Production of Nanocrystalline Ni-20Cr Coatings for High-Temperature Applications

Presynthesized nanocrystalline Ni-20Cr powder was deposited on SA 516 and T91 boiler steels by a high-velocity oxy-fuel spraying process. Ni-20Cr powder was synthesized by the ball milling approach. The high-temperature oxidation behavior of bare and coated samples was then studied under cyclic isothermal conditions at 900 °C for 50 cycles. The kinetics of oxidation was established using weight change measurements for the bare and coated boiler steels. Uncoated and coated samples of T91 steel were exposed to the superheated zone of a power plant boiler at 750 °C under cyclic conditions for 15 cycles. Each cycle consisted of 100 h of heating followed by 1 h of cooling. Attempts were made to study the kinetics of erosion–corrosion using weight change and thickness loss data for the samples. Different characterization techniques were used to study the oxidized and eroded–corroded samples, including x-ray diffraction, scanning electron microscopy/energy-dispersive spectroscopy, and x-ray mapping analyses. The Ni-20Cr alloy powder coating was found to offer excellent oxidation resistance to the base steels and was successful in reducing the weight gain of SA 516 steel by 98.5 % and that of T91 steel by 65 %. The coating was observed to reduce the erosion–corrosion rate of T91 steel by 86 % in terms of thickness loss. This indicates that the investigated nanostructured coating can be a better choice over conventional coating for erosion–corrosion control of boiler tubes.     

Corrosion resistance of Ni‐50Cr HVOF coatings on 310S alloy substrates in a metal dusting atmosphere

Metal dusting attack has been examined after three 168 h cycles on two Ni‐50Cr coatings with different microstructures deposited on 310S alloy substrates by the high velocity oxy‐fuel (HVOF) thermal‐spray process. Metal dusting in uncoated 310S alloy specimens was found to be still in the initiation stage after 504 h of exposure in the 50H₂:50CO gas environment at 620 °C. Dense Ni‐50Cr coatings offered suitable resistance to metal dusting. Metal dusting was observed in the 310S substrates adjacent to pores at the interface between the substrate and a porous Ni‐50Cr coating. The porosity present in the as‐deposited coatings was shown to introduce a large variability into coating performance. Carbon formed by decomposition of the gaseous species accumulated in the surface pores and resulted in the dislodgement of surface splats due to stresses generated by the volume changes. When the corrosive gas atmosphere was able to penetrate through the interconnected pores and reach the coating–substrate interface, the 310S substrate was carburized, metal dusting attack occurred, and the resulting formation of coke in the pores led to local failure of the coating.     

Investigations on the Behavior of HVOF and Cold Sprayed Ni-20Cr Coating on T22 Boiler Steel in Actual Boiler Environment

High temperature corrosion accompanied by erosion is a severe problem, which may result in premature failure of the boiler tubes. One countermeasure to overcome this problem is the use of thermal spray protective coatings. In the current investigation high velocity oxy-fuel (HVOF) and cold spray processes have been used to deposit commercial Ni-20Cr powder on T22 boiler steel. To evaluate the performance of the coatings in actual conditions the bare as well as the coated steels were subjected to cyclic exposures, in the superheater zone of a coal fired boiler for 15 cycles. The weight change and thickness loss data were used to establish kinetics of the erosion-corrosion. X-ray diffraction, surface and cross-sectional field emission scanning electron microscope/energy dispersive spectroscopy (FE-SEM/EDS) and x-ray mapping techniques were used to analyse the as-sprayed and corroded specimens. The HVOF sprayed coating performed better than its cold sprayed counterpart in actual boiler environment.     

Untersuchungen zum Einfluss des Stickstoffs auf das Lochkorrosionsverhalten hochlegierter austenitischer Cr‐Ni‐Mo‐Stähle

Investigation of the influence of nitrogen on the pitting corrosion of high alloyed austenitic Cr‐Ni‐Mo‐steels Austenitic stainless steels (18% Cr, 12% Ni, Mo gradation between 0.5 to 3.6%) had been gas‐nitrided. By stepwise removal, samples could be prepared with various surface content of nitrogen up to 0.45%. The susceptibility against pitting corrosion of these samples had been tested by two methods: – determination of the stable pitting potential in 0.5 M NaCl at 25°C – determination of the critical pitting temperature in artificial sea water (DIN 81249‐4) The influence of nitrogen to both determined parameter can be described well by PRE = Cr + 3,3 · Mo + 25 · N That means for the investigated steel composition and the used corrosion system there is no influence of molybdenum on the effectiveness of nitrogen.     

