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.     

Vacuum sintering of WC-8 wt.% Co hardmetals from WC powders with different dispersity

The effect of sintering temperature and particle size of tungsten carbide WC on phase composition, density and microstructure of hardmetals WC-8 wt.% Co has been studied using X-ray diffraction, scanning electron microscopy and density measurements. The sintering temperature has been varied in the range from 800 to 1600 °C. The coarse-grained WC powder with an average particle size of 6 μm, submicrocrystalline WC powder with an average particle size of 150 nm and two nanocrystalline WC powders with average sizes of particles 60 and 20 nm produced by a plasma-chemical synthesis and high-energy ball milling, respectively, have been used for synthesis of hardmetals. It is established that ternary Co₆W₆C carbide phase is the first to form as a result of sintering of the starting powder mixture. At sintering temperature of 1100-1300 °C, this phase reacts with carbon to form Co₃W₃C phase. A cubic solid solution of tungsten carbide in cobalt, β-Co(WC), is formed along with ternary carbide phases at sintering temperature above 1000 °C. Dependences of density and microhardness of sintering hardmetals on sintering temperature are found. The use of nanocrystalline WC powders is shown to reduce the optimal sintering temperature of the WC-Co hardmetals by about 100 °C.     

Laser surfacing of nickel-based composite war-resisting coatings reinforced with tungsten carbide

Investigations were carried out into the phase and structural state of the gradient coating produced by laser surfacing using tungsten carbide powders in a cobalt coating and a nickel alloy. The results show that the structure contains the WC carbide with the particles of the carbide forming spherical agglomerates, a nickel solid solution, alloyed with iron and cobalt, Me₂W₆ intermetallic phase, where Me = Fe, Cr and also CrO₂ oxide. It is shown that the layers after reheating are characterized by the more extensive dissolution of the carbide and agglomerates and the formation of chromium-containing inclusions. The distribution of the elements and microhardness values in the cross section of the deposited coating was determined.     

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.     

Enhancing the adhesion of diamond films on cobalt-cemented tungsten carbide substrate using tungsten particles via MPCVD system

To increase the adhesion of diamond films and avoid the negative effects of using cobalt, previous treatments have employed tungsten particles to cover the surface of the 6 wt.% cobalt-cemented tungsten carbide (WC-Co) substrate. The surface of the tungsten particles is transformed into W₂C and WC, which attracts and traps carbon. Through the process of nucleation, the carbon forms around the tungsten particles, thereby satisfying the conditions necessary for the formation of diamond film. Using Raman spectroscopy, we determined that diamond films of good quality with excellent adhesive properties and a hardness level as high as 27.78 GPa could be produced following pretreatment with 2.0 μm tungsten particles. Rockwell indentation tests indicate that addition of tungsten particles promotes the interfacial adhesion of diamond films with WC-Co substrates. We determined that using smaller tungsten particles decreased the number of gaps and cavities on the surface of the substrate, thereby enhancing the adhesion of the diamond film.     

Fabrication and microstructural characterization of nano-structured WC/Co coatings

In the present investigation, the microstructure of nano tungsten carbide/cobalt (WC/Co) coating layers fabricated by detonation-gun spraying has been studied. Phase identification and three-dimensional distribution of constituent elements have been accomplished by using an ultra high-resolution transmission electron microscope (TEM) and a three-dimensional atom probe tomography (3D-APT), respectively. The microstructures of WC/Co coating layer containing superfine carbides were observed in various forms, i.e., unmelted, partially melted and fully melted regions. TEM and APT results revealed that the WC phase has been decomposed into crystalline W₂C, W and complex amorphous phases during high temperature detonation spraying and rapid quenching process.     

Synthesis of nanostructured tungsten carbide via metal-organic chemical vapor deposition and carburization process

Nanostructured tungsten carbide particles were successfully synthesized by metal-organic chemical vapor deposition in a spouted bed followed by carburization in CH₄/H₂ atmosphere in the temperature range 700–900 °C. The carburization process was a little bit complex, which involved the coating of carbon on the outer surface of the decomposed W(CO)₆ precursor particles and then followed by carbon diffusion into the particles, leading to the formation of nanostructured WC via an intermediate metastable phase W₂C. The carbon deficient phase W₂C was formed initially at lower carburization temperature and then transformed to stable WC phase by increasing the temperature and holding time.     

