Erosion-corrosion properties of different WC-Co-Cr coatings deposited by the HVOF process—influence of metallic matrix composition and spray powder size distribution

WC-Co-Cr coatings were sprayed by the High Velocity Oxygen Fuel (HVOF) process and characterised by scanning electron microscopy (SEM), X-ray diffraction (XRD) and erosion corrosion tests. Powders with different relative amounts of Co and Cr in the matrix and different powder grain size distributions were examined. At constant spray conditions the powders gave coatings of different quality as regards erosion-corrosion performance. At low erosive conditions the erosion-corrosion resistance increased when increasing Cr-content from 5 to 8.5 wt.%. However, when the erosivity was increased by increasing test velocity, an increase of Cr content from 5 to 8.5 wt.% showed no improvement in coating quality. Powder grain size distribution was found to be an important parameter, strongly affecting the coating quality. Powders with narrow grain size distributions gave coatings of higher quality than powders with wider grain size distributions. A reduction of the heat input during spraying reduced the degree of WC decomposition and improved the coating properties when the spray powder contained a large fraction of small grains.     

Mechanical properties of cold-sprayed and thermally sprayed copper coatings

The present investigation compares the mechanical properties of cold-sprayed and thermally sprayed copper coatings. The mechanical properties of the Cu-coatings are determined by in plane tensile test using micro-flat tensile specimen technique. A deeper view into the type of obtained defects, their stability and their influence on coating performance, is supplied by subsequent failure analyses and the comparison to annealed copper coatings. The results demonstrate that cold-sprayed coatings, processed with helium as propellant gas, show similar performance as highly deformed bulk copper sheets and respective changes in properties after annealing. In the as-sprayed condition, cold-sprayed coatings processed with nitrogen and thermally sprayed coatings show rather brittle behavior. Whereas subsequent annealing can improve the properties of the cold-sprayed coating, processed with nitrogen, such heat treatments have only minor influence on the tensile properties of thermally sprayed copper coatings. The investigation of failure modes for the as-sprayed states and after different heat treatments provided further information concerning particle–particle bonding and the effect of oxides on mechanical properties.     

Microstructure evolution and thermal stability of an Fe-based amorphous alloy powder and thermally sprayed coatings

High velocity oxy-fuel (HVOF) thermal spraying has been used to produce coatings of an Fe–18.9%Cr–16.1%B–4.0%C–2.8%Si–2.4%Mo–1.9%Mn–1.7%W (in at.%) alloy from a commercially available powder (Nanosteel SHS7170). X-ray diffraction (XRD), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) were employed to investigate the powder, as-sprayed coatings and annealed coatings which had been heated to temperatures in the range of 550–925 °C for times ranging from 60 to 3900 min. Microhardness changes of the coatings were also measured as a function of annealing time and temperature. The powder was found to comprise amorphous and crystalline particles; the former had a maximum diameter of around 22 μm. The coating was composed of splat like regions, arising from rapid solidification of fully molten powder, and near-spherical regions from partially melted powder which had a largely retained its microstructure. The amorphous fraction of the coating was around 50% compared with 18% for the powder. The enthalpies and activation energies for crystallization of the amorphous phase were determined. Crystallization occurred in a two stage process leading to the formation of α-Fe (bcc), Fe_1.1Cr_0.9B_0.9 and M₂₃C₆ phases. DSC measurements showed that the first stage occurred at 650 °C. Annealing the coating gave a hardening response which depended on temperature and time. The as-sprayed coating had a hardness of 9.2 GPa and peak hardnesses of 12.5 and 11.8 GPa were obtained at 650 and 750 °C, respectively. With longer annealing times hardness decreased rapidly from the peak.     

