The role of microstructure in the mechanism of high velocity erosion of Cr3C2-NiCr thermal spray coatings: Part 1 — As-sprayed coatings

Carbide based thermal spray coatings are routinely applied to mitigate erosion under industrial conditions. However, the mechanism of erosion response under aggressive high velocity impact conditions remains unclear. In this work Cr₃C₂-25%NiCr thermal spray coatings were eroded at an impact velocity of 150 m/s by 20-25 µm alumina grit. Coatings were deposited by High Velocity Air Fuel (HVAF) and High Velocity Oxygen Fuel (HVOF) thermal spray techniques to generate a range of coating quality spanning that applied industrially. In Part 1 of this two-part series, the mechanism of erosion as a function of coating composition and microstructure variation is discussed. The HVOF coating underwent significant in-flight dissolution of the carbide phase. The erosion response of the supersaturated NiCr matrix was characterised by brittle cracking and fracture. The HVAF coating retained a high carbide content with minimal phase dissolution. However, the rapid solidification of the matrix material made the coating prone to brittle interphase cracking during impact. On a larger scale, splat based erosion mechanisms played a significant role, especially in the HVOF coating. The mechanisms of impact response of these coatings were dependent upon the depth of erodent penetration and could not, therefore, be extrapolated from erosion testing at lower velocities.     

High temperature erosion of Cr3C2-NiCr thermal spray coatings — The role of phase microstructure

Cr₃C₂-NiCr thermal spray coatings are extensively applied to mitigate erosion at temperatures above 450-550 °C. The aim of this work was to extend the current comparison based knowledge towards a mechanistic interpretation of the high temperature erosion of Cr₃C₂ based thermal spray coatings. Coatings that span the range of industrial quality were assessed. They were eroded under high temperature (700 °C and 800 °C), aggressive (impact velocity 225-235 m/s) conditions designed to simulate the high velocity erodent impacts within a turbine environment. The influence on the erosion response of high temperature induced changes in the coating microstructure and composition with extended in-service exposure was assessed by heat treating selected samples to generate a steady state microstructure prior to testing. In spite of the marked variation in coating microstructure the erosion rates were comparable across the range of coatings tested. The significance of this conclusion is discussed in terms of the erosion mechanism.     

Thermal shock behavior of nanostructured and conventional Al2O3/13 wt%TiO2 coatings fabricated by plasma spraying

The thermal shock behavior of three kinds of Al₂O₃/13 wt%TiO₂ coatings fabricated by plasma spraying was studied in this paper. One kind of those coatings was derived from conventional fused and crushed feedstock powder available commercially; the other two kinds of coatings were derived from nanostructured agglomerated feedstock powders. These two nano coatings possess moderate pores and pre-existing microcracks, they were composed of fused structure and three-dimensional net or skeleton-like structure. For conventional coatings, the pores and pre-existing cracks were bigger, sharp-point and mostly distributed between splats. Thermal shock tests for the three coatings were performed by water quenching method. Testing result showed the two kinds of nano coatings had much higher thermal shock resistance than the conventional coatings. The improved thermal shock resistance for nano coatings could attribute to their improved microstructure and crack propagation mode. The damage evolution and failure mechanism of coatings was quite different at thermal shock temperature of 650 °C and 850 °C, which was explained by a simple model. Different crack propagating modes in nanostructured and conventional coatings during thermal shock tests were due to their different microstructures in these two kinds coatings. The stress state of coating surfaces during the thermal cycles was also discussed in this paper.     

Characterisation of HVOF sprayed Cr3C2-50(Ni20Cr) coating and the influence of binder properties on solid particle erosion behaviour