Corrosion characteristics of the wrought Ni‐Cr‐Mo alloys

This paper concerns the wrought, nickel‐chromium‐molybdenum (Ni‐Cr‐Mo) alloys, a family of materials with a long history of use in the chemical process industries. Their attributes include resistance to the halogen acids and resistance to pitting, crevice attack, and stress corrosion cracking in hot, halide salt solutions. The purpose of this paper is to characterize the performance of the Ni‐Cr‐Mo alloys in several key chemicals, using iso‐corrosion diagrams. These indicate the expected corrosion rates over wide ranges of concentration and temperature. Furthermore, the differences between individual Ni‐Cr‐Mo alloys, and their behavior relative to the stainless steels are defined. The data indicate benefits of both a high chromium content and a copper addition, as used in Hastelloy® C‐2000® alloy.     

Comparative study on corrosion protection properties of electroless Ni‐P‐ZrO2 and Ni‐P coatings on AZ91D magnesium alloy

Electroless Ni‐P‐ZrO₂ and Ni‐P coatings on AZ91D magnesium alloy were prepared, and their corrosion protection properties were compared in this paper. The potentiodynamic curves and electrochemical impedance spectroscopy (EIS) of the coated magnesium alloy in 3.5% NaCl solution showed that the corrosion performance of Ni‐P‐ZrO₂ composite coating was superior to that of Ni‐P coating. The same conclusion was obtained with salt spray and immersion tests. The corrosion morphologies of two kinds of coatings with various immersion time intervals in 3.5% NaCl solution indicated that most corrosion products concentrated on the nodules boundaries of Ni‐P coating and blocked corrosion pit was the main corrosion form. For the Ni‐P‐ZrO₂ coating, tortuous nodules boundaries were not the weak sites of the coating and corrosion initiated from the nickel phosphor alloy around the nanometer powders. Open corrosion pits occurred on the composite coating surface, and the coating was corroded gradually. Thus, the Ni‐P‐ZrO₂ coating exhibited better corrosion protection property to magnesium alloy substrate than Ni‐P coating.     

High Temperature Corrosion Behavior of Cold Spray Ni-20Cr Coating on Boiler Steel in Molten Salt Environment at 900 °C

Cold spray is an emerging technology that produces high density metallic coatings with low oxide contents and high thermal conductivity, which makes them ideal for high temperature corrosion resistance. In the current investigation, Ni-20Cr alloy powder was deposited on SA 516 boiler steel (0.19C-1.07Mn-0.020S-0.25P-0.010Si-balance Fe) by cold spray process. Oxidation kinetics was established for the uncoated and cold spray Ni-20Cr coated boiler steel in an aggressive environment of Na₂SO₄-60%V₂O₅ at 900 °C for 50 cycles by the weight change technique. X-ray diffraction, FE-SEM/EDAX, and x-ray mapping techniques were used to analyze the oxidation products. Uncoated steel suffered corrosion in the form of intense spalling and peeling of its oxide scale, which may be due to the formation of unprotective Fe₂O₃ oxides. The Ni-20Cr coating was successful in reducing the weight gain of the steel by 87.2% which may be due to the formation of oxides of nickel and chromium.     

Oxidation mechanisms of Cr‐containing steels and Ni‐base alloys at high‐temperatures –. Part I: The different role of alloy grain boundaries

It is essential for materials used at high‐temperatures in corrosive atmosphere to maintain their specific properties, such as good creep resistance, long fatigue life and sufficient high‐temperature corrosion resistance. Usually, the corrosion resistance results from the formation of a protective scale with very low porosity, good adherence, high mechanical and thermodynamic stability and slow growth rate. Standard engineering materials in power generation technology are low‐Cr steels. However, steels with higher Cr content, e.g., austenitic steels, or Ni‐base alloys are used for components applied to more severe service conditions, e.g., more aggressive atmospheres and higher temperatures. Three categories of alloys were investigated in this study. These materials were oxidised in laboratory air at temperatures of 550°C in the case of low‐alloy steels, 750°C in the case of an austenitic steel (TP347) and up to 1000°C in the case of the Ni‐base superalloys Inconel 625 Si and Inconel 718. Emphasis was put on the role of grain size on the internal and external oxidation processes. For this purpose various grain sizes were established by means of recrystallization heat treatment. In the case of low‐Cr steels, thermogravimetric measurements revealed a substantially higher mass gain for steels with smaller grain sizes. This observation was attributed to the role of alloy grain boundaries as short‐circuit diffusion paths for inward oxygen transport. For the austenitic steel, the situation is the other way round. The scale formed on specimens with smaller grain size consists mainly of Cr₂O₃ with some FeCr₂O₄ at localized sites, while for specimens with larger grain size a non‐protective Fe oxide scale is formed. This finding supports the idea that substrate grain boundaries accelerate the chromium supply to the oxide/alloy phase interface. Finally, in the Ni‐base superalloys deep intergranular oxidation attack was observed, taking place preferentially along random high‐angle grain boundaries.     