Electrochemical behavior of thermally sprayed stainless steel coatings in 3.4% NaCl solution

Four types of stainless steel coatings prepared by a high velocity oxy-fuel spraying system (HVOF) were studied. Differences among coated steels were related to the spraying parameters, which influenced the behavior of the samples against the corrosion. The electrochemical behavior of the stainless steel coatings was strongly influenced by porosity, the presence of micro- and macro-cracks, and also of un-melted particles. Once the electrolyte reached the steel substrate via these defects, the galvanic pair formed between the coating and substrate-accelerated corrosion, leading to the depletion of the coating.     

In-situ observation of crack propagation in thermally sprayed coatings

In-situ observation of thermally sprayed coating fractures may complement classical fractographic analysis to study specific failure mechanisms. In this paper, fracture of free-standing plasma sprayed ceramic (alumina) and metallic (stainless steel 316L) coatings during 3-point bending (3PB) was observed in-situ using a scanning electron microscope (SEM) in order to identify the most important failure mechanisms. Observations were supplemented by fractographic analysis of fractured specimens.     

Methods and application of residual stress analysis on thermally sprayed coatings and layer composites

Coating and layer composite manufacturing most commonly involves high temperature gradients and intensive heat transfer between the different composite materials. This can be noticed not only for thermal spraying, but also for other coating techniques. The combination of temperature gradients and materials with different thermophysical properties leads to the formation of thermal stresses in the composite, which are superimposed by stress generating effects during coating solidification, phase transformation or recrystallization. The final state of residual stresses affects the structural and functional properties of the coating as well as the component reliability during operation. Therefore, residual stress analysis is an important tool for the optimization of coatings and layer composite manufacturing processes in order to ensure stability of the processes, adhesion and compatibility of the coating, and finally, the reliability of the components in various technical systems.The most common residual stress measurement techniques are described and compared, with the focus on the incremental hole drilling and milling method. The advantages and disadvantages of the methods are discussed with respect to their application on industrial machine parts. The typical application fields for the different methods are given with respect to the specific measurement principles. The incremental hole drilling method is presented in more detail with application examples that illustrate the suitability of this method for the optimization of thermal spraying processes in industrial layer composite manufacturing by managing the heat and mass transfer in a most appropriate way.     

Microstructure and properties of thermally sprayed silicon nitride-based coatings

The preparation of thermally sprayed, dense, Si₃N₄-based coatings can be accomplished using composite spray powders with Si₃N₄ embedded in a complex oxide binder matrix. Powders with excellent processability were developed and produced by agglomeration (spray drying) and sintering. Optimization of the heat transfer into the powder particles was found to be the most decisive factor necessary for the production of dense and well-adhering coatings. In the present work, different thermal spray processes such as detonation gun spraying (DGS), atmospheric plasma spraying (APS) with axial powder injection, and high-velocity oxyfuel spraying (HVOF) were used. The coatings were characterized using optical and scanning electron microscopy (SEM), x-ray diffraction (XRD), and microhardness testing. The wear resistance was tested using a rubber wheel abrasion wear test (ASTM G65). In addition, thermoshock and corrosion resistances were determined. The microstructure and the performance of the best coatings were found to be sufficient, suggesting the technical applicability of this new type of coating.     

Laser-assisted spraying and laser treatment of thermally sprayed coatings

In the present study, surface engineering research related to thermally sprayed wear and corrosion resistant coatings modified by in-situ and post-treatment by novel high power lasers (Nd:YAG and diode lasers) has been carried out. The main aim of the study was to create experimental based information and knowledge on simultaneous remelting of thermally sprayed (plasma, HVOF, flame) single layers for production of metallurgically bonded, dense corrosion and wear resistant coatings on surfaces of steels. The main focus of research was to estimate the needed processing parameters, which enable simultaneous laser-assisted thermal spraying. The microstructures and hardness-profiles for the coatings prepared by laser-assisted thermal spraying are also introduced.     