The coating Cr₃C₂ with 50 wt.% Ni20Cr deposited by high velocity oxy-fuel (HVOF) spray process was characterized in detail to investigate the effect of annealing on the solid particle erosion behaviour and understand the influence of the binder properties. Systematic characterization of the coating was carried out using electron microscopy (scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electron probe microanalysis (EPMA)), X-ray diffraction (XRD), microindentation and nanoindentation techniques. The solid particle erosion tests were done on the as-sprayed coating and coatings annealed at 400 °C, 600 °C and 800 °C using silica erodent particles. The coefficient of restitution of the coated samples was also measured by WC ball impact tests to simulate dynamic impacts. The as-sprayed coating consisted of primary carbides and binder that was a mixture of amorphous and nanocrystalline phases. Annealing leads to recrystallisation of binder phase and precipitation of secondary carbides. The coating hardness and binder ductility change with annealing temperature. The erosion resistance improves with annealing up to 600 °C. In the as-sprayed coating, the amorphous phase, inter-splat boundaries and the elastic rebound characteristics affect the erosion response. While in the case of the coating annealed at 600 °C, the presence of ductile crystalline binder, fine carbide precipitates and embedment of erodent particles together improve solid particle erosion resistance.     

The effect of plasma spray parameters on the cavitation erosion of Al2O3-TiO2 coatings

This paper reports a study of how the choice of plasma spray parameters, used during deposition of Al₂O₃-13%TiO₂ coatings on carbon steel, influences the cavitation erosion properties of such coatings. The parameters studied are the power feeding rate and hydrogen flow rate. The surface and cross section of coatings before and after cavitation were also observed by scanning electron microscopy (SEM). The phases present in the coatings were characterized by X-ray diffraction method (XRD). The microscopic observations were used to study the inter-lamellar connection, porosity, unmelted particles and so on inside the coating. We also measured the roughness, microhardness, adhesion strength and cavitation erosion of the coatings. The XRD results showed that the coating includes different allotropes of Al₂O₃ such as α and γ. The cavitation erosion studies of the coatings were conducted by ultrasonic cavitation testing on the basis of ASTM G32 standard. It was found that cavitation erosion is accelerated around the unmelted particles and porosities. The results reveal that the cavitation resistance of the coating is determined by its microstructure and that increasing discontinuities (inside the coating) reduce its cavitation resistance. We have found that the coating obtained at hydrogen gas flow rate of 16 L/min and powder feeding rate of 20 g/min has the best cavitation resistance.     

Hot corrosion behavior of detonation gun sprayed Cr3C2–NiCr coatings on Ni and Fe-based superalloys in Na2SO4–60% V2O5 environment at 900 °C

The present work investigates the hot corrosion resistance of detonation gun sprayed (D-gun) Cr₃C₂–NiCr coatings on Superni 75, Superni 718 and Superfer 800 H superalloys. The deposited coatings on these superalloy substrates exhibit nearly uniform, adherent and dense microstructure with porosity less than 0.8%. Thermogravimetry technique is used to study the high temperature hot corrosion behavior of bare and Cr₃C₂–NiCr coated superalloys in molten salt environment (Na₂SO₄–60% V₂O₅) at high temperature 900 °C for 100 cycles. The corrosion products of the detonation gun sprayed Cr₃C₂–NiCr coatings on superalloys are analyzed by using XRD, SEM, and FE-SEM/EDAX to reveal their microstructural and compositional features for elucidating the corrosion mechanisms. It is shown that the Cr₃C₂–NiCr coatings on Ni- and Fe-based superalloy substrates are found to be very effective in decreasing the corrosion rate in the given molten salt environment at 900 °C. Particularly, the coating deposited on Superfer 800 H showed a better hot corrosion protection as compared to Superni 75 and Superni 718. The coatings serve as an effective diffusion barrier to preclude the diffusion of oxygen from the environment into the substrate superalloys. It is concluded that the hot corrosion resistance of the D-gun sprayed Cr₃C₂–NiCr coating is due to the formation of desirable microstructural features such as very low porosity, uniform fine grains, and the flat splat structures in the coating.     

The performances of TiB2-contained iron-based coatings at high temperature

The TiB₂-contained composite Fe-B-C coatings are deposited by the plasma transferred-arc (PTA) powder surfacing process. The coating's thermal ability, arc ablation resistance and wear resistance at high temperature were analyzed. It is concluded that TiB₂-contained composite Fe-B-C coating having excellent wear resistance at 600 °C and tempering resistance at 900 °C. Furthermore, this coating can effectively resist the arc ablation (120 A arc currents) within 7 s.     

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.     