Nickel-chromium plasma spray coatings: A way to enhance degradation resistance of boiler tube steels in boiler environment

Boiler tube steels, namely low carbon steel ASTM-SA-210-Grades A1 (GrA1), 1Cr-0.5Mo steel ASTM-SA213-T-11 (T11), and 2.25Cr-1 Mo steel ASTM-SA213-T-22(T22), were used as substrate steels. Ni-22Cr-10Al-1Y powder was sprayed as a bond coat 150 μm thick before a 200 μm final coating of Ni-20Cr was applied Coatings were characterized prior to testing in the environment of a coal fire boiler. The uncoated and coated steels were inserted in the platen superheater zone of a coal fired boiler at around 755°C for 10 cycles, each 100 h. Coated steels showed lower degradation (erosion-corrosion) rate than uncoated steels showed. The lowest rate was observed in the case of Ni-20Cr coated T11 steel. Among the uncoated steels, the observed rate of degradation was the lowest for the T22 steel.     

Untersuchungen zum Einfluss des Stickstoffs auf das Lochkorrosionsverhalten hochlegierter austenitischer Cr‐Ni‐Mo‐Stähle (Teil II)

Investigation of the influence of nitrogen on the pitting corrosion of high alloyed austenitic Cr‐Ni‐Mo‐steels (Part II) Austenitic stainless steel (18% Cr, 12% Ni, Mo gradation between 0,06 to 3,6%) had been solution nitrided. By step‐by‐step removing, the samples could be prepared with various surface contents of nitrogen from 0.04 to 0.42%. In two test series the influence of nitrogen had been determined. The susceptibility against pitting corrosion of these samples had been tested by the chronopotentiostatical method. For the investigated steel composition and the used corrosion system there is no infuence of molybdenum on the effectiveness of nitrogen. The effectiveness of nitrogen can be described by the factor 25 in the PRE. By the investigation of the surfaces with the XPS analysis, it could be shown that the passivation and the pit nucleation is influenced by nitrogen. In these ranges NO_x, NH_x, and NH_z‐spectra have been detected. Bound Mo was found in steels containing molybdenum. It is assumed that the repassivation mechanisms of N and Mo work independently of each other. With the results efforts are supported to improve the pitting corrosion resistance also at molybdenum poor steels by surface nitriding or nitrogen alloying. The achieved results justify the assumption that the observed positive effect of the nitrogen may be extented to even higher nitrogen contents. A prerequisite for this is avoiding secondary phases in the matrix. The adverse influence of small particles is known well.     

Comparative High Temperature Analysis of HVOF-Sprayed and Detonation Gun Sprayed Ni�C20Cr Coating in Laboratory and Actual Boiler Environments

High-velocity-oxy-fuel (HVOF) spray and detonation-gun (D-gun) spray techniques were used to deposit Ni?C20Cr coatings on a commonly used boiler steel ASTM-SAE 213-T22. The specimens, with and without coating, were subjected to molten salt (Na₂SO₄?C60%V₂O₅) deposition in a laboratory furnace at 900 °C to determine hot-corrosion resistance. Specimens were also exposed to the superheater zone of a thermal power plant boiler at an average temperature of 700 °C under cyclic conditions to ascertain their erosion-corrosion (E-C) behavior. Mass-change measurements were taken to approximate the kinetics of corrosion and erosion-corrosion. In the case of E-C, the thickness lost data were also taken at the end of the exposure. The exposed specimens were characterized by X-ray diffraction (XRD) and field-emission scanning electron microscopy/energy dispersive spectroscopy (FE-SEM/EDS). The HVOF-sprayed coating was found to be intact during exposure to both given environments; whereas the D-gun coating showed spallation of its oxide scale during exposure to the molten salt environments. An overall analysis of the results indicated that the HVOF-sprayed Ni?C20Cr coating should be a better choice for the given boiler applications.     