Influence of silane on corrosion resistance of magnesium alloy AZ31 with thermally sprayed aluminum coatings

Aluminum coatings on Mg alloy AZ31 were fabricated using the thermal spraying technique, and then sealed with silane.The surface morphology and chemical groups were discerned using scanning electron microscopy and examined using Fourier transformation infrared spectroscopy, respectively.The salt fog tests and the potentiodynamic electrochemical technique were applied to evaluate the influence of silane on corrosion of the AZ31 alloy with aluminum coatings.The results showed that the corrosion resistance of ...     

Microstructure and adhesion of 100Cr6 steel coatings thermally sprayed on a 35CrMo4 steel substrate

Thermally sprayed of 100Cr6 steel coatings are widely used to combat degradation of components and structures due to mechanical wear. In this paper, the microstructure and adhesion energy of 100Cr6 steel coatings thermally sprayed on a 35CrMo4 steel substrate are investigated. The microstructure characteristics of the deposits are studied using the combined techniques of X-ray diffraction (XRD), optical microscopy, scanning electron microscopy (SEM) including energy-dispersive spectroscopy (EDS). The practical work of adhesion of flame-sprayed 100Cr6 on steel substrate is determined using a four-point delamination bending test. The influence of a molybdenum bond coat on the adhesion is also studied. Microstructure suggests that the coating is mainly constructed by splats of γ-phase (fcc) and FeO. Phase analysis also confirms that during spraying process, a stable α-phase (bcc) was transformed into a new γ-phase (fcc). The highest values of the fracture energy are obtained for the 35CrMo4 substrate/100Cr6 steel deposit type samples. On the contrary, when a molybdenum bond coat is introduced (composite system 35CrMo4 substrate/Mo bond coat/100Cr6 steel deposit), the fracture energy decreases in a ratio of approximately three. So, the presence of a Mo bond coat as a barrier between the coating and the substrate has a negative role on the adhesion.     

Corrosion and tribocorrosion behaviour of thermally sprayed ceramic coatings on steel

This research aims at investigating the corrosion and tribocorrosion behaviour of thermally sprayed ceramic coatings deposited on steel specimens and exposed to a 3.5% NaCl solution. The coatings have been prepared by plasma spraying Cr₂O₃ and Al₂O₃/13% TiO₂ powders on a Ni/20% Cr bond coating. Combined wear-corrosion conditions have been achieved by sliding an alumina antagonist on the lateral surface of coated steel cylinders, during their exposure to the aggressive solution.Polarization resistance values monitored during 3 days exposures and polarization curves recorded at the end of the immersion period show that both coatings only partially protect steel substrate from corrosion. Sliding conditions (under 2 N load and 20 rpm or 10 N and 100 rpm) induce a limited increase of the substrate corrosion rates, likely as a consequence of an increase in the defect population of the ceramic coatings.On Cr₂O₃-coated specimens, tribocorrosion is more severe at 10 N and 100 rpm, while on Al₂O₃/13% TiO₂-coated specimens, a stronger corrosion attack is achieved at 2 N and 20 rpm. Profilometer analysis and wear track observations by optical and scanning electron microscopes evidence that on both coatings abrasion of the surface asperities produce both a surface polishing effect and, at high loads, the formation of a tribofilm, more continuous on Al₂O₃/13% TiO₂. On this coating the tribofilm reduces the amount of surface defects and limits the corrosion attack to a certain extent.     

Microstructure and properties of flame sprayed tungsten carbide coatings

This article reports on feasibility experiments carried out with oxy-acetylene spray system with various oxygen to fuel ratios using two different tungsten carbide powders and powder feeding methods, to evaluate the newly developed fused WC, synthesised by transferred arc thermal plasma method. Transferred arc thermal plasma method is more economical and less energy intensive than the conventional arc method and results in a fused carbide powder with higher hardness. The microstructure and phase composition of powders and coatings were analysed by optical and scanning electron microscopy, energy dispersive spectroscopy and X-ray diffraction. Carbon content of the powders and coatings were determined to study the decarburisation of the material during spraying process. Coatings were also characterised by their hardness and abrasive wear. The effects of metallurgical transformation and phase content are related to wear performance. The results demonstrate that the powders exhibit various degree of phase transformation during the spray process depending on the type of powder, powder feeding and spray parameters. The carbon loss during the spray process in excess of 45% resulted in reduced hardness and wear resistance of the coatings. Coatings with high amount of WC and W₂C along with FeW₃C showed higher wear resistance. Thus, coatings of high wear resistance can be produced using fused tungsten carbide powder with WC and W₂C phases, which can be economically synthesised by thermal plasma transferred arc method.     

