Characterizations and hot corrosion resistance of Cr3C2-NiCr coating on Ni-base superalloys in an aggressive environment

In the current study, Cr₃C₂-NiCr coating was deposited on the Ni-base superalloys by using high velocity oxyfuel (HVOF) process for high temperature corrosive environment applications. Optical microscopy (OM), x-ray diffraction (XRD), scanning electron microscopy/energy-dispersive analysis (SEM/EDAX), microhardness tester, and electro probe microanalyzer (EMPA) techniques were used to characterize the coating with regard to coating thickness, porosity, microhardness, and microstructure. The thermogravimetric technique was used to establish kinetics of corrosion. The hot corrosion behaviors of the bare and Cr₃C₂-NiCr coated superalloys were studied after exposure to aggressive environment of Na₂SO₄-60% V₂O₅ salt mixture at 900 °C under cyclic conditions. The structure of the as-sprayed Cr₃C₂-NiCr coating mainly consisted of γ-nickel solid solution along with minor phases of Cr₇C₃ and Cr₂O₃. Coating has porosity less than 1.5% and microhardness in the range of 850–900 Hv (Vickers hardness). Some inclusions, unmelted and semimelted powder particles were observed in the structure of the coatings. The Cr₃C₂-NiCr coating has imparted necessary resistance to hot corrosion, which has been attributed to the formation of oxides of nickel and chromium, and spinel of nickel-chromium. This article was originally published inBuilding on 100 Years of Success, Proceedings of the 2006 International Thermal Spray Conference (Seattle, WA), May 15–18, 2006, B.R. Marple, M.M. Hyland, Y.-Ch. Lau, R.S. Lima, and J. Voyer, Ed., ASM International, Materials Park, OH, 2006.     

Erosion Performance of HVOF-Sprayed Cr3C2-NiCr Coatings

Cr₃C₂-NiCr coatings were deposited by high-velocity oxygen fuel (HVOF) spraying process under spray conditions of different flows of oxygen and propane gases, and spray distances. The orthogonal regression experimental design method was used for systematic investigation of the influence of spray parameters on the erosion performance of Cr₃C₂-NiCr coatings. Erosion tests were performed at different jet angles of abrasive particles. The erosion mechanism of Cr₃C₂-NiCr coatings was examined through the surface morphology and cross-sectional microstructure of the eroded coatings. The correlations of the carbide particle size and carbide content with the erosion rate were examined. It was found that the erosion occurred dominantly by spalling of splats from the lamellar interfaces. The spalling resulted from the propagation of cracks parallel to the interfaces between the lamellae exposed to the surface and underlying coating. The carbide particle size and content in the coating influenced significantly the erosion performance of Cr₃C₂-NiCr coatings.     

爆炸喷涂Cr3C2-NiCr涂层的激光重熔工艺

借助半导体激光器对爆炸喷涂Cr3C2-NiCr涂层进行激光重熔处理。通过扫描电镜观察涂层激光重熔前后的形貌,测试涂层激光重熔前后的显微硬度,并对涂层进行盐雾试验和残余应力分析。结果表明,当激光功率为300 W,激光扫描速度为100 mm?min-1时,涂层的激光重熔效果最好。当涂层经过上述激光重熔工艺参数处理后,涂层中富Ni的NiCr合金相得到细化且均匀性提高,涂层的显微硬度、耐磨性和耐腐蚀性进一步提高,涂层中部的残余应力均转变为压应力。     

HVOF喷涂Cr3C2-NiCr涂层的磨粒磨损性能

探讨了氧气流量、燃气流量和喷涂距离三个喷涂工艺参数对ＨＶＯＦ喷涂Ｃｒ３Ｃ２－ＮｉＣｒ涂层硬度和磨粒磨损性能的影响。结果表明,燃气流量、氧气流量和喷涂距离对涂层的显微硬度和磨粒磨损性能的规律有所不同。在较高的燃气流量、适中的氧气流量和喷涂距离条件下,涂层具有较高的显微硬度;而氧气流量和燃气流量对涂层的磨粒磨损性能影响较大,适中的燃气流量条件下,涂层的磨粒磨损失重量较低,高的氧气流量条件下,磨损失重量     

