Engineering HVOF-Sprayed Cr3C2-NiCr Coatings: The Effect of Particle Morphology and Spraying Parameters on the Microstructure, Properties, and High Temperature Wear Performance

Chromium carbide-based thermally sprayed coatings are widely used for high temperature wear applications (typical temperature range from 540 to 900 °C). In these extreme environments at those temperatures, several phenomena will degrade, oxidize, and change the microstructure of the coatings, thereby affecting their wear behavior. Although it can be easily conceived that the Cr₃C₂-NiCr coating microstructure evolution after high temperature exposure will depend on the as-sprayed microstructure and spraying parameters, very little has been done in this regard. This study intends to develop a better understanding of the effect of spraying parameters on the resulting chromium carbide coating microstructure after high temperature operation and high temperature sliding wear properties. The microstructures of different coatings produced from two morphologies of Cr₃C₂-NiCr powders and under a window of in-flight particle temperature and velocity values were characterized through x-ray diffraction and scanning electron microscopy. Sliding wear at 800 °C was performed and the wear behavior correlated with the spraying parameters and coating microstructure. Vickers microhardness (300 gf) of the coatings before and after sliding wear was also measured.     

High-Temperature Erosion of HVOF Sprayed Cr3C2-NiCr Coating and Mild Steel for Boiler Tubes

The comparison of the high-temperature erosion behavior of a High-velocity oxyfuel (HVOF) sprayed Cr₃C₂-NiCr coating with mild steel for circulating fluidized bed boiler tubes was investigated. Results showed that the erosion rate of the mild steel at 800 °C was four times that at 300 °C at an erosion angle of 30°. However, the erosion rate of the HVOF sprayed Cr₃C₂-NiCr coating was not influenced by the temperature in the range of 300-800 °C. It was found that the erosion resistance of HVOF sprayed Cr₃C₂-NiCr coating was more than three times higher than that of the mild steel at 700-800 °C. In addition to the ploughing on the coating surface, the cracking along splat interfaces in the coating was clearly observed on the cross-sectional microstructure. The results indicate that the erosion performance of the HVOF sprayed Cr₃C₂-NiCr coating is controlled by the cohesion between splats and can be further enhanced by improving splat cohesion.     

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.     

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.     

Hot Corrosion Behavior of HVOF Sprayed Coatings on ASTM SA213-T11 Steel

Cr₃C₂-NiCr, NiCr, WC-Co and Stellite-6 alloy coatings were sprayed on ASTM SA213-T11 steel using the HVOF process. Liquid petroleum gas was used as the fuel gas. Hot corrosion studies were conducted on the uncoated as well as HVOF sprayed specimens after exposure to molten salt at 900 °C under cyclic conditions. The thermo-gravimetric technique was used to establish the kinetics of corrosion. XRD, SEM/EDAX and EPMA techniques were used to analyze the corrosion products. All these overlay coatings showed a better resistance to hot corrosion as compared to that of uncoated steel. NiCr Coating was found to be most protective followed by the Cr₃C₂-NiCr coating. WC-Co coating was least effective to protect the substrate steel. It is concluded that the formation of Cr₂O_3, NiO, NiCr₂O₄, and CoO in the coatings may contribute to the development of a better hot-corrosion resistance. The uncoated steel suffered corrosion in the form of intense spalling and peeling of the scale, which may be due to the formation of unprotective Fe₂O₃ oxide scale.     

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.     

High-Temperature Erosive Behavior of Plasma Sprayed Cr<Subscript>3</Subscript>C<Subscript>2</Subscript>-NiCr/Cenosphere Coating

This research examines the deposition of Cr₃C₂-NiCr/cenosphere and Cr₃C₂-NiCr coatings on MDN 321 steel through the process of plasma spray. In this process, the solid particle erosion test is established at 200, 400, 600 °C with 30° and 90° impact angles. Alumina erodent is adopted to investigate the erosive behavior of the coating at higher temperatures. The properties of the Cr₃C₂-NiCr/cenosphere coating are established based on the microhardness, the adhesive strength, the fracture toughness, and the ductility. To quantify volume loss as a result of erosion, an optical profilometer is used. At higher temperature, decrease in the erosion volume loss of Cr₃C₂-NiCr/cenosphere and Cr₃C₂-NiCr coatings is observed. The erosion-resistive property of Cr₃C₂-NiCr/cenosphere coating is higher than that of MDN 321 steel by 76%. This property is influenced by high-temperature stability of mullite, alumina, and protective oxide layer that is formed at elevated temperatures. The morphology of eroded coating discloses a brittle mode of material removal.     

