Microstructure of electroplated hard chromium coatings after plasma nitrocarburizing

Plasma nitrocarburizing was carried out on the hard chromium coating deposited on SM45C mild carbon steel substrate by electroplating. After plasma nitrocarburizing at 720 °C for 20 h, a 6–7-μm-thick nitride layer consisting of CrN and Cr₂N was formed on the surface of Cr coating with the microhardness of about 950–1100 HV0.1. Due to the effect of annealing caused by plasma nitrocarburizing process at higher temperature and the Cr being a strong carbide-forming element, the carbon in steel substrate diffused outward into the Cr coating and reacted with Cr forming Cr carbide interface layer between the Cr electroplating and substrate. The nitrogen going into the microcracks and the volume increase accompanied by Cr nitride and carbide formation would cause the microcracks inherent to hard chromium plating disappear and improve its corrosion resistance. The microstructures of nitride and carbide layers were studied using X-ray diffraction and cross-sectional transmission electron microscopy.     

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.     

2Cr13钢的表面气体渗氮处理

用光学金相显微镜、扫描电子显微镜、X射线衍射(XRD)仪及显微硬度计对经气体渗氮处理的2Cr13钢试样进行了组织结构分析,并利用销-盘摩擦磨损试验机对渗氮的盘与未渗氮销摩擦副进行摩擦磨损试验.结果表明,520℃×20 h渗氮可使2Cr13马氏体不锈钢的渗氮层深度达到165 μm,处理后试样的显微硬度约为处理前的2.5倍.处理后试样的耐磨性能得到了较大的提高,渗氮盘试样的磨损表面未出现裂纹,而未渗氮销的磨损表面存在严重的裂纹.     

Effect of the initial microstructure on the plasma nitriding behavior of AISI M2 high speed steel

The nitriding behavior of AISI M2 steel was studied on samples previously submitted to two different heat treatments in order to investigate the effects of the initial microstructure on the thickness and hardness of nitrided layer. Prior to nitriding, one group of samples was fully annealed while the other group was quenched and tempered, thus acquiring the lowest and highest hardness respectively. Plasma nitriding was performed at 450 °C for 8 h with a mixture of N₂ and H₂ in a plasma reactor working under floating potential. Structural and mechanical properties of nitrided layers were characterized using X-ray diffraction (XRD), optical microscopy and microhardness testing. Variations in surface roughness were obtained by 3D surface profilometry analysis. The thicker nitrided layer was obtained for the fully annealed samples, in which the nitrided layer is composed of γ′-Fe₄N and ε-Fe_2-3N phases plus a diffusion zone. For the hardened-tempered samples, the nitrided region mainly consisted of a diffusion zone. Plasma nitriding increased the surface hardness of the fully annealed samples by 330% and that of the quenched-tempered samples by 50%. The nitrided depth was also estimated using cross-sectional microhardness profiles; giving about 140 µm and ∼ 70 µm for the fully annealed and quenched-tempered samples, respectively. Due to the grain to grain nitrogen diffusion, plasma nitriding also increased the surface roughness. The largest roughness was obtained for the fully annealed samples, in accordance with the largest nitrided depth. The difference in the nitriding behavior was explained on the basis of the microstructural aspects of the substrates such as the concentration of the freely dispersed alloying elements and the level of compressive residual stresses.     

Effect of prior plasma nitriding applied to a hot-work tool steel on the scratch-resistant properties of PACVD TiBN and TiCN coatings

Ternary TiBN and TiCN coatings on a hot-work tool steel substrate with and without plasma nitriding (PN) prior to plasma-assisted chemical vapour deposition (PACVD) were investigated. Compositional analysis with a radio frequency glow discharge optical emission spectroscope (rf-GDOES) showed mixtures of TiBN + TiN and TiCN + TiN in the PACVD TiBN and TiCN coatings, respectively. Each coating layer had a compositional gradient across the coating depth and slightly into the substrate. The microhardness profiles (HV_0.1) of the substrate with and without PN from the interface with the coating to the substrate core were determined. The depth of the effective nitrided diffusion layer was confirmed from the examination of its optical microstructure. The adhesion of these two coatings to the substrate was evaluated through scratch tests in the progressive mode. It was found that with increasing load, both of the coatings on the substrate with and without prior nitriding deteriorated in the same failure modes. Critical loads corresponding to the first microcracking related to cohesive failure, spallation related to adhesive failure, breakthrough and worn out were determined and used to quantify the scratch resistance of these coatings. With PN prior to PACVD, both the cohesion and adhesion properties of the TiBN and TiCN coatings were remarkably improved. This improvement was attributed to a functionally gradient hardness configuration from the coating through the nitrided diffusion layer to the substrate.     