超音速火焰喷涂Cr3C2-NiCr涂层磨粒磨损行为

采用橡胶轮磨损实验机，对不同工艺条件下三种类型粉末制备的HOVF Cr3C2-25％NiCr涂层进行了磨粒磨损实验，发现该涂层的磨损失重量与磨程基本呈现线性关系，磨损率远低于低碳钢。氧气流量，燃气流量适中的条件下制备的涂层磨损率较低，用团聚致密化工艺制备的粉末沉积的涂层耐磨粒磨损性能较好，涂层的磨损机制主要为先期的粘结相优先切削和随后的碳化物剥落，其中碳化物的剥落对磨损过程起制约作用。     

Mechanical and tribological properties of plasma-sprayed Cr3C2-NiCr, WC-Co, and Cr2O3 coatings

Mechanical properties such as Young’s moduli and fracture toughness of plasma-sprayed Cr₃C₂-NiCr, WC-Co and Cr₂O₃ coatings were measured. The tribological properties of the three kinds of coatings were investigated with a block-on-ring self-mated arrangement under water-lubricated sliding. Furthermore, the influences of the mechanical properties on the tribological properties of the coatings were also examined. It was found that the Young’s moduli, bend strengths and fracture toughness of the coatings were lower than the corresponding bulk materials, which may be attributed to the existence of pores and microcracks in the coatings. Among the three kinds of coatings, the magnitude of wear coefficients, in decreasing order, is Cr₃C₂-NiCr, WC-Co and Cr₂O₃, and the wear coefficient of Cr₂O₃ coating was less than 1 × 10⁻⁶mm³N⁻¹m⁻¹. The wear mechanisms of the coatings were explained in terms of microcracking and fracturing, and water deteriorated wear performance of the coatings. The higher the fracture toughness and the lower the porosity and length of microcracking of the coating, the more the wear-resistance of the coating.     

Cr3C2-NiCr涂层的高温抗氧化和热耐腐蚀性

采用大气等离子喷涂技术制备Cr3C2-NiCr复合涂层,并对制备的Cr3C2-NiCr涂层试样进行800 ℃×100 h氧化和熔盐（Na2SO4+25 wt%NaCl）热腐蚀试验。利用X射线衍射仪（XRD）和带能谱的扫描电镜(SEM/EDX)分析氧化、腐蚀涂层表面和截面的成分及结构变化,探讨其高温氧化、腐蚀机理。结果表明：等离子喷涂Cr3C2-NiCr涂层具有层状组织结构,喷涂过程中无明显相分解或氧化。高温氧化后的Cr3C2-NiCr涂层表面及层片界面形成了连续、致密的Cr2O3保护膜,涂层表现出优异的抗高温氧化性能。在热腐蚀过程中,腐蚀盐破坏了涂层表面及层片界面形成的氧化膜,腐蚀性元素沿着涂层中的孔洞及层片界面扩散到涂层内部,涂层发生“活化氧化”,耐腐蚀性较差。     

Properties of Cr3C2-NiCr cermet coating sprayed by high power plasma and high velocity oxy-fuel processes

The structure, hardness, and shear adhesion strength have been investigated for Cr₃C₂-NiCr cermet coatings sprayed onto a mild steel substrate by 200 kW high power plasma spraying (HPS) and high velocity oxy-fuel (HVOF) processes. Amorphous and supersaturated nickel phases form in both as-sprayed coatings. The hardness of the HVOF coating is higher than that of the HPS coating, because the HVOF coating contains more nonmelted Cr₃C₂ carbide particles. On heat treating at 873 K, the amorphous phase decomposes and the supersaturated nickel phase precipitates Cr₃C₂ carbides so that the hardness increases in the HPS coating. The hardness measured under a great load exhibits lower values compared with that measured with a small load because of cracks generated from the indentation. The ratio of the hardnesses measured with different loads can be regarded as an index indicating the coating ductility. The ductility of the HVOF coating is higher than that of the HPS coating. Adhesion strength of the HVOF coating was high compared with the HPS coating. The adhesion of the coatings is enhanced by heat treating at 1073 K, and that of the HVOF coating is over 350 MPa.     

