Development of dense corrosion resistant coatings by an improved HVOF spraying process

For 6 years, we have developed corrosion resistant coatings to protect steel structures in the marine environment by using a thermal spray technique. This paper summarizes the major developments and results obtained. Such a coating requires primarily impermeability and secondarily homogenous and clean microstructure. In order to make denser and highly corrosion resistant coatings, we selected spray materials and improved fabrication processes. HastelloyC was a suitable material for High Velocity Oxy-Fuel (HVOF) spraying to form corrosion resistant coatings because of its high resistance against thermal oxidation as well as seawater corrosion, especially crevice and pitting corrosion. An inert gas shroud system was attached with a commercial HVOF apparatus and this attachment increased the in-flight velocity of spray particles over 750 m s^?1 and simultaneously suppressed oxidation significantly. In addition, some new methods were designed to evaluate the sprayed particle’s state and the coating properties with high accuracy and sensitivity. Thermal energy of in-flight spray particles was revealed by molten fraction of spray particles, determined by quantitative analysis of melted and unmelted particles captured in an agar gel. Through-porosity of the coatings with open porosity below 0.1% was determined by using Inductively Coupled Plasma analysis of dissolved substance from substrate through the penetrating path of the coatings. The coating of HastelloyC nickel base alloy by the HVOF spraying with the gas shroud attachment had zero through-porosity and 0.2 mass% of oxygen content. The laboratory corrosion tests showed that the on-shroud HastelloyC coating was comparable to the bulk material of HastelloyC in terms of corrosion resistance. This coating, formed on steel, demonstrated an excellent protective performance over 10 months in the marine exposure test.     

Thermal spraying of a nitrogen alloyed austenitic steel

Stainless steel coatings provide an alternative to protect steel surfaces against corrosive attack. The 316 L stainless steel coatings have been conventionally produced by different spraying processes for such applications. Because the nitrogen alloyed stainless steels exhibit not only superior mechanical properties, but also better corrosion behaviour than conventional stainless steels, in this study the coatings of a nitrogen alloyed austenitic steel were produced using a high velocity oxy-fuel (HVOF) spraying process and an atmospheric plasma spraying (APS) process. Due to much stronger deformation strengthening, the coatings deposited by the HVOF spraying process presented a much higher microhardness than the coatings deposited by the APS process. Moreover, the coatings deposited by the HVOF spraying process were also more corrosion resistant than the coatings deposited by the APS process, because the oxidation of the powder material during HVOF spraying was much lower than that during APS. Compared with the coatings of the conventional stainless steel 316 L, the nitrogen alloyed steel coating deposited by the HVOF spraying process showed a much better corrosion performance.     

喷涂距离对Fe基非晶涂层孔隙影响的研究

热喷涂涂层中孔隙的存在会降低涂层的耐蚀性,减少涂层寿命,而热喷涂工艺参数很大程度上影响涂层的孔隙率。本文采用计算机数值模拟和设计验证实验的分析方法,重点研究了JP-8000超音速火焰喷涂系统(HVOF)制备Fe基非晶涂层工艺参数中喷涂距离与涂层孔隙的关联性。利用商用计算软件Fluent计算平台,研究加入粉末粒子前,喷枪内火焰温度和速度的变化规律,以及加入非晶粉末后,不同喷涂距离条件下颗粒飞行过程的温度和速度的变化规律。仿真结果表明,喷涂距离为360~380 mm时,非晶粉末颗粒在撞击基板时处于半融化状态,颗粒在基板上具有良好的流动性,可获得孔隙率较低的涂层。验证实验结果与仿真结果一致。X射线衍射结果表明,粉末、不同喷涂距离所制备的涂层以及同成分的非晶条带均为完全非晶态结构。SEM和孔隙率统计结果表明,喷涂距离为370 mm时,涂层截面的孔隙较少,且孔隙率最低,为0.57%,验证了计算模拟优化的最佳喷涂距离范围。     

Microstructural characterisation of high velocity oxyfuel thermally sprayed Stellite 6