Thermal shock resistance of FeMnCrAl/Cr3C2-Ni9Al coatings deposited by high velocity arc spraying

FeMnCrAl/Cr₃C₂ and FeMnCrAl/Cr₃C₂-Ni9Al coatings were deposited onto low-carbon steel substrates by high velocity arc spraying. The cross-section and interface microstructures of the coatings were analyzed by optical microscopy (OM). The thermal shock resistance of the coatings was investigated. The characteristics of the coatings after the thermal cycling test were studied by OM, field emission scanning electron microscopy, and energy dispersion spectrometry. The results show that laminated structures with pores, oxide phases, and unmelted particles were found on all the prepared coatings. The FeMnCrAl/Cr₃C₂ coating with a Ni9Al interlayer registered the best thermal shock resistance, which may be attributed to the interdiffusion between the low-carbon steel substrates and the Ni9Al arc-sprayed coating that converted the mechanical bond between the substrates and the coatings to a metallurgical one.     

Effect of (NaPO3)6 concentrations on corrosion resistance of plasma electrolytic oxidation coatings formed on AZ91D magnesium alloy

Different plasma electrolytic oxidation (PEO) coatings were prepared on AZ91D magnesium alloy in electrolytes containing various concentrations of (NaPO₃)₆. The morphologies, chemical compositions and corrosion resistance of the PEO coatings were characterized by environmental scanning electron microscopy (ESEM), X-ray diffractometer (XRD), energy dispersive analysis of X-rays (EDAX), potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) test. The results showed that the PEO coatings were mainly composed of MgO, Mg₂SiO₄, MgAl₂O₄ and amorphous compounds. As the (NaPO₃)₆ concentrations increased from 0 to 10 g/l, the thickness and surface roughness of the coatings approximately linearly increased; the MgO and Mg₂SiO₄ phase increased within the concentration range of 0–3 and 0–5 g/l, and then decreased within the range of 3–10 and 5–10 g/l, respectively, while the MgAl₂O₄ phase gradually decreased. Moreover, the corrosion resistance of the coatings increased within the range of 0–5 g/l and then decreased within the range of 5–10 g/l. The best corrosion resistance coating was obtained in electrolyte containing 5 g/l (NaPO₃)₆, it had the most compact microstructure. Besides, a reasonable equivalent circuit was established, and the fitting results were consistent with the results of the EIS test.     

Erosion of oxide scales formed on Cr3C2-NiCr thermal spray coatings

Cr₃C₂-NiCr thermal spray coatings are extensively used to mitigate high temperature erosive wear in fluidised bed combustors and power generation/transport turbines. The aim of this work was to characterise the variation in oxide erosion response as a function of the Cr₃C₂-NiCr coating microstructure. Erosion was carried out at 700 °C and 800 °C with erodent impact velocities of 225-235 m/s. The erosion behaviour of the oxide scales formed on these coatings, was influenced by the coating microstructure and erosion temperature. Development of the carbide microstructure with extended heat treatment lead to variations in the erosion-corrosion response of the Cr₃C₂-NiCr coatings.     

Investigation on the corrosion and oxidation resistance of Ni-Al2O3 nano-composite coatings prepared by sediment co-deposition

Ni-Al₂O₃ composite coatings were prepared by using sediment co-deposition (SCD) technique from a Watt's type electrolyte containing nano-Al₂O₃ particles. The corrosion resistance and high temperature oxidation resistance of resulting composite coatings were investigated. It was found that the incorporation of nano-Al₂O₃ particles in Ni matrix refined the Ni crystal and changed the preferential orientation of composite coatings. Meanwhile, the corrosion and oxidation resistance were improved after the incorporation of nano-Al₂O₃ particles into Ni matrix. The nano-Al₂O₃ content in deposits plays an important role for improving the corrosion and oxidation protection. The corrosion and oxidation resistance of Ni-Al₂O₃ nano-composite coatings produced via SCD technique are superior to that of CEP technique. Compared to pure Ni and Ni-Al₂O₃ composite coatings fabricated using CEP technique, the Ni-7.58 wt.% Al₂O₃ composite coating obtained by SCD technique exhibits better corrosion resistance and enhanced high temperature oxidation resistance. Moreover, the mechanism of corrosion and high temperature oxidation resistance of Ni-Al₂O₃ nano-composite coatings are discussed.     