超音速火焰喷涂Cr3C2-NiCr涂层在NaOH 溶液中的腐蚀及冲蚀腐蚀磨损性能

目的 分析超音速火焰喷涂制备的Cr3C2-NiCr涂层在碱性环境中的腐蚀及冲蚀腐蚀磨损性能,揭示涂层腐蚀及冲蚀腐蚀磨损失效机制。方法 利用超音速火焰喷涂技术在45#钢表面制备Cr3C2-NiCr金属陶瓷涂层,采用光学显微镜、显微硬度仪、碱性环境腐蚀性能试验台、电化学分析仪、冲蚀腐蚀磨损试验机、电子天平、扫描电子显微镜,分别对组织结构、显微硬度、碱性环境下耐蚀性能、耐冲蚀腐蚀磨损性能、冲蚀腐蚀磨损损失质量及表面形貌进行测试。结果 Cr3C2-NiCr涂层呈典型层状结构,内部随机分布着孔隙及氧化物,涂层孔隙率及显微硬度平均值分别为1.3%和817HV0.1。在pH=11的NaOH溶液中,涂层的电化学腐蚀电位为-0.38 V,腐蚀反应生成的氧化物可有效阻止腐蚀继续进行,长期浸泡过程中,腐蚀介质通过裂纹或穿透性孔隙渗入涂层内部直至基体表面,并发生腐蚀反应,形成的腐蚀产物逐渐累积并排出至涂层表面,最终形成体积较大且呈团絮状的腐蚀产物。在碱性腐蚀环境下,腐蚀介质加剧冲蚀磨损中的材料消耗。相同条件下,涂层腐蚀冲蚀磨损损失质量明显小于基体材料,涂层的冲蚀腐蚀磨损失效机制主要有腐蚀产物脱落、硬质颗粒剥落、粘结相磨耗、缺陷处因疲劳裂纹整体脱落。结论 在碱性环境中,Cr3C2-NiCr涂层具有较强的耐腐蚀性能,腐蚀介质能加快涂层冲蚀磨损进程,磨损后表面为非光滑表面,使涂层具有较优的抗冲蚀磨损性能,故Cr3C2-NiCr涂层可显著改善基体表面的综合使用性能。     

High-velocity oxyfuel Cr<Subscript>3</Subscript>C<Subscript>2</Subscript>-NiCr replacing hard chromium coatings

Comparative wear and corrosion properties of Cr₃C₂-NiCr (CC-TS) (a high-velocity oxyfuel [HVOF]) and hard chromium (HC) coatings obtained on a steel substrate have been studied. The structural characterization was done before and after measurements by optical microscopy, scanning electron microscopy, and scanning white light interferometry. Wear and corrosion properties were evaluated by ball on disk (ASTM G99-90), rubber wheel (ASTM G65-91), and electrochemical measurements of open circuit and polarization curves. The best corrosion and wear resistance was for the CC-TS obtained by HVOF. The open-circuit potential values measured for both samples after 18 h of immersion were: −0.240 and −0.550 V, respectively, for CC-TS and HC, versus Ag/AgCl,KCl_sat. Three orders of magnitude lower volume loss were found for CC-TS (HVOF) after friction tests compared with HC.     

