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

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

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.     

Toughening and strengthening mechanism of plasma sprayed nanostructured Al2O3–13 wt.%TiO2 coatings

The starting materials of Al₂O₃, TiO₂, ZrO₂ and CeO₂ nanoparticles were agglomerated into sprayable feedstock powders and plasma sprayed to form nanostructured coatings. There were net structures and fused structures in plasma sprayed nanostructured Al₂O₃–13 wt.%TiO₂ coatings. The net structures were derived from partially melted feedstock powders and the fused structures were derived from fully melted feedstock powders. The nanostructured Al₂O₃–13 wt.%TiO₂ coatings possessed higher hardness, bonding strength and crack growth resistance than conventional Metco 130 coatings which were mainly composed of lamellar fused structures. The higher toughness and strength of nanostructured Al₂O₃–13 wt.%TiO₂ coatings were mainly related to the obtained net structures.     

Corrosion Behavior of Bare,Cr3C2-25%(NiCr), and Cr3C2-25%(NiCr)+0.4%CeO2-Coated Superni 600 Under Molten Salt at 900 °C

Cr₃C₂-25(NiCr) and Cr₃C₂-25(NiCr)+0.4%CeO₂ coatings were deposited on nickel-based superalloy Superni 600 by Detonation-gun technique. Studies were conducted on bare and coated alloys in molten salt environment (Na₂SO₄-25%NaCl) at 900 °C under cyclic condition. Characterization of the corrosion product was done using field emission scanning electron microscopy/energy dispersive spectroscopy and x-ray diffraction techniques. The bare Superni 600 shows penetration of corrosion beneath the metal layer thereby indicating internal oxidation. The coating of Cr₃C₂-25(NiCr) with 0.4%CeO₂ leads to the formation of adherent scale.     

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.     

Oxidation and Hot Corrosion Resistance of HVOF WC-NiCrFeSiB Coating on Ni- and Fe-based Superalloys at 800 °C

The present work evaluates the oxidation and hot corrosion resistance of high velocity oxy-fuel (HVOF) sprayed WC-NiCrFeSiB coating deposited on Ni-based superalloy (Superni 75) and Fe-based superalloy (Superfer 800H). The coated as well as uncoated specimens were exposed to air and molten salt (Na₂SO₄-25% NaCl) environment at 800 °C under cyclic conditions. The thermogravimetric technique was used to establish the kinetics of corrosion. The corrosion products were characterized using the combined techniques of x-ray diffraction (XRD), scanning electron microscopy (SEM), and electron probe micro analyser (EPMA). The WC-NiCrFeSiB coating provides necessary resistance against oxidation and hot corrosion to both the nickel and iron-based superalloys in the given environmental conditions at 800 °C. The oxides of active elements of the coatings, formed in the surface scale as well as at the boundaries of nickel and tungsten rich splats, have contributed for the oxidation and hot corrosion resistance of WC-NiCrFeSiB coatings, as these oxides act as barriers for the diffusion/penetration of the corrosive species through the coatings. This article is an invited paper selected from presentations at the 2007 International Thermal Spray Conference and has been expanded from the original presentation. It is simultaneously published in Global Coating Solutions, Proceedings of the 2007 International Thermal Spray Conference, Beijing, China, May 14-16, 2007, Basil R. Marple, Margaret M. Hyland, Yuk-Chiu Lau, Chang-Jiu Li, Rogerio S. Lima, and Ghislain Montavon, Ed., ASM International, Materials Park, OH, 2007.     