Characterization and residual stresses of WC-Co thermally sprayed coatings

The present investigation has been conducted in order to determine the residual stresses of an as-ground WC-12Co coating of two different thicknesses, by means of two different methods. Firstly, X-ray diffraction techniques, which allowed the determination of the surface residual stresses of the coating by means of the method called “sin²ψ” method. Secondly, an incremental hole drilling technique together with the integral method, which allowed the analysis of the non-uniform through-thickness residual stresses present in the coatings. It has been determined that the surface residual stresses are of a compressive nature, which could be due to the grinding that was applied to the coatings in order to achieve the desired thicknesses. On the contrary, the results of the incremental hole drilling tests indicated that the through-thickness residual stress distributions are not uniform and are characterized by the presence of tensile peak stresses, at depths in the range of ~ 50-125 μm. Such stresses were observed to decrease towards the coating-substrate interface where the compressive component of the stress state becomes greater than the tensile component. It has been found that the mean residual von Mises stress is higher in the thinner coating than in the thicker one, of approximately 180 and 107 MPa, respectively.     

Influence of HVOF parameters on the corrosion and wear resistance of WC-Co coatings sprayed on AA7050 T7

Thermal spray WC-based coatings are widely used in the aircraft industry mainly for their resistance to wear, reworking and rebuilding operations and repair of worn components on landing gear, hydraulic cylinders, actuators, propeller hub assemblies, gas turbine engines, and so on. The aircraft industry is also trying to use thermal spray technology to replace electroplating coatings such as hard chromium. In the present work, WC-Co coatings were built up on an AA 7050 aluminum alloy using high velocity oxygen fuel (HVOF) technology and a liquid nitrogen cooling prototype system. The influence of the spray parameters (standard conditions, W19S, increasing the oxygen flux, W19H, and also increasing the carrier gas flux, W19F) on corrosion, friction, and abrasive wear resistance were also studied. The coatings were characterized using optical (OM) and scanning electron (SEM) microscopy, and X-ray diffraction (XRD). The friction and abrasive wear resistance of the coatings were studied using Rubber Wheel and Ball on Disk tests. The electrochemical studies were conducted using open-circuit potential (E_OC) measurements and electrochemical impedance spectroscopy (EIS). Differences among coated samples were mainly related to the variation of the thermal spray parameters used during the spray process. No significant differences were observed in the wear resistance for the coatings studied, and all of them showed a wear rate around 10 times lower than that of the aluminum alloy. The results of mass loss and wear rate were interpreted considering different mechanisms. Comparing the different spray parameters, the oxygen flux (higher flame temperature) produced the sample which showed the highest corrosion resistance in aerated and unstirred 3.5% NaCl solution. Aluminum ions were detected on the surface almost immediately after the immersion of samples W19S and W19F in chloride solution, showing that the electrolyte reached the substrate and galvanic corrosion probably occurred. For sample W19H, aluminum ions were not detected even after 120 min of immersion in NaCl solution.     