Cr3C2-NiCr/TiSiN-CrAlN复合涂层制备及高温摩擦学行为研究

目的 基于表面耐高温薄膜和高承载金属陶瓷涂层性能优势协同的设计思想,制备Cr3C2-NiCr/ TiSiN-CrAlN复合涂层,提高硬质薄膜机械性能和不同温度下的摩擦学性能。方法 采用超音速火焰喷涂(HVOF)和电弧离子镀(AIP)技术制备Cr3C2-NiCr/TiSiN-CrAlN复合涂层,通过扫描电子显微镜、X射线衍射仪、纳米压入仪、划痕仪和高温摩擦磨损试验机等对复合涂层的微观结构、机械性能和不同温度下的摩擦磨损行为进行系统研究。结果 Cr3C2-NiCr/TiSiN-CrAlN复合涂层微观结构致密,界面结合良好,其顶层耐高温薄膜由CrAlN结合层和TiSiN-CrAlN交替多层构成,总厚度约6.7 μm,低于不锈钢表面直接沉积TiSiN-CrAlN薄膜的厚度(约9.6 μm)。Cr3C2-NiCr支撑层微观结构和形貌影响其表面沉积TiSiN-CrAlN薄膜的结晶性。Cr3C2-NiCr/TiSiN-CrAlN复合涂层具有优异的机械性能,其纳米硬度和弹性模量分别高达(37.3±2.6)GPa和(506.1±10.6)GPa,结合力相比不锈钢表面TiSiN-CrAlN多层膜显著提高。得益于Cr3C2-NiCr支撑层的引入,复合涂层在不同温度下的摩擦因数和磨损率均比单一薄膜的低,其摩擦因数在900 ℃下可稳定保持在0.44左右,磨损率约为3.13×10^?5 mm³/(N.m),表现出良好的高温摩擦学性能。此外,磨损机制分析表明,500 ℃以下主要为磨粒磨损和黏着磨损,摩擦因数较大、不稳定,但磨损率基本不变;700 ℃时由于Cr3C2-NiCr层的支撑作用而无明显的疲劳磨损,氧化磨损发生;900 ℃时氧化磨损主导,摩擦界面生成主要成分为TiO2、Cr2O3的摩擦反应膜。结论 采用HVOF和PVD相结合的方法在不锈钢表面制备的Cr3C2-NiCr/TiSiN-CrAlN复合涂层具有良好的机械性能和优异的高温摩擦学性能,可进一步改善耐高温薄膜的综合性能,具有良好的应用前景。     

Plasma spray coating of spray-dried Cr2O3/wt.% TiO2 powder

An agglomerated Cr₂O₃/wt.%TiO₂ powder has been fabricated by the spray drying process under different parameters. The spray-dried powder has well-agglomerated particles of spherical shape. In the conditions of the high slurry feed rate and low binder concentration in the slurry, the powder has large cavities inside some particles and ruggedness over their surface. The optimum plasma spray feed rate has been found by examining the spraying behavior of the powder and melted state of particles. The plasma spray coating has been performed under different process variables such as spraying distance and plasma power. These parameters strongly affect the characteristics of the coated layer: microstructure, hardness, and bond strength.     

Use of microhardness as a simple means of estimating relative wear resistance of carbide thermal spray coatings: Part 2. wear resistance of cemented carbide coatings

A selection of WC-Co and Cr₃C₂-25%NiCr coatings produced by plasma spray and high velocity oxygen fuel (HVOF) deposition techniques were subjected to various wear tests designed to simulate abrasion, cavitation, sliding, and particle erosion type wear mechanisms. All of the coatings were at least 200 μm thick and were deposited onto stainless steel substrates. In Part 1 of this contribution, the microstructures of the coatings were characterized and their mechanical properties were assessed using microindentation procedures. In this second part of the article, the behavior of the coatings when subjected to the various wear tests is reported and the utility of microhardness testing as an indication of relative wear resistance is discussed. It is shown that correctly performed, appropriate microhardness measurements are a good indication of abrasion resistance and sliding wear resistance, and also correlate well with cavitation resistance in Cr₃C₂-NiCr. The measurements were less useful for predicting erosion resistance for both Cr₃C₂-NiCr and WC-Co, however, and for abrasion resistance when WC-Co was ground against SiC. Here the contribution of micromechanisms involving fracturing and brittle failure is greater than that indicated by the coating microhardness, which is essentially a measurement of resistance to plastic deformation under equilibrium conditions.     

