear, and Corrosion Properties of Quenched 30CrMnSiA Steel

The oil-quenched 30CrMnSiA steel specimens have been pulse plasma-nitrided for 4 h using a constant 25% N₂-75% H₂ gaseous mixture. Different nitriding temperatures varying from 400 to 560 °C have been used to investigate the effects of treatment temperature on the microstructure, microhardness, wear, and corrosion resistances of the surface layers of the nitrided specimens. The results show that significant surface-hardened layer consisting of compound and diffusion layers can be obtained when the oil-quenched steel (α′-Fe) are plasma-nitrided at these experimental conditions, and the compound layer mainly consists of ε-Fe_2-3N and γ′-Fe₄N phases. Lower temperature (400-500 °C) nitriding favors the formation of ε-Fe_2-3N phase in surface layer, while a monophase γ′-Fe₄N layer can be obtained when the nitriding is carried out at a higher temperature (560 °C). With increasing nitriding temperature, the compound layer thickness increases firstly from 2-3 μm (400 °C) to 8 μm (500 °C) and then decreases to 4.5 μm (560 °C). The surface roughness increases remarkably, and both the surface and inner microhardness of the nitrided samples decrease as increasing the temperature. The compact compound layers with more ε-Fe_2-3N phase can be obtained at lower temperature and have much higher wear and corrosion resistances than those compound layers formed employing 500-560 °C plasma nitriding.     

304 不锈钢低温离子渗氮及氮碳共渗处理

目的研究304不锈钢离子渗氮层和氮碳共渗层的组织、硬度及耐磨、耐蚀性能,并考察渗层的磨损机理。方法利用离子渗氮及氮碳共渗工艺在304不锈钢表面获得硬化层,利用XRD,OM及共聚焦显微镜、显微硬度仪、电化学测试仪,分析处理前后渗层的组织、相结构及渗层的硬度及耐磨耐蚀性能。结果 304不锈钢氮碳共渗和渗氮层主要为S相层,在相同工艺条件下,氮碳共渗工艺获得的渗层为γN+γC的复合渗层,且厚度大于单一渗氮层。渗氮层和氮碳共渗层硬度约为基体硬度的3.5倍。在干滑动摩擦条件下,氮碳共渗层比渗氮层具有更好的耐磨性能;渗氮层的磨损机理为磨粒磨损的犁沟效应和断裂,氮碳共渗层的磨损机理为磨粒磨损的犁沟和微切削。电化学测试表明,渗氮层和氮碳共渗层的耐蚀性能均优于基体。结论 304不锈钢在420℃进行离子渗氮和氮碳共渗处理后,硬度和耐磨性能可大幅提高,且氮碳共渗处理效果更佳。     

Corrosion properties of plasma nitrided AISI 410 martensitic stainless steel in 3.5% NaCl and 1% HCl aqueous solutions

Samples of an AISI 410 martensitic stainless steel were plasma nitrided at a temperature of 420 °C, 460 °C or 500 °C for 20 h. The composition, microstructure and hardness of the nitrided samples were characterised using a variety of analytical techniques. In particular, the corrosion properties of the untreated and plasma nitrided samples were evaluated using anodic polarisation tests in 3.5% NaCl solution and immersion tests in 1% HCl acidic water solution. The results showed that plasma nitriding produced a relatively thick nitrided case consisting of a compound layer and a nitrogen diffusion layer on the 410 stainless steel surface. Plasma nitriding not only increased the surface hardness but also improved the corrosion resistance of the martensitic stainless steel. In the immersion test, nitrided samples showed lower weight loss and lower corrosion rate than untreated one. In the electrochemical corrosion tests, the nitrided samples showed higher corrosion potentials, higher pitting potentials and greatly reduced current densities. The improved corrosion resistance was believed to be related to the iron nitride compound layer formed on the martensitic stainless steel surface during plasma nitriding, which protected the underlying metal from corrosive attack under the testing conditions.     