Abstract

High velocity oxyfuel (HVOF) thermal spraying with an oxygen-propylene combustion flame was used to deposit coatings of a Co–Cr–W–C alloy (similar in composition to Stellite 6) from gas atomised feedstock powder. The microstructural characteristics of the deposits were investigated using the combined techniques of X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). In particular, the tripod polishing technique was used to prepare large areas of electron transparent membrane for TEM analysis; these areas were typically of the order of several hundred square micrometres. Accordingly, SEM and TEM analysis could be directly correlated, providing a clear understanding of the overall nature of the coatings. The coatings exhibited characteristic splatlike, layered morphologies due to the deposition and resolidification ofmolten or semimolten powder particles. The as sprayed microstructure consisted of a face centred cubic Co rich metallic matrix with a small fraction of CoCr₂O₄ spinel oxide. The latter formed either as intersplat lamellae or intrasplat globules. Under the HVOF spray conditions employed, a high proportion of the feedstock powder appeared to have been fully melted prior to impact on the substrate, with partially or unmelted powder accounting for < 20% of the microstructure. Formation of the M₇C₃ phase, normally present in Stellite 6, appeared to have been suppressed by the high cooling rate during spray deposition.     

Response of nanocrystalline cerium-based conversion coatings on Al 2024-T3 to chloride environments

Nanocrystalline cerium-based conversion coatings were found to be effective at retarding corrosion of Al 2024-T3 in sodium chloride environments. Cerium oxide coatings were deposited by spraying an aqueous solution made with cerium chloride onto cleaned panels. After deposition, the coatings were treated in a phosphate solution, which produced dense, nanocrystalline coatings composed of hydrated cerium phosphate. Visually, the coatings appeared to inhibit corrosion and the formation of salt tails for at least 14 days in ASTM B117 neutral salt spray corrosion testing. Cross-sectional imaging using transmission electron microscopy and compositional depth profiling using Auger spectroscopic analysis after salt spray exposure revealed that an aluminum oxide layer was present on the surface of the cerium phosphate coating.     

Surface Refinement of Metal Foams

Aluminium foams produced via the PM‐process are characterized by a moderate specific strength, a high surface roughness, and a poor wear behavior; to increase their mechanical properties and to improve the surface finish, wear and corrosion resistance; thermally sprayed coatings can be applied. The quality of the coating depends on the coating material, the chosen process, the preparation of the surface and spraying parameters. Aluminium alloys and iron based alloys for abrasive applications were deposited via electric arc spraying, ceramic coatings against wear were deposited by means of plasma spraying. Hard metallic coatings for severe abrasive applications were applied by high‐velocity‐oxyfuel spraying (HVOF). The results proved the suitability of this technique to significantly enhance the mechanical properties and the surface finish of metal foams. The specific strength and stiffness of the new composite materials outperform pure metal foams. The corrosion behavior was tested performing a salt spray test.     

Herstellung HVOF gespritzter,feinststrukturierter Cermetschichten unter Verwendung von feinen WC‐12Co Pulvern

Manufacturing of HVOF sprayed, finest structured cermet coatings using fine WC‐12Co powders The continuous increase in productivity and performance of modern sheet metal forming processes combined with the employment of novel, high strength materials cause high wear on tool systems. Coating technologies like thermal spraying provide a high potential to functionalize and to protect the surface of forming tools. However, it has to be ensured that the high shape and dimensional accuracy of the tool contour is preserved after the application of a wear protective coating. This aim cannot be achieved using currently applied, thermally sprayed coating systems with conventional, coarse grained microstructure. To solve this problem, novel finest structured coatings have been developed in this study by thermal spraying of fine WC‐12Co powders using the HVOF technique. For this purpose the influence of varying HVOF combustion gas compositions on the spray process as well as on the corresponding coating properties has been investigated. Next to a high surface quality the focus was placed on achieving coatings with high hardness and corresponding high wear resistance, low porosity as well as a good adhesive strength on the substrate material.     

