Improvement of microstructural and tribological properties of APS carbide coatings via PTA surface melting

ABSTRACT

In the current study, WC-Co and Cr₃C₂-NiCr coatings deposited on 90MnCrV8 steel surface via an atmospheric plasma spray (APS) system were modified by the plasma transferred arc (PTA) welding method. Microstructural defects including micro-cracks, voids, pores, and non-uniform zones were determined in the APS deposited layers. The microstructural defects were terminated by the PTA melting process due to the dissolving pool at high temperature. Strong metallurgical bonding between the coating layer and substrate and columnar dendrites and inter-dendritic precipitates were observed during the PTA melting process. Following the PTA melting process, MC, M₃C, and M₇C₃ hard phases were formed in the coating layers. The hardness and wear performance of the coating layers significantly increased due to the PTA surface modification. The main reason for the significant increases in wear performance corresponded to the newly formed hard carbide phases and elimination of microstructural defects via the PTA surface modification.     

Evaluation of vanadium carbide coatings on AISI H13 obtained by thermo-reactive deposition/diffusion technique

Vanadium carbide coatings on AISI H13 steel were prepared by thermo-reactive deposition/diffusion process (TRD) in molten salt bath for 1 to 6 h at 920 °C and 1000 °C, respectively. The obtained coatings were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDX) and X-ray diffraction analysis (XRD). Equiaxed grains were observed throughout the coatings. The grain size gradually increased from the coating/substrate interface to the top surface. The coatings were composed of ordered state V₆C₅ phase and disordered state VC_x (x = 0.83-0.88) phases and had a preferential orientation of (111) and (200) planes. The values of nano-indentation hardness and elastic modulus of the coating are 28.1 ± 0.7 GPa and 421 ± 14 GPa, respectively. The growth of the vanadium carbide coating by the TRD process followed a parabolic kinetics with an activation energy of 199.3 kJ/mol. The variation of the coating thickness on the AISI H13 steel with treating time and temperature can be determined.     

Microstructure and wear behavior of stellite 6 cladding on 17-4 PH stainless steel

This paper deals with the investigation of the microstructure and wear behavior of the stellite 6 cladding on precipitation hardening martensitic stainless steel (17-4PH) using gas tungsten arc welding (GTAW) method. 17-4 PH stainless steel is widely used in oil and gas industries. Optical metallography, scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) were employed to study the microstructure and wear mechanisms. X-ray diffraction analysis was also used to identify phases formed in the coating. The results showed that the microstructure of the surface layer consisted of carbides embedded in a Co-rich solid solution with a dendritic structure. In addition, the dendritic growth in the coating was epitaxial. Primary phases formed during the process were Co (fcc), Co (hcp), lamellar eutectic phases, M₂₃C₆ and Cr₇C₃ type carbides. The results of the wear tests indicated that the delamination was the dominant mechanism. So, it is necessary to apply an inter-layer between the substrate and top coat.     

Microchemical and microstructural studies in a PTA weld overlay of Ni-Cr-Si-B alloy on AISI 304L stainless steel

Ni-Cr-Si-B alloy coatings deposited on AISI 304L stainless steel substrate using plasma transferred arc welding process were studied with respect to the microchemical and microstructural modifications that take place during the process. The coating was characterized for (1) interface integrity and dilution (2) type, morphology and distribution of secondary phases in the coating (3) elemental redistribution between substrate and coating and (4) different phases that form during the deposition process. Formation of a transition zone of only 760 μm width was understood in terms of interdiffusion of Fe and Ni across the interface. Preferential redistribution of carbon to the surface of the coating was observed. It was explained on the basis of difference in thermodynamic activity. Apart from γ-Ni solid solution, the other primary phases identified in Ni-Cr-Si-B alloy were Cr₂B, Cr₇C₃ and Cr₃C₂. The observed changes in microstructure, microchemistry and hardness have been understood based on the phase transitions of the Ni rich alloy during solidification and cooling on the substrate.     

Properties and Tribological Performance of Vanadium Carbide Coatings on AISI 52100 Steel Deposited by Thermoreactive Diffusion

Vanadium carbide coatings were formed on AISI 52100 steel specimens by thermoreactive diffusion and characterized using nanoindentation, x-ray diffraction, and chemical analysis. The deposition process formed a 4-µm coating of vanadium carbide (V₄C₃) with an average grain size of 33 nm and a [200] crystallographic texture. The hardness and elastic modulus of the coatings were determined to be 35 ± 7.5 GPa and 334 ± 67 GPa, respectively. Friction and wear of the coatings were examined in reciprocating sliding contact against tungsten carbide (WC) balls in dry and in an abrasive environment. It was determined that in the abrasive environment, the V₄C₃ coating provided wear protection comparable to WC.     