Cr3C2-NiCr and WC-Ni thermal spray coatings as alternatives to hard chromium for erosion-corrosion resistance

Cr₃C₂-NiCr and WC-Ni coatings are widely used for wear applications at high and room temperature, respectively. Due to the high corrosion resistance of NiCr binder, Cr₃C₂-NiCr coatings are also used in corrosive environments. The application of WC-Ni coatings in corrosive media is not recommended due to the poor corrosion resistance of the (pure Ni) metallic matrix. It is well known that the addition of Cr to the metallic binder improves the corrosion properties. Erosion-corrosion performance of thermal spray coatings is widely influenced by ceramic phase composition, the size of ceramic particles and also the composition of the metallic binder. In the present work, two types of HVOF thermal spray coatings (Cr₃C₂-NiCr and WC-Ni) obtained with different spray conditions were studied and compared with conventional micro-cracked hard chromium coatings. Both as-sprayed and polished samples were tested under two erosion-corrosion conditions with different erosivity. Tungsten carbide coatings showed better performance under the most erosive condition, while chromium carbide coatings were superior under less erosive conditions. Some of the tungsten carbide coatings and hard chromium showed similar erosion-corrosion behaviour under more and less erosive conditions. The erosion-corrosion and electrochemical results showed that surface polishing improved the erosion-corrosion properties of the thermally sprayed coatings. The corrosion behaviour of the different coatings has been compared using Electrochemical Impedance Spectroscopy (EIS) and polarization curves. Total material loss due to erosion-corrosion was determined by weight loss measurements. An estimation of the corrosion contribution to the total weight loss was also given.     

CuCo2Be表面热喷涂制备Cr3C2-NiCr涂层的微观结构及高温摩擦磨损行为

选用等离子喷涂技术在CuCo2Be合金表面制备了Cr3C2-NiCr/NiAl复合涂层。以Al2O3陶瓷球为对偶材料运用UMT-2摩擦磨损试验机对基体和复合涂层进行高温摩擦磨损试验,并选用共聚焦激光扫描显微镜、扫描电镜、能谱仪、XRD等分析测试手段,详细研究了CuCo2Be合金表面等离子喷涂涂层物相组成、微观形貌及涂层和基体的高温滑动摩擦磨损行为,结果表明:CuCo2Be合金表面等离子喷涂获得的复合涂层致密,涂层为层状结构,物相组成呈现非晶态。通过高温摩擦磨损研究,结果表明:500℃摩擦磨损磨损过程中,涂层及CuCo2Be合金基体的磨损机制为:疲劳磨损和粘着磨损及少量氧化磨损的共同作用,从磨损的体积形貌来看涂层磨损量明显小于未喷涂之前的基体材料,等离子喷涂工艺制备的Cr3C2-NiCr/NiAl涂层质量优异,提高了材料的高温耐磨性。     

超声冲击处理提高超音速等离子喷涂Cr3C2-NiCr涂层性能

Cr₃C₂-NiCr涂层是中高温下理想的耐磨、抗氧化、耐蚀涂层,常用于高温下的燃气冲蚀磨损、磨粒磨损、微动磨损、硬表面磨损等场合.文中采用超音速等离子喷涂的方法在CuCrZr合金表面制备Cr₃C₂-NiCr涂层,并采用超声冲击的方法对涂层进行后处理.结果表明,经超声冲击处理后,涂层孔隙率由2.34%降低至1.83%;涂层的平均显微硬度由8.9 GPa提高至9.6 GPa,且硬度分布更均匀;在650℃下进行热震试验,涂层的热震寿命显著提高,热震裂纹的扩展路径也发生了变化.     