Microstructure and Properties of HVOF-Sprayed WC-(W,Cr)<Subscript>2</Subscript>C-Ni Coatings

The composition WC-(W,Cr)₂C-Ni is one of the standard compositions used for the preparation of thermally sprayed coatings by high velocity oxy-fuel (HVOF) spraying. Surprisingly, this composition has been poorly investigated in the past. Frequent use of commercial designations WC-‘CrC’-Ni, WC-Cr₃C₂-Ni, and WC-NiCr indicates the insufficient knowledge about the phase compositions of these powders and coatings. The properties of these coatings differ significantly from those of WC-Co and WC-CoCr coatings. In this paper, the results of different series of experiments conducted on HVOF-sprayed WC-(W,Cr)₂C-Ni coatings are compiled and their specific benefits pointed out. The focus of this study is on the analysis of the microstructures and phase compositions of the feedstock powders and coatings. Unlike WC-Co and Cr₃C₂-NiCr, WC-(W,Cr)₂C-Ni is not a simple binary hard phase—binder metal composite. The phase (W,Cr)₂C with unknown physical and mechanical properties appears as a second hard phase, which is inhomogeneously distributed in the feedstock powders and coatings. As examples of coating properties, the oxidation resistance and dry sliding wear properties are compared with those of WC-10%Co-4%Cr coatings.     

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.     

Influence of the Spray Angle on the Characteristics of Atmospheric Plasma Sprayed Hard Material Based Coatings

This paper presents an investigation of the influence of the spray angle on thermally sprayed coatings. Spray beads were manufactured with different spray angles between 90 and 20° by means of atmospheric plasma spraying (APS) on heat-treated mild steel (1.0503). WC-12Co and Cr₃C₂-10(Ni20Cr) powders were employed as feedstock materials. Every spray bead was characterized by a Gaussian fit. This opens the opportunity to analyze the influence of the spray angle on coating properties. Furthermore, metallographic studies of the surface roughness, porosity, hardness, and morphology were carried out and the deposition efficiency as well as the tensile strength was measured. The thermally sprayed coatings show a clear dependence on the spray angle. A decrease in spray angle changes the thickness, width, and form of the spray beads. The coatings become rougher and their quality decreases.     

Performance of high-velocity oxyfuel-sprayed coatings on an fe-based superalloy in Na2SO4-60%V2O5 environment at 900 °C Part I: Characterization of the coatings

This article demonstrates the successful formulation of NiCrBSi, Cr₃C₂-NiCr, Ni-20Cr, and Stellite-6 coatings on an Fe-based superalloy by a high-velocity oxyfuel (HVOF) process for hot corrosion applications. The microstructure, porosity, coating thickness, phase formation, and microhardness properties of the coatings have been characterized using the combined techniques of optical microscopy, x-ray diffraction, scanning electron microscopy/energy-dispersive x-ray analysis. A microhardness tester was used to determine the hardness of the coatings. The coatings in general exhibit characteristic splat-like, layered morphologies due to the deposition and resolidification of successive molten or semimolten powder particles. The NiCrBSi, Cr₃C₂-NiCr, and Ni-20Cr coatings have shown a nickel-base face-centered cubic (fcc) structure as a principal phase, whereas Stellite-6 coating has an fcc Co-rich metallic matrix. Oxides/spinel oxides are formed in small fraction as intersplat lamellae or globules oriented parallel to the substrate surface. Coatings possess some unmelted/partially melted particles, inclusions, and porosity less than 2%. The microhardness of the coatings is found to be higher than the superalloys. The Cr₃C₂-NiCr coating has indicated a maximum microhardness of 990 Hv, while a Ni-20Cr coating has shown a minimum value of about 600 Hv. This article is focused on the characterization of HVOF coatings. The hot corrosion behavior of these coatings in a molten salt (Na₂SO₄-60%V₂O₅) environment at 900 °C under cyclic conditions is being presented as part II included in this issue.     