A study on coatability of marble dust on metal substrates

Marble dust is a hazardous construction/industrial waste generated during the extraction, cutting and polishing of marble-producing rocks. The present work explores the potential of marble dust to be used as a coating material on metal substrates. For this, the high-velocity oxy-fuel (HVOF) spraying route is adopted to deposit marble dust coatings on four different metallic substrates: mild steel, inconel, aluminum, and copper. Liquefied petroleum gas is used as the fuel and nitrogen as the carrier gas while the coating deposition is performed by varying the spray distance over a range from 50 mm to 250 mm. The coating microstructure is studied using a scanning electron microscope (SEM) and the developed phases are identified using an x-ray diffractometer. The developed coatings are characterized in terms of deposition efficiency, coating thickness and adhesion strength. It is found that the coatings exhibit fairly good interfacial adhesion and thickness values that varied quite significantly with the spray distance. Maximum deposition efficiency of about 68 % is obtained for the copper substrate when the deposition is performed at a spray distance of 100 mm. This experimental investigation thus shows that despite being a waste, marble dust is eminently coatable on several metallic substrates.     

High Velocity Oxy Fuel Spraying of Cold Work Tool Steels‐ A Novel Approach to Thick Coatings for Wear Protection Applications

Within this work, HVOF sprayed coatings based on X220CrVMo13‐4 cold work steel were applied to a S235JR construction steel substrate. The investigations focus on the influence of particle size and spray parameters on the coating microstructure, analyzed by means of optical microscope (OM) and scanning electron microscopy (SEM). Additional XRD measurements and micro hardness plots across the interface between substrate material and coating were carried out. Furthermore, the influence of particle size on the detected phases and coating porosity was studied. The results were compared with an X220CrMoV13‐4 reference sample produced by HIP.     

Failure analysis of the outside coating on the process roller

A failure case of the outside coating on the process roller is presented in this study. The coating consists of WC-Co, which is deposited on 45 steel by High Velocity Oxygen Fuel (HVOF) spraying. The spalling of coatings has been found in the middle of the roller. Rust was also observed on the coatings of the roller. The failure analysis of the coating was performed in terms of composition analysis, and microstructure observation etc. In addition, the effects of sandblasting post-treatments were compared on the residual sand on the interface between the coating and substrate. And the effect of substrate material is investigated on the corrosion of coatings. It was concluded that the sandblasting particles remained on the substrate surface have effects on the failure of the coating. The peeling-off coating on the roller is also related with the formation of iron oxides. Less sand can be remained on the substrate surface when air purging and brushing is used after the sand-blasting compared with only air purging or non-treatment is applied. The stainless steel shows excellent corrosion resistance than the low carbon steel when they are used as substrate for WC-Co coatings during the wet/dry cyclic corrosion tests.     

On the role of particle state and deposition procedure on mechanical,tribological and dielectric response of high velocity oxy-fuel sprayed alumina coatings

It is well known that the high velocity oxy-fuel based thermal spray process impart high density and reduced porosity in coatings compared to those produced by other ambient thermal spray processes. The benefits of HVOF have largely remained in the domain of metals and cermets and limited investigations have been carried out in ceramic coatings. The ability to produce high density ceramic coatings (e.g. alumina) offers potential in high performance applications in the field of wear, corrosion resistance and dielectric coatings. However, due to extreme operational limits of the HVOF process, the fundamentals of process–structure–property relationships are not fully understood.In this paper, we report an integrated approach to establish processing–microstructure–property correlations in order to optimize coatings for such applications. This approach involves diagnostic studies, microstructure development and its resultant influence on properties of high velocity oxy-fuel (HVOF) sprayed alumina coatings. The diagnostic studies were aimed to investigate the effects of fuel gas/oxygen ratio and amount of total gas flow on the particle temperature and velocity. Furthermore, splats and coatings were deposited to investigate the relationship between diagnostic data, melting behavior and droplet substrate interactions. Such a comprehensive study, coupled with property measurements of the coatings, demonstrates critical operational variables among deposition procedure, coating microstructure and the deposit properties.     