Preparation of nanostructured Ni/Al2O3 composite coatings in high magnetic field

Ni/Al₂O₃ composite coatings were prepared by a novel method from a modified Watt's type electrolyte containing nano-Al₂O₃ particles, where a high magnetic field was imposed in the direction parallel to an electrolytic current instead of mechanical agitation. Effects of magnetic field on the content of particles, surface morphology, microhardness and wear resistance of plating layer were investigated. It was found that the high magnetic field played an important role in the formation of composite coatings. The amounts of nano-Al₂O₃ particles in the composite coating increased with increasing of magnetic flux density and reached a maximum value at 8 T, then reduced slightly. The microhardness and wear resistance of the nanocomposite coatings also enhanced with increasing of magnetic flux density as compared to that of pure Ni coating fabricated in the absence of magnetic field. That was because the co-deposited nano-Al₂O₃ particles were uniformly distributed in the Ni matrix and contributed to greatly increase the microhardness and wear resistance of the composite coatings. Moreover, the mechanism of action of high magnetic field was discussed preliminarily.     

Oxidation behavior of arc-sprayed FeMnCrAl/Cr3C2-Ni9Al coatings deposited on low-carbon steel substrates

FeMnCr/Cr₃C₂ and FeMnCrAl/Cr₃C₂ coatings, using Ni9Al arc-sprayed coating as an interlayer on low-carbon steel substrates, were deposited by high velocity arc spraying (HVAS) on the cored wires. The high temperature oxidation behavior of the arc-sprayed FeMnCrAl/Cr₃C₂-Ni9Al and FeMnCr/Cr₃C₂ coatings on the low-carbon steel substrates was studied during isothermal exposures to air at 800 °C. The surface and interface morphologies of the coatings after isothermal oxidation after 100 h were observed and characterized by optical microscopy, field emission scanning electron microscope, energy dispersion spectrum, and X-ray diffraction. The results showed that the oxidation weight gains of the coatings were significantly lower than that of the low-carbon steel substrate. Moreover, the FeMnCrAl/Cr₃C₂-Ni9Al coating registered the lowest oxidation rate. This favorable oxidation resistance is due to the Al and Cr contents of the aforementioned coating that inhibits the generation of Fe and Mn oxides. This is attributed to the interdiffusion between the substrates and the Ni9Al arc-sprayed coating, which can convert the mechanical bonding between substrates and coatings into a metallurgical one, thereby inhibiting the oxidation of interface between the low-carbon steel and the coating.     

Dominant microstructural feature over photocatalytic activity of high velocity oxy-fuel sprayed TiO2 coating

TiO₂ photocatalytic coatings were deposited through high velocity oxy-fuel spray using anatase powder and rutile powder as feedstock. The as-sprayed TiO₂ coating was composed of anatase phase and rutile phase. The anatase content in the coating was significantly influenced by fuel gas flow and melting condition of spray powder. A high anatase content of 35% was achieved for the coating deposited using rutile powder. The anatase content in the coating deposited using anatase powder reached 55-65%. The as-sprayed TiO₂ coating was photocatalytically reactive for degradation of acetaldehyde in air. The photocatalytic activity was influenced by spray conditions. The surface morphology and phase structure of coatings deposited at different spray conditions were investigated to clarify the relationship between the coating microstructure and activity. It is found that the photocatalytic activity is significantly influenced by anatase content and surface area.     