Performance of Detonation Gun-Sprayed Ni-20Cr Coating on ASTM A213 TP347H Steel in a Boiler Environment

Detonation gun-sprayed coatings are known for their high density, high bond strength, moderate substrate heating, superior surface finish, better wear/corrosion resistance, and low cost. In this study, detonation gun-spraying technique was used to deposit Ni-20Cr coating on a commonly used boiler steel ASTM A213 TP347H. The specimens with and without coating were subjected to cyclic oxidation testing at an elevated temperature of 700 °C in actual boiler environment to ascertain the usefulness of the coating. The mass change technique was used to establish the kinetics of erosion-corrosion. XRD and SEM/EDS techniques were used to analyze the exposed samples. The uncoated sample suffered from erosion, and a significant mass loss was recorded. It was observed that overall mass loss was reduced by 83% and thickness loss by 53% after the application of the coating. The detonation gun-sprayed Ni-20 Cr coating was found to be suitable to impart erosion resistance to the given steel in the actual boiler environment.     

奥氏体不锈钢热浸镀铝层的抗氧化特性

为进一步提高奥氏体不锈钢0Cr18Ni9Ti的高温使用性能,对该钢进行了热浸镀铝处理和抗高温氧化性能的试验.试验结果表明:经热浸镀铝处理后,奥氏体不锈钢0Cr18Ni9Ti的抗高温氧化性能明显得到改善,其热浸镀铝层的抗高温氧化行为符合抛物线规律.1 000℃抗氧化试验表明:在高温氧化过程中,表层Al2O3氧化膜及扩散层中的金属间化合物FeAl相和β-NiAl相起到抗氧化作用.     

1Cr18Ni9Ti与1Cr13不锈钢的焊接试验

通过钨极氩弧焊方法,对 1Cr18Ni9Ti 与 1Cr13 实施焊接.采用光学显微镜、扫描电镜对 1Cr13 马氏体型与 1Cr18Ni9Ti 奥氏体型不锈钢焊接接头进行金相组织、断口形貌观察及分析;利用显微硬度计、电子万能拉伸机测量焊接接头的力学性能;并通过海水模拟溶液浸泡试验,测量焊接接头极化曲线和交流阻抗谱.结果表明,通过手工钨极氩弧焊,采用直流正接接法,在合适的工艺下(焊接电流为 80 A,焊接速度为 110 mm/min),能够获得外观平整、组织均匀,力学性能与电化学性能符合要求的焊接接头.

Abstract：

The stainless steels of 1Cr18Ni9Ti and 1Cr13 were welded through deterministic craft by tungsten inert-gas (TIG) welding. The microstructure and fracture pattern of weld joints of 1Cr13martensite and 1Cr18Ni9Ti austenite stainless steels were observed and analyzed by means of LOM and SEM, the mechanical properties of the weld joints were measured with micro-hardness tester and electronic universal stretcher, and the polarization curves and AC impedance spectroscopy of weld joints were tested by seawater immersion test of simulation solution. The results show that adopting manual TIG welding through electrode negative to direct current soldering machine to weld 1Cr18Ni9Ti austenite stainless steel and 1Cr13 martensite stainless steel is feasible; under suitable process (welding current is 80 A, welding speed is 110 mm/min), weld joints can obtain good appearance and uniform structure; mechanical properties and galvano-chemistry properties can meet use requirements.     

Development of Re‐based diffusion barrier coatings on nickel based superalloys

A diffusion barrier type coating with a duplex layer structure, an inner σ‐(Re, W, Cr, Ni) as a diffusion barrier and outer Ni‐aluminide as an Al reservoir, was formed on a Nickel based, single crystal, superalloy (TMS‐82 +) and on Hastelloy X. Oxidation properties of both the alloys with or without the diffusion barrier coating were investigated in air under thermal cycling between room temperature and 1423 K for up to 360 ks. The inner σ layer with a composition (at%) of (35–40) Re, (15–20) W, (15–25) Cr and (15–25) Ni was produced by electrodeposition of Ni‐70Re and Ni‐20W films from aqueous solutions followed by Cr‐pack cementation at temperatures between 1473 and 1573 K, and the outer Ni‐aluminides of β‐(Ni,Cr)Al + γ′‐(Ni,Cr)₃Al was formed by electrodeposition of a Ni film, followed by Al pack cementation. After the 360 ks oxidation it was found that the structure and composition of both σ layer and alloy substrate were retained with little change. Furthermore, there was little Al in the σ layer. It could be concluded that the Re‐based alloys such as σ (Re(W),Cr,Ni) are very promising candidates as a diffusion barrier between the outer Al‐reservoir layer and alloy substrate at temperature of 1423 K. It was found that the Re(W)‐Cr‐Ni acts as a diffusion barrier for both inward diffusion of Al and outward diffusion of alloying elements in the alloy substrate.     