铝镁合金等离子喷涂复相陶瓷涂层微观组织

为解决铝镁合金表面耐磨性差的问题,利用机械球磨法和PVA造粒技术制备复合陶瓷粉末,采用等离子喷涂技术在XGFH-3铝镁合金表面制备了反应复相陶瓷涂层,利用扫描电镜(SEM)、X射线衍射仪(XRD)分析了喷涂复合粉末和复相陶瓷涂层的形貌及组成.结果表明,复合粉末随着球磨时间的延长明显趋于扁平化和均匀化,并且生成了Al₃Ti,Ni₄Ti₃等新相.而在喷涂过程中Al₃Ti和Ni₄Ti₃中间相又会消失,涂层中出现了MgAl₂O₄和Ti₅Si₃等新相,基体和涂层之间有元素扩散,这使得涂层有良好的结合强度.     

Towards engineering isotropic behaviour of mechanical properties in thermally sprayed ceramic coatings

It is widely recognized by the scientific community that thermal spray coatings exhibit anisotropic behaviour of mechanical properties, e.g., the elastic modulus values of the coating in-plane (i.e., parallel to the substrate surface) or through-thickness (i.e., perpendicular to the substrate surface) will tend to be significantly different due to their anisotropic microstructures. This work shows that thermally sprayed ceramic coatings may exhibit isotropic mechanical behaviour similar to that of bulk materials even when exhibiting the typical anisotropic coating microstructure. Elastic modulus values on the in-plane and through-thickness directions were measured via Knoop indention and laser-ultrasonic techniques on a coating produced via flame spray (FS) using a nanostructured titania (TiO₂) powder. No significant differences were found between the coating directions. In addition, four major cracks with similar lengths were observed originating near or at the corners of Vickers indentation impressions on the coating cross-section (i.e., a typical characteristic of bulk ceramics), instead of two major cracks propagating parallel to the substrate surface, which is normally the case for these types of coatings. It was observed by scanning electron microscopy (SEM) that coatings tended to exhibit an isotropic behaviour when the average length of microcracks within the coating structure oriented perpendicular to the substrate surface was about twice that of the microcracks aligned parallel to the substrate surface. Modelling, based on scalar crack densities of horizontal and vertical cracks, was also used to estimate when thermal spray coatings tend to exhibit isotropic behaviour.     

Mechanical properties of suspension plasma sprayed hydroxyapatite coatings submitted to simulated body fluid

Home synthesized (HA) powder was formulated with water and alcohol to obtain a suspension used to plasma spray coatings onto titanium substrate. The deposition process was optimized and the resulting coatings were soaked in simulated body fluid (SBF) for the periods of 3, 7, 14, 28, and 60 days at controlled temperature of 37 °C. The microstructural research enabled to find in the as-sprayed deposits two characteristic zones: (i) dense zone corresponding to the lamellas, observed usually in thermally sprayed coatings; (ii) sintered zone containing fine hydroxyapatite grains corresponding to the fine solids from initial suspension. The sintered zone disappears after soaking in SBF and the pores get filled by the reprecipitated calcium phosphates. The adhesion of the soaked coatings to the substrate was characterized by the critical load in the scratch test and was about 10 to 12 N. The Young modules of the coatings were determined with help of depth-sensing indentation test by the use of the technique developed by Oliver and Pharr. The modules were not depending on the time of soaking and their mean values were 15.6 and 28.4 GPa, depending on the coating operational parameters. The scratch test enables to determine the hardness of the coatings, which remained fairly constant during the time of soaking in the range of 3 to 5 GPa. This hardness was compared to that the Martens microhardness which doubled with time of soaking to reach up to 1 GPa.     

晶须增韧等离子喷涂陶瓷涂层的可控制备与力学性能研究

针对新一代航空发动机和重型燃气轮机对长寿命、高韧性热障涂层的迫切需求,本文通过喷雾造粒法制备了长径比为10的ZrO2晶须复合YSZ喷涂粉末,采用SAPS技术制备了YSZ/ZrO2晶须増韧陶瓷复合涂层,对复合涂层的工艺参数进行优化,研究了熔融指数对陶瓷复合涂层微观结构的影响规律;通过狭缝法收集单个摊片的实验,阐明了ZrO2晶须增韧YSZ陶瓷涂层的形成机理,建立了晶须増韧陶瓷涂层的微观结构与热力学性能的内在关系。基于晶须弥散分布于复合涂层未熔颗粒区的特征,相比纳米结构YSZ涂层,YSZ/ZrO2晶须増韧陶瓷复合涂层的断裂韧性与热循环寿命均提高一倍。     