Hot corrosion resistance of high-velocity oxyfuel sprayed coatings on a nickel-base superalloy in molten salt environment

No alloy is immune to hot corrosion attack indefinitely. Coatings can extend the lives of substrate materials used at higher temperatures in corrosive environments by forming protective oxides layers that are reasonably effective for long-term applications. This article is concerned with studying the performance of high-velocity oxyfuel (HVOF) sprayed NiCrBSi, Cr₃C₂−NiCr, Ni−20Cr, and Stellite-6 coatings on a nickel-base superalloy at 900 °C in the molten salt (Na₂SO₄-60% V₂O₅) environment under cyclic oxidation conditions. The thermogravimetric technique was used to establish kinetics of corrosion. Optical microscope, x-ray diffraction, scanning electron microscopy/electron dispersive analysis by x-ray (SEM/EDAX), and electron probe microanalysis (EPMA) techniques were used to characterize the as-sprayed coatings and corrosion products. The bare superalloy suffered somewhat accelerated corrosion in the given environmental conditions. whereas hot corrosion resistance of all the coated superalloys was found to be better. Among the coating studied, Ni−20Cr coated superalloy imparted maximum hot corrosion resistance, whereas Stellite-6 coated indicated minimum resistance. The hot corrosion resistance of all the coatings may be attributed to the formation of oxides and spinels of nickel, chromium, or cobalt.     

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

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

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

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

Microstructure and adhesion of Cr3C2-NiCr vacuum plasma sprayed coatings

Vacuum plasma spraying (VPS) was used to spray a Cr₃C₂-NiCr coating of ∼ 150, 300 and 450 μm in thickness onto a plain carbon steel substrate, employing a commercially available Cr20Ni9.5C powder. The splat microstructures observed in the coating were found to consist of a NiCr matrix with a predominant Cr₃C₂ phase, besides Cr₇C₃ and Cr₂O₃. The adhesion of the coating to the substrate was evaluated by means of interfacial indentation techniques. It has been found that the interfacial toughness value changes from 7.6 to 10.1 MPa m^1/2 when the thickness increases from 150 to 450 μm. Also, it has been found that the parameter Kca_o, determined by linear regression from the Kca versus 1 / e² curve by means of the interfacial indentation model advanced by Chicot et al., has a value of ∼ 9.8 MPa m^1/2.     

Comparative study of Cr3C2-NiCr coatings obtained by HVOF and hard chromium coatings

In the present work the corrosion resistance of micro-cracked hard chromium and Cr₃C₂-NiCr (HVOF) coatings applied on a steel substrate have been compared using open-circuit potential (E_OC) measurements, electrochemical impedance spectroscopy (EIS) and polarization curves. The coatings surfaces and cross-section were characterized before and after corrosion tests using optical microscopy (OM) and scanning electron microscopy (SEM). After 18 h of immersion, the open-circuit potential values were around −0.50 and −0.25 V/(Ag∣AgCl∣KCl_sat) for hard chromium and Cr₃C₂-NiCr, respectively. The surface analysis done after 12 h of immersion showed iron on the hard chromium surface inside/near surface cracks, while iron was not detected on the Cr₃C₂-NiCr surface even after 18 h. For longer immersion time hard chromium was more degraded than thermal sprayed coating. For hard chromium coating a total resistance values between 50 and 80 kΩ cm² were measured and two well-defined time constants were observed, without significant change with the immersion time. For Cr₃C₂-NiCr coating the total impedance diminished from around 750 to 25 kΩ cm² as the immersion time increased from 17 up to 132 h and two overlapped time constants were also observed. Polarization curves recorded after 18 h of immersion showed a lower current and higher corrosion potential for Cr₃C₂-NiCr coating than other samples studied.     

A study on hot corrosion behaviour of Ni–5Al coatings on Ni- and Fe-based superalloys in an aggressive environment at 900 °C

Ni–5Al coating was deposited on Ni- and Fe-based superalloys by high velocity oxy fuel (HVOF) process to enhance their high-temperature corrosion resistance. Hot corrosion studies were conducted on bare as well as HVOF-coated superalloy specimens after exposure to a molten salt environment at 900 °C under cyclic conditions. Each cycles consisted of 1 h heating in the silicon carbide tube furnace followed by 20 min cooling in air. Thermogravimetric technique was used to approximate the kinetics of corrosion. Techniques like X-ray diffraction (XRD), scanning electron microscopy/energy dispersive X-ray analysis (SEM/EDAX) were used to characterize the corrosion products. The coatings and the oxide scale formed on the exposed surface were found to be intact with the superalloys. Superfer 800 with Ni–5Al coating has provided a good protection to the superalloys in the given molten salt environment.     