Characterization of plasma sprayed Fe-17Cr-38Mo-4C amorphous coatings crystallizing at extremely high temperature

A Fe-17Cr-38Mo-4C alloy powder was plasma sprayed by three processes: an 80 kW low-pressure plasma spray (LPPS), a 250 kW high-energy plasma spray (HPS), and a 40 kW conventional plasma spray (APS). The as-sprayed coating obtained by the LPPS process is composed of only amorphous phase. As-sprayed coatings obtained by the HPS and APS processes are a mixture of amorphous and crystalline phases. The three as-sprayed coatings exhibit a high hardness of 1000 to 1100 DPN. The amorphous phase in these coatings crystallizes at a high temperature of about 920 K. A very fine structure composed of hard ϰ-phase and carbides is formed after crystallization. The hardness of the coating obtained by LPPS reaches a maximum of 1450 DPN just after crystallization on tempering and retains a high hardness more than 1300 DPN after tempering at high temperatures of 1173 or 1273 K. The corrosion potential of the amorphous coating is the highest among the three coatings and higher than that of a SUS316L stainless steel coating. The anodic polarization measurements infer that the corrosion resistance of the amorphous coating is superior or comparable to SUS316L stainless steel coating in H₂SO₄ solution.     

Chemical and Phase Composition of Powders Obtained by Electroerosion Dispersion from WC – Co Alloys

The dependence of the chemical and phase composition of dispersed powders on the mode and medium of electroerosion dispersion and the content of cobalt in the initial alloy is considered. It is shown that the dissociation of carbon from tungsten carbide occurs even in dispersion in liquid hydrocarbon-bearing media (kerosene and industrial oils). The phase composition is primarily determined by the dispersion medium and the content of cobalt in the initial alloy. Compound tungsten-cobalt carbides and even a Co₇W₆ intermetallic are determined in all the powders.     

电弧电压对低能等离子喷涂WC-Co涂层组织及性能的影响

使用烧结破碎的WC-12%Co粉末,采用轴向送粉等离子喷涂系统制备WC-Co涂层。保持电弧电流不变,增加工作气体中的氢气含量来提高电弧电压,以研究电弧电压对于涂层微观结构的影响。使用X射线衍射仪(XRD)分析WC-Co涂层的脱碳相变,使用扫描电子显微镜(SEM)观察粉末的熔化程度、扁平化状态和涂层的微观结构,使用MH-6维氏硬度计和MM200磨损试验机分别测量了涂层的显微硬度和耐磨性。结果表明,提高电弧电压有利于粉末的熔化。根据熔化程度的不同,粉末会呈现四种典型的扁平化状态。提高电弧电压促使碳化钨脱碳生成的W_2C和Co_3W_9C_4,涂层中硬质相体积增加,钴基体积减小。适当提高电弧电压有利于增加涂层的硬度和耐磨性,但过高的电弧电压会恶化涂层质量,反而降低涂层的硬度和耐磨性。     

Synthesis of Cr-doped APT in the evaporation and crystallization process and its effect on properties of WC-Co cemented carbide alloy

WC grain size has significant effect on WC-Co cemented carbide alloy properties. In order to inhibit WC grain growth during sintering process, grain growth-inhibitor Cr₃C₂ is usually added to tungsten carbide powder in advance through mechanical milling. While, homogeneous distribution of Cr₃C₂ in the tungsten carbide powder is difficult to achieve and result in abnormal growth of WC grains. For this purpose of growth-inhibitor uniform distribution, (CH₃COO)₃Cr is added into ammonium tungstate solution during evaporation and crystallization process to prepare Cr-doped APT powder, which can be used as precursor for ultrafine-grained WC-Co cemented carbide alloy preparation. Compared with conventional APT powder, the Cr-doped APT has smaller particle size and bulk density, moreover, chromium is evenly distributed within it. The Cr-doped APT is then used to produce Cr-doped tungsten powder, which also has smaller particle size than that of conventional tungsten powder. Cr-doped tungsten powder is subsequently prepared into tungsten carbide powder and WC-Co cemented carbide alloy through carbonization and sintering process, respectively. Compared with conventional WC-Co cemented carbide alloy, the obtained WC-Co cemented carbide alloy has smaller mean WC grain size (0.36 μm), and more uniform microstructure. Furthermore, the phenomenon of WC grain abnormal growth during sintering process is not observed, because the grain growth-inhibitor Cr₃C₂ is well dispersed in tungsten carbide and cobalt composite powder. Results show that the obtained WC-Co cemented carbide alloy presents better mechanical properties (HRA, bending strength, coercive force) than those of conventional WC-Co cemented carbide alloy. Accordingly, the novel addition of (CH₃COO)₃Cr during the evaporation and crystallization process is the key factor of ultrafine-grained WC-Co cemented carbide alloy production.     