Cr_3C_2-NiCr涂层等离子喷涂工艺参数的优化

采用正交试验方法研究了等离子喷涂工艺参数对Cr_3C_2-NiCr涂层显微硬度的影响,并应用极差分析方法对试验结果进行了分析.结果表明,影响涂层性能的因素从主到次依次为喷涂距离、电流、送粉气流量和电压.Cr_3C_2-NiCr涂层最佳的等离子喷涂工艺参数是电流500 A,电压65 V,喷涂距离100 mm,送粉气流量7 L/min.采用优化后的等离子喷涂工艺制备的涂层,粒子熔化充分,涂层均匀致密,孔隙率低,界面结合良好,是高质量的热喷涂涂层.     

Preparation and wear performance of NiCr/Cr3C2-NiCr/hBN plasma sprayed composite coating

NiCr clad hexagonal BN powder (NiCr/hBN) was added to NiCr/Cr₃C₂ feedstock to improve the tribological properties of chromium carbide nichrome coating. The microstructure, flowability and apparent density of the composite powder, as well as the structure and mechanical properties of the plasma sprayed coating were characterized. The friction and wear behavior of the NiCr/Cr₃C₂-NiCr/hBN coating from ambient temperature up to 800 °C was evaluated on a ball-on-disk wear tester and compared with that of NiCr/Cr₃C₂ coating and NiCr/Cr₃C₂-NiCr/BaF₂·CaF₂ coating. The results show that NiCr cladding can reduce the decarburization of Cr₃C₂ and oxidation of hBN during the thermal spray. The main wear mechanisms of the NiCr/Cr₃C₂-NiCr/hBN composite coating are ploughing and adhesive wear. Layered hexagonal BN particle reduce the direct contact and severe adhesion between friction pairs, thus decreasing the friction coefficient. The NiCr/Cr₃C₂-NiCr/hBN composite coating shows a promising application in the high temperature environment with the request of both wear resistance and friction reduction.     

Evaluation of cyclic hot corrosion behaviour of detonation gun sprayed Cr3C2-25%NiCr coatings on nickel- and iron-based superalloys

In the present investigation, Cr₃C₂-NiCr cermet coatings were deposited on two Ni-based superalloys, namely superni 75, superni 718 and one Fe-based superalloy superfer 800H by detonation-gun thermal spray process. The cyclic hot-corrosion studies were conducted on uncoated as well as D-gun coated superalloys in the presence of mixture of 75 wt.% Na₂SO₄ + 25 wt.% K₂SO₄ film at 900 °C for 100 cycles. Thermogravimetric technique was used to establish the kinetics of hot corrosion of uncoated and coated superalloys. X-ray diffraction, FE-SEM/EDAX and X-ray mapping techniques were used to analyze the corrosion products for rendering an insight into the corrosion mechanisms. It was observed that Cr₃C₂-NiCr-coated superalloys showed better hot-corrosion resistance than the uncoated superalloys in the presence of 75 wt.% Na₂SO₄ + 25 wt.% K₂SO₄ film as a result of the formation of continuous and protective oxides of chromium, nickel and their spinel, as evident from the XRD analysis.     

Microhardness as a simple means of estimating relative wear resistance of carbide thermal spray coatings: Part 1. characterization of cemented carbide coatings

A selection of WC-Co and Cr₃C₂-25%NiCr coatings deposited by plasma spraying and high velocity oxygen fuel (HVOF) were tested. The microstructures of the coatings were characterized, and their mechanical properties were assessed using Knoop microindentation procedures. The coatings were also subjected to various wear tests. All of the coatings were at least 200 μm thick and were deposited onto stainless steel substrates. The wear tests simulated abrasion, cavitation wear, sliding wear, and particle erosion wear. In this first part of a two-part contribution, the microstructures of the coatings are characterized and a discussion on the evaluation of mechanical properties from the microindentation response is presented. The nature of microhardness testing as applied to thermal spray coatings is evaluated as a means of assessing resistance to plastic flow, elasticity, and brittleness. In Part 2, the results of the various wear simulations are reported, and the utility of microhardness as an indicator of wear resistance is examined.