Heat treatment effects on the tribological performance of HVOF sprayed Co-Mo-Cr-Si coatings

The tribological behavior of high-velocity oxyfuel sprayed Co-28%Mo-17%Cr-3%Si coatings, both assprayed and after heat treatments at 200, 400, and 600 °C for 1 h, has been studied. The as-sprayed coating contains oxide stringers and is mostly amorphous. It has low hardness (∼6.7 GPa) and toughness and undergoes adhesive wear against 100Cr6 steel. The friction coefficient increases up to ∼0.9, so the flash temperature reaches a critical oxidation value; then, friction decreases and increases again. This phenomenon occurs periodically. Much adhesive wear occurs in the first stage. Abrasive wear prevails against alumina pin: the coating wear rate is lower because it possesses good plasticity. Thermal effects still occur. The 600 °C treatment causes formation of submicrometric crystals. Hardness increases (∼8.8 GPa), adhesive wear is prevented, the friction coefficient has no peaks. Against the alumina pin, wear rates remain similar to the as-sprayed case. Nevertheless, the friction coefficient has no peaks and its final value is lowered (from 0.84 to 0.75). 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-corrosion behavior of nano-particle-reinforced Ni matrix composite alloying layer by duplex surface treatment in aqueous slurry environment

The present study concerns a duplex surface treatment of AISI 316L stainless steel to enhance the erosion-corrosion resistance. The duplex surface treatment consisted of Ni/nano-SiC and Ni/nano-SiO₂ predeposited by brush plating and a subsequent surface alloying with Ni-Cr-Mo-Cu by double glow process of the substrate. Results showed that under alloying temperature (1000 °C) condition, the amorphous nano-SiO₂ particles still kept the amorphous structure, whereas the nano-SiC particles had been completely decomposed and Ni, Cr reacted with SiC to form Cr_6.5Ni_2.5Si and Cr₂₃C₆. The electrochemical corrosion behaviors of composite alloying layers compared with the single alloying layer and 316L stainless steel were measured under a range of hydrodynamic conditions by recording the current response, open circuit potential, potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS). Results showed that the increase of the impact velocity had significant influence on the current density of composite alloying layer with brush plating Ni/nano-SiC particles interlayer obtained under flowing condition at a potential of 200 mV, whereas there were only small fluctuations occurred at current response of composite alloying layer with brush plating Ni/nano-SiO₂ particles interlayer. The results of potentiodynamic polarization indicated that, with increasing impact velocity under slurry flow conditions, the corrosion potentials of test materials decreased and the corrosion current densities of test materials increased. The corrosion resistance of composite alloying layer with brush plating Ni/nano-SiO₂ particles interlayer was prominently superior to that of single alloying layer under slurry flow conditions; the corrosion resistance of composite alloying layer with brush plating Ni/nano-SiC particles interlayer was evidently lower than that of single alloying layer, but higher than that of 316L stainless steel under slurry flow conditions. The results of EIS indicated that, with respect to the R_tot obtained in sand-free flow, the impacts of sand particles dramatically decreased the R_tot values of composite alloying layer with brush plating Ni/nano-SiC particles interlayer, single alloying layer and 316L stainless steel, whereas the impact action slightly decreased that of composite alloying layer with brush plating Ni/nano-SiO₂ particles interlayer. The weight loss rate studies suggested that the highly dispersive nano-SiO₂ particles were helpful to improve the erosion-corrosion resistance of composite alloying layer, whereas the carbides and silicide phase were deleterious to that of composite alloying layer due to the fact that preferential removal of matrix around the precipitated phase takes place by the chemical attack of aggressive medium.