The role of microstructure in the mechanism of high velocity erosion of Cr3C2-NiCr thermal spray coatings: Part 2 — Heat treated coatings

In Part 1 of this two part series the variation in erosion mechanisms as a function of as-sprayed coating microstructure was presented. The oxidation resistance of Cr₃C₂-NiCr coatings means that they are used in high temperature applications where WC-Co based systems are no longer suitable. High temperature exposure has been shown to generate microstructural development in these coatings, leading to variations in coating hardness. In this work the effect of such coating development on the high velocity erosion response is investigated. The HVAF and HVOF coatings of Part 1 were heat treated for up to 30 days at 900 °C to generate a range of coating microstructures up to steady state. Erosion was performed under the same conditions as in Part 1. Heat treatment increased the ductility of the NiCr phase, enabling ductile erosion deformation to occur. Intersplat sintering reduced the significance of splat based erosion mechanisms and forced mass loss to become dictated by the phase microstructure. Such developments improved the quantified erosion resistance of both coating systems relative to the as-sprayed conditions. The coating microhardness was shown to be a poor indicator of erosion response across the range of coating microstructures investigated.     

超音速火焰喷涂Cr3C2/NiCr涂层抗加沙空蚀性分析

采用HVOF技术在1Cr18Ni9Ti不锈钢基体上制备了Cr3C2/NiCr涂层,借助XRD,TEM,SEM等方法分析了涂层的组织形貌及相组成.以1Cr18Ni9Ti奥氏体不锈钢作为对比材料,用磁致伸缩空蚀仪配备扬沙装置测试了涂层在清水以及含沙水中抗空蚀性能.结果表明,涂层呈层状结构,含有未熔颗粒和少量孔隙,涂层由Cr3C2,Cr7C3,Cr23C6及NiCr等相组成;在清水试验中,1Cr18Ni9Ti不锈钢抗空蚀性能良好,与空蚀过程中1Cr18Ni9Ti奥氏体不锈钢产生加工硬化有直接关系;在含沙40 kg/m3试验水中,Cr3C2/NiCr涂层呈现出较好的抗空蚀性能,与涂层自身相组成以及较高硬度有关.Cr3C2/NiCr涂层破坏总是从孔隙等薄弱环节开始,而1Cr18Ni9Ti奥氏体不锈钢的破坏起始于晶界和孪晶界.     

A comparative study of tribological behavior of plasma and D-gun sprayed coatings under different wear modes

In recent years, thermal sprayed protective coatings have gained widespread acceptance for a variety of industrial applications. A vast majority of these applications involve the use of thermal sprayed coatings to combat wear. While plasma spraying is the most versatile variant of all the thermal spray processes, the detonation gun (D-gun) coatings have been a novelty until recently because of their proprietary nature. The present study is aimed at comparing the tribological behavior of coatings deposited using the two above techniques by focusing on some popular coating materials that are widely adopted for wear resistant applications, namely, WC-12% Co, A1₂O₃, and Cr₃C₂-MCr. To enable a comprehensive comparison of the above indicated thermal spray techniques as well as coating materials, the deposited coatings were extensively characterized employing microstructural evaluation, microhardness measurements, and XRD analysis for phase constitution. The behavior of these coatings under different wear modes was also evaluated by determining their tribological performance when subjected to solid particle erosion tests, rubber wheel sand abrasion tests, and pin-on-disk sliding wear tests. The results from the above tests are discussed here. It is evident that the D-gun sprayed coatings consistently exhibit denser microstructures and higher hardness values than their plasma sprayed counterparts. The D-gun coatings are also found to unfailingly exhibit superior tribological performance superior to the corresponding plasma sprayed coatings in all wear tests. Among all the coating materials studied, D-gun sprayed WC-12%Co, in general, yields the best performance under different modes of wear, whereas plasma sprayed Al₂O₃ shows least wear resistance to every wear mode.     