超音速火焰喷涂制备纳米和微米结构WC-η涂层的耐熔锌腐蚀性能

以钨氧化物、钴氧化物和炭黑为原料, 通过原位还原碳化反应制备纳米WC-η(η为Co₃W₃C、Co₆W₆C等缺碳相)复合粉, 粉末平均粒径为155 nm。该复合粉经团聚造粒制备得到具有高致密性和良好流动性的热喷涂粉末。以此纳米结构和商业化的微米结构低碳WC-12Co粉末作为喂料, 通过超音速火焰喷涂制备硬质合金涂层。结果表明, 纳米结构涂层中生成了一定量等轴状的W₂C相, 裂纹主要沿晶界或相界面扩展, 而微米结构涂层中除W₂C外还含有较多的W相, 主要包裹在WC颗粒表面, 穿晶断裂比例较高, 裂纹扩展路径较平滑。由于纳米结构涂层组织致密、晶粒细小、界面积大, 因此比微米结构涂层具有更高的硬度和断裂韧性。两种涂层在熔融锌液中浸泡200 h后, 微米结构涂层中产生了较多的横向和纵向裂纹, 导致材料的大面积剥落和基材腐蚀; 纳米结构涂层中没有发生锌的浸蚀, 在局部产生了少量纵向裂纹, 裂纹间隙被钨钴氧化物所填充, 反而抑制了熔锌对涂层的腐蚀, 因此纳米结构涂层表现出更高的耐熔锌腐蚀性能。     

Study on corrosion resistance of aluminium coating deposited on magnesium-zinc-yttrium-calcium alloy by cold spray

Pure aluminium coatings were prepared on magnesium-zinc-yttrium-calcium alloy substrate via cold spraying technology with different scanning speeds and working gas temperature. The correlation between the corrosion resistance of the coatings and the different spraying process was studied. While the working gas temperature is 600 °C and the scanning speed is 1 mm/s, aluminium coating has less porosity and the coating was well combined with the substrate. Higher temperature of working gas increases the plastic deformation of particles, which lead to a dense aluminium coating. The relationship of corrosion resistance on working gas temperature and scanning speed of aluminium coatings has also been investigated by immersion corrosion test and electrochemical impedance spectroscopic techniques. The results show that the cold sprayed aluminium coatings revealed a lower porosity and higher corrosion resistance with the decreasing scanning speed and the increasing temperature of working gas. The porosity and corrosion current densities were 0.938 vol.% and 2.427 ⋅ 10⁻⁶ A/cm². The experimental results show that the aluminium coating prepared by cold spraying has a good protective effect on magnesium alloy.     

Characterization of Thermal Spray Coatings

The ability to characterize fully the microstructure of a coating is paramount for understanding the in-service properties and eventual optimization of the coating. This article discusses sample preparation and subsequent analytical techniques (LOM, SEM, XRD, WDS, and QIA) for several cermet thermal spray coatings and provides a detailed analysis of as-sprayed microstructures in addition to processing trends for several FeCrAIY-carbide coatings. It was found that the splats produced in these high velocity oxy-fuel (HVOF) coatings tended to exhibit a predominantly dendritic structure most likely retained from the gas atomization process that produced the original powder. Chemical analysis showed that the carbides tend to breakdown during spraying producing a complex mixture of oxides and various carbides. Finally, image analysis revealed that as the carbides in the pre-sprayed powder were increased, more carbides and oxides with less FeCrAIY and thinner coatings were found. These techniques allow the thorough characterization of thermal spray cermet coatings, which in turn should further the understanding of the thermal spray processes and help provide superior coatings in the future.     

40Cr钢表面涂敷层的磨损和腐蚀磨损研究

用掺有 10 %(w)CeO2 粉末的及未掺的KF 2 0 1铁基高强度耐磨合金粉末 ,对淬火态 40Cr钢材表面进行喷涂、喷熔和激光涂敷等表面处理 ,考察了用这 3种工艺制作的 6种涂层的显微组织、硬度分布、无润滑磨损和腐蚀磨损。结果表明 ,涂层的磨损抗力和腐蚀磨损抗力都比 40Cr钢基底的大为提高。激光涂敷层的磨损抗力达到淬火态 40Cr钢基底的 5倍以上 ,在 5 %盐水 +石英砂内进行腐蚀磨损试验 ,激光涂敷层的腐蚀磨损抗力达到 40Cr钢基底的 2倍以上。在KF 2 0 1粉末中掺入CeO2 ,Ce能使涂层组织细化 ,涂层磨损抗力与腐蚀磨损抗力得到进一步的提高。     