碳化硼对电弧喷涂涂层性能的影响

将碳化硼(B4C)陶瓷粉末和其它合金元素与304L不锈钢带轧制成粉芯丝材,采用电弧喷涂技术制备金属陶瓷复合涂层.研究了B4C在电弧喷涂中的应用.利用XRD,SEM对涂层的形貌、相组成和磨损表面进行了分析.利用自行设计的高温磨粒磨损装置和高温冲蚀设备分别评价了B4C对涂层耐高温磨粒磨损性能和耐高温冲蚀性能的影响.结果表明,粉芯丝材喷涂工艺良好,B4C陶瓷与粉芯中其它组分反应,可以形成含Fe3B,CrB,FexN i23-xB6,Fe23(C,B)6,(Cr,Fe)7C3和Fe3C等硬质相的复合涂层,大幅度提高了涂层的硬度和耐磨耐冲蚀性能.     

Cemented carbide surface modifications using laser treatment and its effects on hard coating adhesion

A pulsed HyBrID copper laser (510 nm, 30 ns, 13.8 kHz) was used for the treatment of cemented carbide substrate before deposition of TiCN/Al₂O₃/TiN coating by the MT-CVD process. The influence of the laser treatment on the surface morphology, surface structure and coating adhesion was investigated based on the laser irradiation dynamics used here. The experimental results showed that a large variety of cemented carbide surface textures could be obtained, depending on the laser intensity and number of applied laser pulses. Moreover, this laser process was found to produce some less carbon non-stoichiometric WC phases such as β-WC_1 − x and α-W₂C. Finally, using the Rockwell C adhesion test as output criteria, two sets of laser parameters were identified that produced a surface with adhesion strength comparable to that of commercial tools pretreated by micro-sandblasting.     

Thermal-sprayed Fe-10CM3P-7C amorphous coatings possessing excellent corrosion resistance

An alloy of Fe-10Cr-13P-7C was thermally sprayed by three different processes: (1) 80 kW low-pressure plasma spraying (LPPS), (2) high-velocity oxyfuel (HVOF) spraying, and (3) 250 kW high-energy plasma spraying (HPS). The as-sprayed coating obtained by the LPPS process was composed of an amorphous phase. In contrast, the as-sprayed coatings obtained by the HVOF and HPS processes were a mixture of amorphous and crystalline phases. The as-sprayed coatings showed a high hardness of 700 DPN. A very fine structure composed of ferrite, carbide, and phosphide was formed, producing a maximum hardness of greater than 1000 DPN in the LPPS coating just after crystallization on tempering. The corrosion re-sistance of the amorphous coating was superior to a SUS316L stainless steel coating in 1N H₂SO₄ solution and 1N HC1 solution. Furthermore, the amorphous coating underwent neither general nor pitting corro sion in1NUCI solution and 6% FeCl₃ 6H₂O solution containing 0.05N HCl, whereas the SUS316L stain less steel coating was attacked aggressively.     

Analytical Studies on the Behavior of Nickel- and Cobalt-Base Shrouded Plasma Spray Coatings at Elevated Temperature in Air

Nickel- and Cobalt-base coatings were developed on boiler-tube steels by the argon-shrouded, plasma spray process. The cyclic behavior of bare and coated boiler-tube steels has been studied in air at 900 °C. Four types of coatings were used: Ni-22Cr-10Al-1Y (NiCrAlY), Ni-20Cr, Ni₃Al and Stellite-6 (St-6). The NiCrAlY has also been used as a bond coat of approximately 150 μm thick before the final coating in all the cases. Oxidation products analyzed in the scale are mostly oxides of the elements present in the coatings and substrate steels. NiCr₂O₄ and CoCr₂O₄ spinels are the most-common observed phases in the scale for nickel- and cobalt-base coatings. The internal oxidation of coatings and diffusion of iron from the base steel to the upper scale occurred during the study. Cracks formed in the scale and coating and may be due to differences in composition of coatings, bond coat, substrate and oxides formed.     

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.     

Properties and tribological performance of ceramic-base chromium and vanadium carbide composite coatings

In the current study, the surface of AISI D2 steel was coated with the powder blends of ferro-vanadium (Fe-V) and ferro-chromium (Fe-Cr). The coatings were performed using a thermo-reactive diffusion (TRD) treatment by the pack cementation method at three different temperatures (900 °C, 1000 °C, and 1100 °C) and three different durations (1 h, 2 h, and 3 h). The structural and mechanical characteristics of the coatings were compared between the treatment groups. For this aim, the types of the formed phases, the microstructure, the microhardness, the surface roughness, and the wear and friction performance of the coated samples were examined. XRD analysis found composite carbide coatings including chromium carbide (Cr-C), vanadium carbide (V-C), and chromium vanadium carbide (Cr-V-C). The coatings' thickness was 11.3–23.2 μm, hardness was 2100–2500 HV, and average surface roughness (R_a) was 0.286–0.550 μm, depending on the treatment condition. The vanadium containing phase contents of the coatings increased with the elevating coating temperatures. The formed composite coating layers caused a change in the appearance of wear track and wear mechanism on the material surface. After the coating process, there found to be a decrease in the friction coefficient as well as an improvement in the wear resistance up to 7 times. In the composite coating layers, the increase in V-C content in comparison to Cr-C led to an enhancement in wear resistance on the material surface.     