Martensitic stainless steel modified by plasma nitrocarburizing at conventional temperature with and without rare earths addition

17-4PH Martensitic stainless steel was plasma nitrocarburized at conventional temperature (560 °C) with and without rare earths (RE) addition. The surface treated layers were characterized by optical microscope, scanning electron microscope equipped with an energy dispersive X-ray analyzer, X-ray diffraction and microhardness test. The wear and corrosion behavior of the modified specimens was studied respectively using pin-on-disc tribometer and anodic polarization tests. The results show that rare earths atoms can diffuse into the surface of the stainless steel. The microstructures of all modified layers are characterized by a compound layer containing three distinct zones but without an evident diffusion zone. The phases on all modified surface layers are mainly of θ-Fe₃C and CrN. It is exciting that the hardness profile of the modified layer is decreased gradually, which is rarely found in plasma nitriding of the stainless steel. The friction coefficient of a specimen can be dramatically decreased by plasma RE nitrocarburizing, whereas the corrosion resistance is deteriorated. In contrast, the corrosion resistance of a plasma nitrocarburized specimen is enhanced but the friction coefficient is not improved as much as that of a plasma RE nitrocarburized one.     

Electrochemical behavior of the Ti6Al4V alloy implanted by nitrogen PIII

Plasma surface treatments have been used very often to enhance the surface properties of metallic materials. In this work, Ti6Al4V titanium alloy was treated by nitrogen plasma immersion ion implantation (NPIII) in order to obtain improvements in its surface properties, such as corrosion resistance evaluated here. The microstructure and corrosion behavior of the implanted and unimplanted samples were evaluated, using, XRD, GDOES and potentiodynamic polarization and impedance electrochemical spectroscopy tests in 0.6 M NaCl solution. It was verified that the NPIII created resistant layers to corrosive attacks. In corrosion tests by polarization, the implanted samples showed corrosion current density reduction of about 10 times compared to the Ti6Al4V alloy without treatment. Besides that, it was also observed a reduction of the passive current density of one order of the magnitude. In all the studied cases, the polarization curves were shifted to more positive values of potentials, indicating a lower tendency of these PIII treated surfaces to corrosion. The implantation process produced a thin TiN surface layer followed by Ti₂N and then a layer with nitrogen in solid solution, all detected by GDOES combined with X-ray diffraction. These layers promoted an excellent polarization resistance of the Ti6Al4V surfaces on impedance spectroscopy tests also. This better performance in these tests can be correlated with the formation of continuous nitride layer, which could retard chloride ions ingress into the substrate.     

Nitrogen diffusion in medical CoCrNiW alloys after plasma immersion ion implantation

CoCr alloys are widely used for medical applications, e.g. total hip replacements or coronary stents. Nevertheless, an increase in the surface hardness and a reduction of the wear rate is still desirable to improve the biocompatibility. Plasma immersion ion implantation (PIII) at different temperatures, acceleration voltages and working pressures is used to determine the nitrogen diffusivity in the CoCr alloys SY21med, L605 and HS188. Depending on the temperature, two different treatment regimes can be distinguished, independent of the ion energy. At low temperatures, a diffusion process with an activation energy of 1.0-1.1 eV is present, indicative of interstitial nitrogen diffusion. Beyond 350 °C, a reduced activation energy of 0.5-0.7 eV is observed. Additionally, a strong dependency of the layer thickness on the working pressure in the range 0.3-0.8 Pa was observed for the temperature dependent diffusion regime, which suggests a synergistic interplay of adsorption and implantation during PIII. Below 500 °C, an increase of the diffusion coefficient by three orders of magnitude was observed for PIII, compared with pure plasma nitriding.     

The Structure and Mechanical Properties of Cr4Mo4V Steel Treated by PIII Carbonitriding

The composition and structure of PIII(plasma immersion ion implantation)carbonitrided Cr4Mo4V steel were analyzed using X-ray photoelectron spectroscopy(XPS),X-ray diffraction(XRD),optical microscopy(OM)and SEM.The results indicate that the nitride and carbide are dispersion phase precipitation and except formation of compound other implantation atoms dissolve into martensite matrix.The total concentration of carbon and nitrogen is about 30 at%near the surface,and still keeps at about 20 at%even at the depth of 8μm.The effect of treatment temperature,implantation time and ratio of N2 to CH4 on the hardness and wear resistance of carbonitrided layer are investigated.It is found that the hardness of Cr4Mo4V steel increases after treatment.The highest hardness of samples is 22.3 GPa,which is about 1.8 times than initial steel.The dry-wear resistance of the samples is also improved after treatment,and the sample with higher hardness shows the better wear resistance.     

等离子浸没式注入表面改性

采用新型的离子注入技术－离等子体浸没式离子注入对４５钢进行了氮离子注入,测定了注入层的氮浓度俄歇剖面会布,显微硬度和摩擦性能,对磨损表面进行了扫描电镜分析。结果表明,采用等离子浸没式离子注入技术能够获得钢表改性效果。