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.     

Formation of amorphous Fe-Cr-Mo-8P-2C coatings by the high velocity oxy-fuel process

Alloy powders of Fe-10%Cr-8%P-2%C(10Cr), Fe-20%Cr-8%P-2%C(20Cr), and Fe-10%Cr-10%Mo-8%P-2%C(10Mo) compositions (in mass%) were sprayed by the high velocity oxy-fuel (HVOF) process under different conditions. The as-sprayed coatings of 10Mo alloy were composed of only an amorphous phase under all the spray conditions, while the as-sprayed coatings of the 10Cr and 20Cr alloys consisted of an amorphous phase with a small amount of crystalline material. The volume fraction of the crystalline material increased slightly with the rise of the flame temperature. The hardnesses of the as-sprayed coatings of the 10Cr and 20Cr alloys were 600 to 700 DPN, respectively, while the 10Mo coating composed of an amorphous phase revealed 560 DPN. The corrosion resistance of the as-sprayed coating of the 10Mo alloy was the best among three amorphous coatings and also superior to the nickel-base self-fluxing alloy and SUS316L stainless steel coatings in 1N H₂SO₄ and 1N HCl solutions.     

Recycling of WC-Co hardmetal sludge by a new hydrometallurgical route

A hydrometallurgical process based on aqua regia treatment of WC-Co hardmetal sludge was developed to simultaneously extract cobalt in solution and forming tungstic acid as residue in a single step. The parameters such as aqua regia concentration, temperature and time of reaction, and pulp density were optimized to process the sludge containing 60.9 wt.% W, 5.99 wt.% Co, 3.38 wt.% Fe and 12.64 wt.% C as the major components. Almost complete leaching of cobalt was achieved with 100 vol.% of aqua regia at 100 °C temperature, 60 min reaction time and 400 g/L pulp density. Complete conversion of tungsten carbide of the sludge to tungstic acid was observed at and below the pulp density of 150 g/L under this condition. The progress of reaction and conversion of tungsten carbide to tunstic acid (H₂WO₄) were investigated by XRD phase identification of the residues under different conditions. The tungstic acid produced from the acid treatment was purified by dissolving tungsten in 11.20 mol/L of ammonia solution at 60 °C while rejecting insoluble metallic impurities as a residue. Tungsten from the ammoniacal solution was recovered by evaporation-crystallization process as high purity (99.97%) ammonium paratunstate (APT, (NH₄)₁₀·H₂W₁₂O₄₂·4H₂O) with low levels of impurities.     

一种新型经济高效非晶涂层的制备与性能表征

利用火焰喷涂技术喷涂自制的气雾化合金粉末取代非晶粉末,制备了NiFeBSiNb非晶纳米晶涂层。分别对粉末和涂层的微观组织结构和热力学性能进行了表征。结果表明,自制的合金粉末球形度较好,大多为球形或椭球形;主要为晶体结构,由Nb₂Ni₂₁B₆晶体相和(Ni,Fe)₂₃B₆固溶体组成。而经过火焰喷涂制备的涂层,形成了非晶相和纳米晶相。通过公式计算此合金体系粉末和涂层形成非晶相的临界冷却速率分别为6.01×10₅K/s和4.56×10₃K/s,解释了在粉末制备过程中较难形成非晶相而喷涂过程中形成非晶结构比较容易。对涂层的摩擦磨损性能进行了测试,涂层摩擦系数仅为0.17,具有优异的耐磨性能。     