Structure and phases in nickel-base self-fluxing alloy coating containing high chromium and boron

The structure of a nickel-base, self-fluxing alloy coating, containing chromium and boron thermal sprayed and fused, was investigated by x-ray diffraction (XRD), scanning electron microscopy (SEM), electron probe microanalysis (EPMA), and transmission electron microscopy (TEM). A lumpy M₆C carbide, a rodlike M₃B₂ boride of tetragonal structure, a rodlike M₇C₃ carbide of hexagonal structure, and a Ni-Ni₃B eutectic phase formed in the coating after fusing. Metals of M₆C, M₃B₂, and M₇C₃ phases are composed of chromium, molybdenum, and nickel; chromium and molybdenum; and mainly chromium, respectively. The nickel phase in the coating has the L1₂ type superlattice structure.     

Effects of relative humidity on tribological properties of boron carbide coating against steel

Boron carbide coatings of 100 nm thick were synthesized on silicon substrate by DC magnetron sputtering using B₄C target with a mixture of Ar and methane (CH₄ at 1.2 vol.%) as processing gases. Tribological properties of the coating were studied in relation to the effects of relative humidity (RH). Reciprocating wear tests using 3 mm diameter steel balls as a counterpart were carried out at three relative humidity conditions. Confocal microscopy was used to observe worn surfaces and the wear scars on the steel balls. Elemental composition of the coating and worn surfaces were characterized using X-ray photoelectron spectroscopy and Auger electron spectroscopy. The tribological properties of boron carbide coating slid against steel ball were strongly affected by relative humidity. Lower and steady friction coefficient and higher wear resistance for both the coating and the steel ball were achieved at higher relative humidity. At high RH, tribochemical reaction occurred in the sliding surfaces, forming boric acid and carbon in a graphitic form on the worn surface of coating and a soft layer on the ball surface. The formation of boric acid on boron carbide coating combined with graphite structure led to the low and stable friction of boron carbide coating in medium and high relative humidity conditions. Smooth layer was formed on the worn surface of the steel ball at high relative humidity due to the tribochemical reaction. Low and steady value of friction coefficient and reduction of wear loss of both steel ball and boron carbide coating were attributed to the formation of the soft layer.     

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.     

Comparative Analysis of the Microstructural Features of 28 wt.% Cr Cast Iron Fabricated by Pulsed Plasma Deposition and Conventional Casting

The effect of pulsed plasma deposition (by an electrothermal axial plasma accelerator) followed by post-heat treatment on the structure and microhardness of a 28 wt.% Cr white cast iron is analyzed and discussed with respect to the microstructure of the conventionally cast monolithic counterpart. The cast iron (as deposited on a 14 wt.% Cr cast iron substrate) had a microhardness of 630-750 HV_0.05; it had layered light contrast/dark contrast structure where dark contrast layers contain fine carbide network. Pulsed plasma deposition followed by heat treatment resulted in a substantial refinement of the microstructure: eutectic M₇C₃ coarse acicular plates in the conventional cast iron were replaced by fine M₇C₃, M₃C₂, M₃C particles (Cr depleted in favor of Fe), while the initial carbide particle of 2-3 μm was reduced to 0.6 μm. Secondary dendrite arm spacing decreased from 15 to 1.3 μm, accordingly. The carbide volume fraction in the post-heat-treated coating remarkably increased with respect to the conventional counterpart resulting in a substantial increase in the coating hardness (1300-1750 HV_0.05). The heat-treated coating displayed higher resistance to three-body abrasion than the as-deposited coating and similar resistance with that of the conventionally cast iron.     

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.     