清水和含沙水中20SiMn和0Cr13Ni5Mo钢的空蚀行为

利用超声振荡空蚀实验机对两种主要的水轮机用金属材料进行了清水和含水水条件下的空蚀行为研究,结果表明,高硬度的0Cr13Ni5Mo不锈钢抗清水和含水沙水的空蚀性能均显著高于低硬度的20SiMn低合金钢,在清水空蚀中0Cr13Ni5Mo不锈钢均匀脱落,而20SiMn低合金钢不均匀脱落,表面出明显的空蚀坑,空蚀和沙子冲蚀磨损的联合作用使得两种材料在含沙水中的空蚀失重显著高于水空蚀,0Cr13Ni5Mo不锈钢在含沙水中的空蚀育期显著缩短。     

应用电极涂层工艺生产1Cr12Ni2W1Mo1V电渣重熔钢

大冶特钢公司应用电极涂层的工艺方法，使碳或硅、锰成分偏低的电极材料在电渣重熔过程中减少这些元素的烧损，甚至提高含量，从而生产出成分完全合格的电渣重熔钢，应用于1Cr12Ni2W1MO1V耐热钢生产取得了良好的结果。     

超音速火焰喷涂WC-10Co4Cr涂层的耐滑动磨损行为

采用超音速火焰喷涂(HVOF)工艺制备微米结构WC-10Co4Cr涂层,分别采用金相显微镜、扫描电镜(SEM)、X射线衍射(XRD)和滑动磨损设备分析涂层的微观结构和滑动磨损行为。结果表明:采用液体煤油燃料HVOF喷涂的微米结构WC-10Co4Cr涂层的脱碳程度较低,涂层中仅出现WC和W2C相,而无η相(Co3W3C、Co6W6C)以及软相W。涂层微观结构致密,孔隙率约为1%,平均显微硬度为1 322HV0.3;在相同试验条件下,WC-10Co4Cr涂层的摩擦因数(约0.8)高于不锈钢(1Cr18Ni9Ti)的摩擦因数(约0.5),其滑动体积损失量仅为不锈钢涂层的1/146,具有优异的抗滑动磨损性能。涂层在滑动磨损过程中首先是粘结相的脱落,然后是WC颗粒的磨损。     

冷喷涂钛涂层与1Cr13不锈钢的电偶腐蚀行为

以氮气为载气,在压力为2.0MPa,载气温度为500℃的状态下,用冷喷涂的方法在1Cr13不锈钢基体上制备了钛金属涂层。经SEM观察,发现涂层的厚度较大,没有直接贯穿到基体的孔隙存在,距离基体越近的区域,涂层的孔隙率越小,XRD分析表明,涂层基本无氧化物相生成;从热力学和动力学两方面研究冷喷涂钛涂层与1Cr13不锈钢的电偶腐蚀行为,发现两者的电偶腐蚀倾向较小。     

焊后热处理对1Cr18Ni9Ti与2Cr13钢焊接接头组织和性能的影响

通过钨极氩弧焊方法,对1Cr18Ni9Ti与2Cr13钢实施焊接,并对焊接接头整体进行焊后热处理。采用OM、SEM对2Cr13与1Cr18Ni9Ti钢热处理前后的焊接接头组织进行分析,利用显微硬度计、电子万能拉伸机测量了焊接接头的力学性能。结果表明,1Cr18Ni9Ti和2Cr13钢焊接接头热处理前焊缝组织为典型的柱状晶,组织为板条马氏体+残留奥氏体+碳化物;热处理后焊缝组织为回火索氏体,而且碳化物析出量也明显增多。拉伸时,热处理前后焊接接头断裂的部位都发生在奥氏体不锈钢热影响区一侧,热处理前后焊接接头的抗拉强度分别约为635.56、649.44 MPa;焊缝区的显微硬度分别约为276、222 HV0.5,热处理后焊接接头的整体显微硬度比热处理前的明显降低。