Corrosion protection of electroplated nickel using silane coupling agent

Abstract

Electroplated nickel was chemically modified using an aminosilane coupling agent (as an alternative to chromate) in order to improve its corrosion performance. Infrared spectroscopy revealed that the silane bonded to the metal satisfactorily. The corrosion behaviour of a nickel electroplated steel workpiece was investigated using potentiodynamic polarisation and electrochemical impedance spectroscopy to optimise the silane deposition conditions. These data confirm that the most effective conditions are dipping in the silane coupling agent solution for 30 s and then curing at 100°C for 40 min.     

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.     

脱碳层对38CrMoAl钢离子渗氮的影响

对表面残存不同厚度脱碳层的38CrMoAl钢塔形试样进行离子渗氮,借助显微硬度计、光学显微镜、扫描电镜等多种手段,对试样渗速、硬度及渗氮前后的微观组织进行研究。结果表明,在残余的脱碳层里存在较严重的魏氏组织;残余脱碳越严重魏氏组织越多;离子渗氮的渗速随着表面脱碳层厚度的增加先增加后降低;魏氏组织中大量的铁素体为氮原子扩散提供了快速渗入通道及形成大量氮化物的场所,在渗层表面形成大量的鱼骨状、网状、脉状氮化物,数量随着脱碳层的增加而增加,并且不断向渗层深处延伸。38CrMoAl钢表面残存脱碳层虽然有加快渗速的作用,但会增加渗层的不良组织,增加渗层剥落的风险。故38CrMoAl钢制工件做普通调质应适当加大加工余量。     

On the corrosion resistance of porous electroplated zinc coatings in different corrosive media

The corrosion resistance of an electroplated (EP) Zn coating whose surface was chemically etched to produce surface defects (pores) is investigated in this work. Impedance and DC polarisation measurements were employed to study the behaviour of such coating in various corrosive media (NaCl, NaOH and rain water). Four different faradaic relaxation processes were clearly revealed in different NaCl concentrations (from 0.1 to 1 M). In the most concentrated solutions at least three relaxation processes at low frequencies (LF) appeared and were related to zinc deposition and dissolution. At lower concentrations and depending on the pH, only one process was observed. The charge transfer resistance (R_ct) and the corrosion current (I_corr) were practically stable in the pH range 5-10. In deaerated NaCl 0.1 M, the EIS diagrams showed two time constants at very close frequencies. From the EIS diagrams the porous nature of the coating was highlighted and showed that the dissolution mechanisms occurred at the base of the pores.     

Delayed cracking in plasma nitriding of AISI 420 stainless steel

The phenomenon of delayed cracking in nitrided layers after DC-plasma nitriding of AISI 420 steel has been observed by optical microscopy. Prior to the plasma treatment, the samples were austenitized at 1303 K for 30 min and then oil quenched. Two tempering conditions were assessed: one group was tempered at 673 K, while another group was tempered at 943 K.All samples were subjected to sputtering, in the plasma chamber, to remove the passive oxide layer, under a 1:1 Ar/H₂ atmosphere. Finally, specimens were plasma nitrided at 673 K for 20 h, with a 1/3: N₂/H₂ relation, at a pressure of 6.5 hPa and 700 V bias in the nitriding chamber.The nitrided layers were analyzed initially by X-ray diffraction (XRD). Detailed observations were conducted at frequent and regular intervals under optical microscopy (OM) and scanning electron microscopy (SEM) with secondary and back-scattered electrons detectors. The results revealed that after an incubation time, even without any external disturbance, cracks are formed and propagate in the nitrided layers. Both groups of samples were equally affected. The presence of precipitated particles and local residual stresses are possible causes of such a phenomenon.     

二次调质离子渗氮工艺参数对35CrMo钢耐蚀性的影响

采用不同的回火温度、渗氮温度和N2与H2的比例,对35CrMo钢进行热处理,通过正交试验分析这些参数对渗氮层耐蚀性的影响。结果表明,最佳的耐蚀性热处理工艺为回火温度550℃、渗氮温度540℃、氮气与氢气流量比为1∶5。XRD分析表明白亮层组织以γ’相为主,并含一定量的α-Fe(N)和ε相,这种组织有很好的耐蚀性,且具有较小的的脆性。     

一种时效硬化钢的深层离子渗氮

对20CrNi3Mn2Al 时效硬化钢进行不同温度和不同时间的离子渗氮处理,优选出最佳渗氮工艺为520~540 ℃×50 h氨气变温深层离子渗氮处理,表层硬度高,化合物层薄,硬度梯度好,表面下0.1 mm处硬度大于900 HV,0.4 mm处硬度大于600 HV,渗氮层深大于0.7 mm,基体硬度为400~450 HV,可用于制造大型重载高速精密齿轮,部分替代渗碳钢,省去渗碳和油淬工序,简化工艺,减少变形。     