大气等离子喷涂制备Fe基非晶涂层及微观结构表征

选用Fe-10W-4Cr-3Ni-2Mo-4B-4Si-1C(质量比)合金粉末作为喷涂原料,采用大气等离子喷涂工艺在1Cr18Ni9Ti不锈钢基底上制备了Fe基涂层。利用扫描电镜、透射电镜和X射线衍射仪表征了粉末和涂层的相组成和微观形貌;用Olycia m3分析软件对涂层的孔隙率进行测定;用热分析系统对喷涂粉末和涂层从室温到1 173K范围的DSC曲线进行记录;同时,测定了涂层的显微硬度和结合强度。结果表明:大气等离子喷涂制备的Fe基涂层与基底的结合良好,涂层较为致密并且存在灰色氧化带组织,表现出典型的层状组织结构;涂层不但具有低的表面粗糙度和孔隙率,而且具有高的显微硬度和结合强度;所制备涂层中的非晶含量约为89.2%(质量分数),涂层中形成的晶相组织为纳米晶结构。     

Microstructural evaluation of tungsten carbide-cobalt coatings

Tungsten carbide-12 wt.% cobalt coatings were deposited using optimized high-energy plasma (HEP) and high-velocity oxygen fuel (HVOF) thermal spray techniques. The coatings were evaluated using transmission electron microscopy, differential thermal analysis, X-ray diffraction, and subjected to wear tests to relate the coating structure to wear performance. Coatings were evaluated in the assprayed condition, as well as after heat treatments in inert atmosphere. The results indicate that a substantial amount of amorphous matrix material is created during the thermal spray process. Carbon and tungsten, liberated through the dissociation of the WC, combine with cobalt present in the starting powder to form amorphous material on solidification. Differential thermal analysis revealed an exothermic reaction for both the HVOF and HEP coatings at approximately 853 and 860 °C, respectively, which did not occur for the powder. Post-coating heat treatment in an inert atmosphere resulted in the recrystallization of the amorphous material into Co₆W₆C and Co₂W₄C, which was dependent on the time and temperature of the heat treatment. Wear testing showed improvement in the wear performance for coatings that were subjected to the heat treatment. This was related to the recrystallization of the amorphous matrix into eta phase carbides. Editor’s Note: This paper was presented at the 4th National Thermal Spray Conference, Pittsburgh, 6-10 May, 1991. The proceedings of this conference will be published by ASM International. Dr. T.F. Bernecki is the Editor of these proceedings.     

Microstructure refinement and alloying of WC-CoCr coatings by electron beam treatment

The corrosion and wear behaviour of HVOF (high velocity oxygen fuel) sprayed WC-CoCr (cermet) coatings were investigated before and after electron beam (EB) remelting. In this regard, the coatings were deposited on INCONEL 617 substrate. The mentioned Ni-based alloy is well known for its good corrosion behaviour in chloride containing media but exhibits not enough good wear properties.The paper investigates the influence of EB-remelting process on sliding wear respectively on corrosion resistance in 1 M NaCl solution of the alloyed surface. Scanning electron microscopy (SEM) and X-Ray Diffraction (XRD) were performed before respectively after the EB-treatment in order to investigate the coating morphology as well as the phase modification achieved through the alloying process. Tribological tests concerning the sliding wear behaviour of the tested materials revealed a significant decrease of the wear rate for both the as-sprayed coating respectively the alloyed surface in comparison with the base material. However, the as-sprayed cermet coating exhibits the lowest wear rate among the investigated samples.The microhardness of the alloyed surface was higher (1100 HV₀₃) in comparison with that of the as-sprayed cermet coating (905 HV₀₃) as a result of new phase formation (especially the η-Co₄W₂C). The corrosion behaviour in salt water of the EB remelted surface was also considerably improved in contrast to the as-sprayed cermet coating.     

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

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

Synthesis of WC-Co composite powders with two-step carbonization and sintering performance study

In this study, WC-Co composite powder was synthesized by two-step carbonization method using W, Co and C as raw materials. X-ray diffraction (XRD) showed that the η phase (Co₆W₆C) was kept at 1100 °C for 1 h under vacuum, and it could be completely carbonized into WC-Co composite powders. The surface morphology of WC-Co composite powders was analyzed by scanning electron microscope (SEM). The effects of η phase and second phase (W phase) on WC morphology and Co phase distribution were investigated. Electron backscattered diffraction (EBSD) was used to analyze WC-10 wt% Co cemented carbide particle distribution. Comparison of transverse rupture strength, hardness and fracture toughness of two kinds of WC-10 wt% Co cemented carbides synthesized by WC-Co composite powders + WC and WC + Co respectively, the cemented carbide of composite powders + WC increases the fracture toughness from 11.4 ± 0.3 MPa·m^1/2 to 12.4 ± 0.3 MPa·m^1/2.