Characterization of plasma sprayed Fe-10Cr-10Mo-(C,B) amorphous coatings

Alloys of Fe-10Cr-10Mo containing a large amount of carbon and/or boron were plasma sprayed by low-pressure plasma spraying (LPPS) and high-energy plasma spraying (HPS). The as-sprayed coatings obtained by the LPPS process are composed of only an amorphous phase, while as-sprayed coatings obtained by the HPS process are a mixture of amorphous and crystalline phases. The amorphous phase in these coatings crystallizes on tempering at about 773 to 873 K, and the crystallization temperatures depend on the content of carbon and boron. Thermal stability of the amorphous phase containing boron is higher than those phases containing carbon. A very fine mixed structure of ferrite and carbide, borocarbide, or boride is formed by decomposition of the amorphous phase, bringing about a hardness of 1200 to 1400 DPN (Vickers hardness). The coatings containing carbon retain a hardness of more than 1000 DPN, even on tempering at temperatures of 1073 K or higher. The anodic polarization behavior of the coatings exhibits an activation-passivation transition in 1N H₂SO₄ solution. The active and passive current densities of the as-sprayed amorphous and tempered crystalline coatings containing carbon is lower than the coatings containing boron. The corrosion resistance of the as-sprayed and crystallized coatings containing carbon is superior to a SUS316L stainless steel coating.     

Rapidly solidified non-equilibrium microstructure and phase transformation of plasma cladding Fe-based alloy coating

The rapidly solidified microstructural and compositional features, the precipitation and transformation of carbides during aging of Fe-based alloy coating prepared by plasma cladding have been investigated. The clad coating materials, whose powder mixture of Fe, Cr, Ni, B, Si and C with a weight ratio of 54.5:35:5:1:2:2.5, is processed using a non-transferred plasma arc. The clad coating adheres with low carbon steel in a good metallurgical bonding and the rate of dilution is 15-20%. Microstructural studies demonstrate that the coating possesses the metastable microstructure comprising the primary dendritic γ-austenite which is a non-equilibrium phase with an extended solid solution of alloying elements and interdendritic eutectic consisting of γ-austenite and (Cr,Fe)₇C₃ carbides. During the high temperature aging at 1253 K for 2 h, the fine spherical (Cr,Fe)₂₃C₆ carbide nucleates within (Cr,Fe)₇C₃ carbide and austenite matrix, and some martensite (α) also forms during cooling. The solidification and evolution sequence of the phase can be represented as follows: L → γ + L → γ + (γ + (Cr,Fe)₇C₃) → (γ + (Cr,Fe)₂₃C₆ + α). Due to the precipitation of (Cr,Fe)₂₃C₆ carbide and uniform distribution of carbide in the as-aged coating, the average hardness becomes higher than that of the as-clad coating.     

Tialite formation from its quasi-amorphous stoichiometric co-precipitated powder by thermal spray process

In this work, the formation of tialite from powders obtained by the co-precipitation method with inorganic salts was investigated. For the co-precipitation process, a solution of aluminum nitrate (Al(NO₃)₃  9H₂O) and titanium tetrachloride (TiCl₄) in ethyl alcohol was co-precipitated with an increase in ammonium hydroxide base. Phase transformations of the quasi-amorphous dried gel with stoichiometric composition of tialite treated in a muffle furnace and in an atmospheric plasma thermal spray deposition were explored. The effect of calcination thermal treating on the tialite formation was evaluated for different temperatures (400, 600, 800, 900, 1000, 1200, 1300, and 1400 °C). The powder was thermally treated by calcination at 600 °C for 6 h prior to the thermal spray process. Dried gel pieces were also calcined at 600 °C for 6 h and ground, the produced powders were thermally sprayed onto a stainless steel substrate and the formed coating was mechanically detached from the substrate and then characterized. It was confirmed that the thermal spray process transformed the quasi-amorphous powders to single tialite phase. The absence of the corundum and rutile phases was attributed to the high heating and cooling rates (~ 10⁶ K/s) supplied by thermal spray processing.     

Photocatalytic Activity of Nanostructured Anatase Coatings Obtained by Cold Gas Spray

This article describes a photocatalytic nanostructured anatase coating deposited by cold gas spray (CGS) supported on titanium sub-oxide (TiO_2?x ) coatings obtained by atmospheric plasma spray (APS) onto stainless steel cylinders. The photocatalytic coating was homogeneous and preserved the composition and nanostructure of the starting powder. The inner titanium sub-oxide coating favored the deposition of anatase particles in the solid state. Agglomerated nano-TiO₂ particles fragmented when impacting onto the hard surface of the APS TiO_2?x bond coat. The rough surface provided by APS provided an ideal scenario for entrapping the nanostructured particles, which may be adhered onto the bond coat due to chemical bonding; a possible bonding mechanism is described. Photocatalytic experiments showed that CGS nano-TiO₂ coating was active for photodegrading phenol and formic acid under aqueous conditions. The results were similar to the performance obtained by competitor technologies and materials such as dip-coating P25^® photocatalysts. Disparity in the final performance of the photoactive materials may have been caused by differences in grain size and the crystalline composition of titanium dioxide.