Influence of plasma nitriding on hydrogen environment embrittlement of 1.4301 austenitic stainless steel

The aim of this work was to study if hydrogen environment embrittlement of DIN 1.4301 austenitic stainless steel can be suppressed by a nitrided surface. DIN 1.4301 was plasma nitrided in a N₂/H₂ discharge. Nitriding produced 3-layered structure consisting of a γ_N top layer, an intermediate γ/γ_C-layer and a diffusion layer. It is assumed that the γ_C phase was formed due to the decomposition of CO originating from the reactor walls and the subsequent incorporation of C into the material. The γ_C phase is characterized by distinct XRD peaks and carbon contents between 0.5 and 4 wt.% as well as nitrogen contents between 0.5 and 8 wt.%. Plastic deformation of the plasma nitrided specimen showed cracks and some delamination of the γ_N layer, whereas the γ/γ_C-layer behaved in a very ductile manner. Even at a plastic deformation of 35% no cracks or any other damage was visible. A tensile test in gaseous hydrogen showed severe embrittlement of the unnitrided steel and the nitrided steel with a γ_N layer. No cracks were observed in areas where just the γ/γ_C-layer was present.     

预氧化+稀土铈对42CrMo钢离子渗氮的影响

针对离子渗氮渗层浅及生产周期长等技术难题,采用预氧化与稀土复合催渗对工程常用结构钢42CrMo进行了离子渗氮.利用显微硬度计、光学显微镜(OM)、扫描电镜(SEM)等对渗氮速率、渗氮层组织、表面形貌等进行了系统的研究.结果表明,经400℃x1 h氧化+0.6 cm2/kg(铈表面积/装炉量)稀土的复合催渗工艺具有最佳催...     

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).     

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。     

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.     

Study of active screen plasma processing conditions for carburising and nitriding austenitic stainless steel

Active screen (AS) is an advanced technology for plasma surface engineering, which offers some advantages over conventional direct current (DC) plasma treatments. Such surface defects and process instabilities as arcing, edge and hollow cathode effects can be minimised or completely eliminated by the AS technique, with consequent improvements in surface quality and material properties. However, the lack of information and thorough understanding of the process mechanisms generate scepticism in industrial practitioners.In this project, AISI 316 specimens were plasma carburised and plasma nitrided at low temperature in AS and DC furnaces, and the treated samples were comparatively analysed. Two diagnostic techniques were used to study the plasma: optical fibre assisted optical emission spectroscopy, and a planar electrostatic probe. Optimum windows of treatment conditions for AS plasma nitriding and AS plasma carburising of austenitic stainless steel were identified and some evidence was obtained on the working principles of AS furnaces. These include the sputtering of material from the cathodic mesh and its deposition on the worktable, the generation of additional active species, and the electrostatic confinement of the plasma within the operative volume of the furnace.     

Intensified plasma-assisted nitriding of AISI 316L stainless steel

In the present study, processing of AISI 316L stainless steel (316ss) has been conducted by intensified plasma-assisted processing (IPAP). The processing parameters (bias voltage, current density, chamber pressure and substrate temperature) of IPAP have been varied in an effort to determine which conditions lead to the formation of a single-phase structure, ‘m’ phase, and evaluate the properties of this phase. The structural characteristics of the nitrided layers produced by IPAP have been investigated by X-ray diffraction analysis. Nanoindentation experiments have been performed over cross-section to determine hardness and elastic modulus profiles. Dry sliding wear and potentiodynamic aqueous corrosion experiments have been conducted to characterize 316ss nitrided by IPAP. IPAP has been successful in producing single-phase m with high hardness and in shorter processing time compared to diode plasma nitriding. The IPAP produced single-phase nitrided layer was found to possess higher hardness (fourfold increase over the unprocessed alloy), excellent wear and corrosion resistance.     

1Cr11Ni2W2MoV钢的离子渗氮

利用脉冲直流辉光等离子技术,对1Cr11Ni2W2MoV马氏体热强不锈钢进行不同工艺参数的离子渗氮。利用光学显微镜、显微硬度计、XRD对渗氮层的显微组织及硬度进行了分析。结果表明,在所选用的离子渗氮工艺参数下,1Cr11Ni2W2MoV钢渗层只由扩散层组成,渗氮温度≤560℃时,渗层主要由固溶N原子的α相组成,并伴有少量的γ'-Fe4N和CrN析出;随着渗氮温度的升高和渗氮时间的延长,固溶N原子的α相逐渐转变成γ'-Fe4N相,当处理温度达到590℃时,渗层主要由γ'-Fe4N和Cr N组成。离子渗氮后渗层的表面硬度较未渗氮前有显著的提高,在一定范围内,渗层的表面硬度和渗层深度都随着渗氮温度和渗氮时间的增加而增加,渗层硬度梯度分布也随着渗氮时间的延长变得平缓。