Tribological Properties of HVOF-Sprayed TiB<Subscript>2</Subscript>-NiCr Coatings with Agglomerated Feedstocks

Boride materials have drawn great attention in surface engineering field, owing to their high hardness and good wear resistance. In our previous work, a plasma-sprayed TiB₂-based cermet coating was deposited, but the coating toughness was significantly influenced by the formation of a brittle ternary phase (Ni₂₀Ti₃B₆) derived from the reaction between TiB₂ and metal binder. In order to suppress such a reaction occurred in the high-temperature spraying process, the high-velocity oxygen-fuel spraying technique was applied to prepare the TiB₂-NiCr coating. Emphasis was paid on the microstructure, the mechanical properties, and the sliding wearing performance of the coating. The result showed that the HVOF-sprayed coating mainly consisted of hard ceramic particles including TiB₂, CrB, and the binder phase. No evidence of Ni₂₀Ti₃B₆ phase was found in the coating. The mechanical properties of HVOF-sprayed TiB₂-NiCr coating were comparable to the conventional Cr₃C₂-NiCr coating. The frictional coefficient of the TiB₂-NiCr coating was lower than the Cr₃C₂-NiCr coating when sliding against a bearing steel ball.     

Wear,erosion and corrosion resistance of HVOF-sprayed WC and Cr3C2 based coatings for electrolytic hard chrome replacement

Thermally sprayed carbide-based coatings are nowadays extensively considered as an alternative to electrolytic hard chrome (EHC) coatings to reduce the environmental impact and the overall cost associated with EHC process. In this investigation, high-velocity oxy-fuel (HVOF) spray process was employed to prepare coatings using the traditional carbide powders namely the WC-10Co4Cr, the Cr₃C₂-25NiCr and a new type of mixed carbide powder WC-40Cr₃C₂-25NiCr. The Powder deposition rate, basic mechanical properties, abrasive wear, slurry erosion and corrosion resistance of the three coatings were then compared with the EHC coating. The results show that WC-10Co4Cr coating exhibited the highest hardness, abrasive wear and slurry erosion resistance followed by WC-40Cr₃C₂-25NiCr, EHC, and Cr₃C₂-25NiCr coating. The deposition efficiency of the powders as per hierarchy was found to be WC-40Cr₃C₂-25NiCr > WC-10Co4Cr > Cr₃C₂-25NiCr and all the HVOF sprayed coatings exhibited higher corrosion resistance than EHC coating. The highest powder deposition efficiency coupled with low density, acceptable tribo-corrosion performance, as well as low post processing cost makes the HVOF sprayed WC-40Cr₃C₂-25NiCr coating a potential candidate to replace the EHC coating.     

The role of microstructure in the high temperature oxidation mechanism of Cr3C2-NiCr composite coatings

Composites of Cr₃C₂-NiCr provide superior oxidation resistance to WC-Co composites, which has seen them applied extensively to components subjected to combined high temperature erosion and oxidation. This work characterises the variation in oxidation mechanism of thermally sprayed Cr₃C₂-NiCr composites at 700 °C and 850 °C as a function of heat treatment. Carbide dissolution during spraying increased the Ni alloy Cr concentration, minimising the formation of Ni oxides during oxidation. Compressive growth stresses resulted in ballooning of the oxide over the carbide grains. Carbide nucleation with heat treatment reduced the Ni alloy Cr concentration. The oxidation mechanism of the composite coating changed from being Cr based to that observed for NiCr alloys.     

Thermal stability of nanostructured Cr3C2-NiCr coatings

The thermal stability behavior of nanostructured Cr₃C₂-NiCr coatings was investigated. The nanostructured Cr₃C₂-NiCr coatings, synthesized using mechanical milling and high-velocity oxygen fuel (HVOF) thermal spraying, were thermally exposed in air at 473, 673, 873, and 1073 K for 8 h. The results show that microhardness of the conventional coating increased slightly with increasing temperature, while that of the nanostructured coating drastically increased from 1020 to 1240 HV₃₀₀ for the same temperature increases. Heat treatment led to increases in scratch resistance and decreases in the coefficient of friction for the nanostructured Cr₃C₂-NiCr coatings. A high density of Cr₂O₃ oxide particles with average size of 8.3 nm was found in the nanostructured coatings exposed to high temperatures, which is thought to be responsible for the observed increase in microhardness and scratch resistance and the decrease in the coefficient of friction of the nanostructured coatings.     