HVOF金属陶瓷涂层的冲蚀失效行为研究现状

超音速火焰喷涂具有粒子飞行速度高、涂层质量好、沉积速度快、材料选择性好以及与基体的结合强度高等优点。冲蚀是水轮机过流部件、轮船螺旋浆、泥浆泵及钻杆等的主要失效形式之一。HVOF技术制备的金属陶瓷涂层因其能显著提高金属零部件的耐冲蚀性能而受到广泛应用。本文对国内外HVOF喷涂金属陶瓷涂层的冲蚀失效行为进行综述,系统归纳了冲蚀颗粒粒径、冲蚀速度、攻角等外部因素及涂层的结合强度、孔隙率、涂层颗粒尺寸、碳化物颗粒的大小等内部因素对HVOF喷涂金属陶瓷涂层冲蚀失效行为的影响机制。并指出综合评价外部服役条件和自身性能参数对涂层冲蚀失效行为的作用机理是本领域今后研究的重点方向之一。     

热输入量对HVOF铁基非晶涂层制备及性能的影响

目的以FeCoCrMoCBYS非晶粉末为喷涂材料,采用几组不同的热输入量,使用超音速火焰喷涂(HVOF)制备成铁基非晶涂层,通过对涂层性能进行分析,研究热输入量对涂层的影响。方法通过调整煤油流量和氧气流量两个参数来控制喷涂时的热输入量。分别利用扫描电镜(SEM)、X射线衍射分析仪(XRD)、差示扫描量热仪(DSC)、维氏显微硬度计等设备,研究热输入量对涂层显微组织和显微硬度的影响,并通过电化学工作站测试涂层在1 mol/L FeCl_2溶液中的极化曲线进而分析其耐蚀性能。结果不同热输入量下制备的涂层均具有较高的非晶含量。保持其他参数不变,随着热输入量的增加,涂层变得更加致密,孔隙率最小达到1.56%。涂层显微硬度先增大后减小,涂层横截面中部位置硬度大于表面和接近基体位置。结论当热输入量达到6.4×10~5 J时,非晶含量高达96.7%,自腐蚀电流密度低,耐腐蚀性最好。     

Influence of the thermal-spray procedure on the properties of a nickel-chromium coating

A modified NiCr coating was thermal-spray projected using different procedures (flame, plasma, HVOF and HFPD) onto stainless steel specimens. This type of coating is normally used as protection against heat, corrosion and erosion actions encountered in superheater and reheater tubes in power plant boilers. The microstructures, porosities, oxide contents and microhardnesses of the coatings were determined. Thermal fatigue tests under an atmosphere similar to power plant service conditions were conducted in an experimental combustion chamber and, finally, the adhesion between the substrate and the coating layer was evaluated by means of tensile tests. The results obtained are discussed, with special attention being paid to the specific characteristics of the different spraying procedures.     

Untersuchung der Einflüsse von Substratrauheit und Spritzpartikelgröße auf die Haftung thermisch gespritzter Schichten

About the influence of substrate roughness and spray particle size on the adhesion of thermal spray coatings The influence of substrate roughness and spray particle size on the adhesion of thermal spray coatings was researched systematically. In addition to established spray materials (Cr₂O₃, WCCo, NiCr) and spraying processes (atmospheric plasma spraying (APS), high velocity flame spraying (HVOF)) different substrate materials (steel, stainless steel, aluminum) were included in the research work as well.     

不同喷涂工艺下NiCoCrAlYTa涂层的显微结构和性能

为探索不同喷涂工艺对NiCoCrAlYTa涂层的显微结构和性能的影响规律,确定最优工艺,采用大气等离子、低压等离子、常规超音速火焰和低温超音速火焰4种工艺在镍基单晶高温合金表面制备了NiCoCrAlYTa涂层。采用X射线衍射(XRD)、扫描电镜(SEM)和显微硬度计等分析手段对喷涂态涂层的相组成、显微结构和显微硬度等进行了表征。结果表明,不同喷涂工艺下涂层的相组成均为γ′-Ni_3Al、β-NiAl和γ-Ni固溶体。低压等离子和超音速火焰喷涂的涂层致密且孔隙率低,其中超音速火焰喷涂的涂层孔隙率低于1%。低压等离子和低温超音速火焰喷涂的涂层氧含量很低,控制在0.3%~0.6%的范围。综合来说,低温超音速火焰喷涂工艺制备的涂层结构致密,孔隙率和氧含量很低。该工艺是沉积NiCoCrAlYTa涂层的首选。