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.     

Thermo-physical and thermal cycling properties of plasma-sprayed BaLa2Ti3O10 coating as potential thermal barrier materials

Increased turbine inlet temperature in advanced turbines has promoted the development of thermal barrier coating (TBC) materials with high-temperature capability. In this paper, BaLa₂Ti₃O₁₀ (BLT) was produced by solid-state reaction of BaCO₃, TiO₂ and La₂O₃ at 1500 °C for 48 h. BLT showed phase stability between room temperature and 1400 °C. BLT revealed a linearly increasing thermal expansion coefficient with increasing temperature up to 1200 °C and the coefficients of thermal expansion (CTEs) are in the range of 1 × 10^− 5–12.5 × 10^− 6 K^− 1, which are comparable to those of 7YSZ. BLT coatings with stoichiometric composition were produced by atmospheric plasma spraying. The coating contained segmentation cracks and had a porosity of around 13%. The microhardness for the BLT coating is 3.9–4.5 GPa. The thermo-physical properties of the sprayed coating were investigated. The thermal conductivity at 1200 °C is about 0.7 W/mK, exhibiting a very promising potential in improving the thermal insulation property of TBC. Thermal cycling result showed that the BLT TBC had a lifetime of more than 1100 cycles of about 200 h at 1100 °C. The failure of the coating occurred by cracking at the thermally grown oxide (TGO) layer due to severe oxidation of bond coat. Based on the above merits, BLT could be considered as a promising material for TBC applications.     

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.     

Phase diagram of In2Te3–Cr3Te4

Based on the results of a physico-chemical analysis, the equilibrium diagram of the In₂Te₃–Cr₃Te₄ section of the In–Cr–Te ternary system has been constructed. The section is quasi-binary and at the basic component ratio of 1:1 the ternary compound In₂Cr₃Te₇ with a peritectic melting character is formed. Both basic components at 300 K have homogeneity regions with limits of 5.5 and 2 mol% from the In₂Te₃ and Cr₃Te₄ sides, respectively.     

Hot corrosion behaviour of plasma sprayed YSZ/Al2O3 dispersed NiCrAlY coatings on Inconel-718 superalloy

Oxide dispersed NiCrAlY bond coatings have been developed for enhancing thermal life cycles of thermal barrier coatings (TBCs). However, the role of dispersed oxides on high temperature corrosion, in particular hot corrosion, has not been sufficiently studied. Therefore, the present study aims to improve the understanding of the effect of YSZ dispersion on the hot corrosion behaviour of NiCrAlY bond coat. For this, NiCrAlY, NiCrAlY + 25 wt.% YSZ, NiCrAlY + 50 wt.% YSZ and NiCrAlY + 75 wt.% YSZ were deposited onto Inconel-718 using the air plasma spraying (APS) process. Hot corrosion studies were conducted at 800 °C on these coatings after covering them with a 1:1 weight ratio of Na₂SO₄ and V₂O₅ salt film. Hot corrosion kinetics were determined by measuring the weight gain of the specimens at regular intervals for a duration of 51 h. X-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy techniques were used to determine the nature of phases formed, examine the surface attack and to carry out microanalysis of the hot corroded coatings respectively. The results show that YSZ dispersion causes enhanced hot corrosion of the NiCrAlY coating. Leaching of yttria leads not only to the formation of the YVO₄ phase but also the destabilization of the YSZ by hot corrosion. For the sake of comparison, the hot corrosion behaviour of a NiCrAlY + 25 wt.% Al₂O₃ coating was also examined. The study shows that the alumina dispersed NiCrAlY bond coat offers better hot corrosion resistance than the YSZ dispersed NiCrAlY bond coat, although it is also inferior compared to the plain NiCrAlY bond coat.