Effects of critical plasma spray parameter and spray distance on wear resistance of Al2O3-8 wt.%TiO2 coatings plasma-sprayed with nanopowders

Effects of plasma spraying conditions on wear resistance of nanostructured Al₂O₃-8 wt.%TiO₂ coatings plasma-sprayed with nanopowders were investigated in this study. Five kinds of nanostructured coatings were plasma-sprayed on a low-carbon steel substrate by varying critical plasma spray parameter (CPSP) and spray distance. The coatings consisted of fully melted region of γ-Al₂O₃ and partially melted region, and the fraction of the partially melted regions and pores decreased with increasing CPSP or decreasing spray distance. The hardness and wear test results revealed that the hardness of the coatings increased with increasing CPSP or decreasing spray distance, and that the hardness increase generally led to the increase in wear resistance, although the hardness and wear resistance were not correlated in the coating fabricated with the low CPSP. The main wear mechanism was a delamination one in the coatings, but an abrasive wear mode also appeared in the coating fabricated with the low CPSP. According to these wear mechanisms, the improvement of wear resistance in the coating fabricated with the low CPSP could be explained because the improved resistance to fracture due to the presence of partially melted regions might compensate a deleterious effect of the hardness decrease.     

钼酸钠常温磷化液的研究

    选择钼酸钠作为磷化液的主促进剂.对其所得磷化膜的耐蚀性和膜重做了检测;用扫描电子显微镜对磷化膜的微观结构进行分析;同时研究了磷化时间和磷化温度对磷化膜性能的影响.     

An experimental study on synthesizing submicron MoSi2-based coatings using electrothermal explosion ultra-high speed spraying method

The MoSi₂-based coatings were synthesized on the surface of the low carbon steel substrate using electrothermal explosion ultra-high speed spraying method. Microstructure, phase structure, elements distribution and microhardness of the coatings were characterized by SEM, XRD, EDS and Vickers hardness tester, respectively. It is found that MoSi₂ coating and MoSi₂ + MoB₂ multiphase coating were in-situ formed. The coatings have compact microstructure, submicron-grain and high hardness. The bonding of coating-substrate is metallurgical one. The hardness and microstructure of the MoSi₂ coating were improved by boron alloying. The average and highest hardness of the MoSi₂ coating are 1340 HV_0.2 and 1390 HV_0.2, respectively, and that of MoSi₂ + MoB₂ multiphase coating are 1650 HV_0.2 and 1785 HV_0.2, respectively.     

Oxidation resistance of refractory γ-TiAlW coatings

The resistance to oxidation of the W-alloyed magnetron sputtered γ-TiAl fine-crystalline 4 μm thick coatings have were investigated in this work. The oxidation tests were performed in an atmosphere of pure oxygen or in the air at a temperature of 1173 K for 120 h. The resistance to high-temperature oxidation was investigated by means of micro-thermogravimetric analysis with continuous or stepwise control of the substrate weight. Before and after the oxidation the morphology of the coatings as well as their chemical and phase composition were investigated by SEM, EDS and EBSD, respectively. The results have been compared with those obtained for the uncoated γ-TiAl substrate.It was found that: (1) the W-alloyed γ-TiAl coatings have a considerably higher oxidation resistance (about four orders of magnitude) than the uncoated γ-TiAl substrates and that their resistance to oxidation increases with the concentration of alloying element in the range of the concentrations investigated in the work; (2) the high resistance to oxidation of the coatings is a result of the thin α-Al₂O₃ layer formation on the surface of the substrate during oxidation; (3) the formation of dense and uniform α-Al₂O₃ layer on the coating surface is due to a fine-crystalline structure of the magnetron deposited γ-TiAlW coating.     

Deposition of Al2O3-TiO2 Nanostructured Powders by Atmospheric Plasma Spraying

Al₂O₃-13%TiO₂ coatings were deposited on stainless steel substrates from conventional and nanostructured powders using atmospheric plasma spraying (APS). A complete characterization of the feedstock confirmed its nanostructured nature. Coating microstructures and phase compositions were characterized using SEM, TEM, and XRD techniques. The microstructure comprised two clearly differentiated regions. One region, completely fused, consisted mainly of nanometer-sized grains of γ-Al₂O₃ with dissolved Ti⁺⁴. The other region, partly fused, retained the microstructure of the starting powder and was principally made up of submicrometer-sized grains of α-Al₂O₃, as confirmed by TEM. Coating microhardness as well as tribological behavior were determined. Vickers microhardness values of conventional coatings were in average slightly lower than the values for nanostructured coating. The wear resistance of conventional coatings was shown to be lower than that of nanostructured coatings as a consequence of Ti segregation. A correlation between the final properties, the coating microstructure, and the feedstock characteristics is given.