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.     

Comparison of Isolated Indentation and Grid Indentation Methods for HVOF Sprayed Cermets

This paper compares the results of two approaches of instrumented indentation for characterization of mechanical properties of HVOF coatings. Three types of HVOF sprayed coatings (Cr₃C₂-NiCr, WC-Co, (Ti, Mo)(C,N)-NiCo) were investigated by the means of isolated nanoindentation and grid indentation methods. The results of the isolated indentation revealed hardness and elastic modulus of the individual phases in very good agreement with the corresponding bulk material. The grid indentation method, based on statistical evaluation of a large number of indentations, was influenced by the carbide-matrix interface, which gave rise to a third peak apart from the two peaks corresponding to the carbides and metallic matrix. As a consequence, the bimodal Gaussian fit was insufficient and a trimodal fit had to be used. The results extracted from low load grid nanoindentations were quite close to the results of isolated indentations whereas higher load grid nanoindentation revealed overall properties of the coating.     

Influence of feedstock powder characteristics and spray processes on microstructure and properties of WC-(W,Cr)2C-Ni hardmetal coatings

The composition WC-(W,Cr)₂C-Ni (commercial designations WC-‘CrC’-Ni, WC-Cr₃C₂-Ni and WC-NiCr) is unique among the WC-based materials used for the preparation of thermally sprayed hardmetal coatings. These coatings show a significantly higher oxidation resistance and high-temperature sliding wear resistance than WC-Co and WC-CoCr coatings do. Unlike WC-Co and Cr₃C₂-NiCr, WC-(W,Cr)₂C-Ni is not a simple binary hard phase-binder metal composite as it is composed of two hard phases: WC and (W,Cr)₂C. Surprisingly this composition has been poorly investigated in the past.In this paper coating microstructures and properties obtained from five commercial feedstock powders of different origins using two different liquid-fuelled high velocity oxy-fuel (HVOF) systems (K2 and JP-5000) were investigated. Additional experiments were performed with one powder using atmospheric and vacuum plasma spraying (APS and VPS, respectively). The microstructures and phase compositions of the powders and the coatings were studied. Focus was on the appearance, composition and distribution of the (W,Cr)₂C phase which might form or might change its Cr/W ratio during the spray process. The composition of the (W,Cr)₂C phase was estimated from the lattice parameters. Hardness HV0.3 was measured for all coatings. The density, Young's modulus and abrasion wear resistance of HVOF-sprayed coatings were studied.     

WC-Co and Cr<Subscript>3</Subscript>C<Subscript>2</Subscript>-NiCr Coatings in Low- and High-Stress Abrasive Conditions

The article deals with the evaluation of abrasive wear resistance and adhesive strength of thermally sprayed coatings. The main attention was paid to differences between low- and high-stress abrasive conditions of the measuring. Conclusions include the evaluation of specific properties of the WC-Co and the Cr₃C₂-NiCr High Velocity Oxygen Fuel coatings and the evaluation of the changes in the behavior of the abrasive media. Mainly, the relationship between the low- and high-stress abrasion conditions and the wear mechanism in the tested materials was described. For the wear test, the abrasive media of Al₂O₃ and SiO₂ sands were chosen. During wear tests, the volume loss of the tested materials and the surface roughness of the wear tracks were measured. The wear tracks on the tested materials and abrasive sands’ morphologies were observed using Scanning Electron Microscopy. It was found that high-stress abrasive conditions change the coatings’ behavior very significantly, particularly that of the Cr₃C₂-NiCr coating. Adhesive-cohesive properties of the coatings and relationships among individual structure particles were evaluated using tensile testing. It was found that the weak bond strength among the individual splats, structure particles, and phases plays a role in the poor wear resistance of the coatings.     

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.