Thermally Sprayed CaZrO3 Coatings

A comparative study of CaZrO₃ coatings prepared by air plasma and flame spray processes is presented. The microstructural characteristics and phases were analyzed and discussed as a function of the spraying temperature achieved with each technique. Vickers hardness tests performed on polished cross sections of the different coatings were used to estimate their porosity. Thermal diffusivity values measured on freestanding thick coatings (500 μm) using the laser flash technique were very low and depended strongly on the pore shape. Crystallization was promoted by treating the coatings at 1200 °C, and the results are explained with aid of the ZrO₂-CaO equilibrium phase diagram.     

Nonlinear Behavior in Compression and Tension of Thermally Sprayed Ceramic Coatings

Mechanical properties of thermally sprayed coatings, especially of ceramics, are strongly influenced by a high density of mesoscopic defects, microcracks of dimensions between fractions of μm up to tens of μm. The anisotropic linear elastic stress–strain relations are valid only at very low deformations, e.g., |e| < 0.05%, with small values of Young’s moduli due to elastic openings and elastic partial closings of microcracks. At higher deformations, e.g., 0.05% < |e| < 0.4%, the stress–strain relations are strongly nonlinear. Under compressive stresses, elastic closing of microcracks leads to a gradual decrease of the microcrack density and to an increase of Young’s modulus in compression. Under tensile stresses, the microcracks slightly grow by inelastic processes; the microcrack density gradually increases and effective Young’s modulus in tension decreases. A two-parametric equation containing linear and quadratic terms is used to describe the nonlinear stress–strain curves of plasma-sprayed ceramic coatings. The effect of nonlinearity on the bending of beams with coatings and the nonlinear combination of external and residual stresses are discussed. The fracture of coatings at higher tensile stresses due to coalescence of the microcracks is mentioned.     

From Powders to Thermally Sprayed Coatings

Since the early stages of thermal spray, it has been recognized that the powder composition, size distribution, shape, mass density, mechanical resistance, components distribution for composite particles play a key role in coating microstructure and thermo mechanical properties. The principal characteristics of particles are strongly linked to the manufacturing process. Coatings also depend on the process used to spray particles and spray parameters. Many papers have been devoted to the relationships existing between coating properties and structures at different scales and manufacturing processes. In many conventional spray conditions resulting in micrometric structures, among the different parameters, good powder flow ability, and dense particles are important features. Thermal plasma treatment, especially by RF plasma, of particles, prepared by different manufacturing processes, allows achieving such properties and it is now developed at an industrial scale. Advantages and drawbacks of this process will be discussed. Another point, which will be approached, is the self-propagating high-temperature synthesis, depending very strongly upon the starting composite particle manufacturing. However, as everybody knows, “small is beautiful” and nano- or finely structured coatings are now extensively studied with spraying of: (i) very complex alloys containing multiple elements which exhibit a glass forming capability when cooled-down, their under-cooling temperature being below the glass transition temperature; (ii) conventional micrometer-sized particles (in the 30-90 μm range) made of agglomerated nanometer-sized particles; (iii) sub-micrometer- or nanometer-sized particles via a suspension in which also, instead of particles, stable sol of nanometer-sized particles can be introduced; and (iv) spray solutions of final material precursor. These different processes using plasma, HVOF or sometimes flame and also cold-gas spray will be discussed together with the production of nanometer-sized particles via the chemical reaction method or by a special type of milling: the cryogenic milling process often referred to as “cryomilling.”     

热喷涂NiCoCrAlYTa+7YSZ热障涂层颗粒沉积行为

分别采用低压等离子喷涂和大气等离子喷涂在K4169基体上收集了NiCoCrAlYTa颗粒沉积物及涂层,并对颗粒沉积物的形貌及涂层性能进行了观察分析。结果表明:低压等离子喷涂收集到的单个NiCoCrAlYTa扁平颗粒主要呈圆盘状,涂层致密且氧含量低。而大气等离子喷涂收集到的扁平颗粒主要呈溅射状,涂层孔隙率和氧含量均较高。又在经镜面抛光的NiCoCrAlYTa涂层和K4169基体上分别收集了7YSZ颗粒沉积物,并对其沉积形貌进行了观察分析,结果表明:在K4169基体上收集到的7YSZ颗粒沉积物主要呈圆盘状,表面存在大量的网状微裂纹及宏观环状贯通裂纹。在镜面抛光的NiCoCrAlYTa涂层表面收集的7YSZ颗粒沉积物,周围有少量的指状溅射物,中心部存在一定数量的网状微裂纹,但宏观环状裂纹消失。     

Surface Pre-treatment for Thermally Sprayed ZnAl15 Coatings

Pre-treatment of substrates is an important step in thermal spraying. It is widely accepted that mechanical interlocking is the dominant adhesion mechanism for most substrate-coating combinations. To prevent premature failure, minimum coating adhesion strength, surface preparation grades, and roughness parameters are often specified. For corrosion-protection coatings for offshore wind turbines, an adhesion strength ≥ 5 MPa is commonly assumed to ensure adhesion over service lifetime. In order to fulfill this requirement, Rz > 80 µm and a preparation grade of Sa3 are common specifications. In this study, the necessity of these requirements is investigated using the widely used combination of twin-wire arc-sprayed ZnAl15 on S355J2 + N as a test case. By using different blasting media and parameters, the correlation between coating adhesion and roughness parameters is analyzed. The adhesion strength of these systems is measured using a test method allowing measurements on real parts. The results are compared to DIN EN 582:1993, the European equivalent of ASTM-C633. In another series of experiments, the influence of surface pre-treatment grades Sa2.5 and Sa3 is considered. By combining the results of these three sets of experiments, a guideline for surface pre-treatment and adhesion testing on real parts is proposed for the considered system.     

Colour Matching in Decorative Thermally Sprayed Glass Coatings

Coloured coatings were obtained on steel by plasma spraying without severe in-flight alteration of pigments, taking profit of the low thermal conductivity of the glassy matrix of glaze particles. Colour matching was studied by mixing 3 different glazes, comparing Grassmann and Kubelka-Munk based algorithms. Results suggest that the latter method should be preferred upon Grassmann method, particularly when the light absorption/dispersion ratios of coloured feedstocks are very different.     

Thermally Sprayed Coatings as Interlayers for DLC-Based Thin Films

This article examines the usefulness of a thick thermally sprayed interlayer (plasma-sprayed Ni-50%Cr, plasma-sprayed Al₂O₃-13%TiO₂, or high-velocity oxygen-fuel-sprayed WC-17%Co) for enhancing the wear resistance and the corrosion protectiveness of a diamond-like carbon (DLC)-based thin film deposited onto a carbon steel substrate. Scratch tests indicate that the Al₂O₃-13%TiO₂ and WC-17%Co interlayers definitely increase the critical spallation load of the thin film, but the Al₂O₃-13%TiO₂ interlayer itself undergoes brittle fracture under high-contact loads. Accordingly, during ball-on-disk tests at room temperature, no cracking and spallation occur in the DLC-based film deposited onto the WC-17%Co interlayer, whereas the one onto the Al₂O₃-13%TiO₂ interlayer is rapidly removed because the interlayer itself is fractured. At 300 °C, by contrast, the DLC-based film on the Al₂O₃-13%TiO₂ interlayer offers the best tribological performance, possibly thanks to the increased toughness of the ceramic interlayer at this temperature. Electrochemical polarization tests indicate that the thin film/WC-Co systems possess the lowest corrosion current density.     

Sealing HVOF Thermally Sprayed WC-CoCr Coatings by Sol-Gel Methods

The offshore industry faces challenges with corrosion resistance in hydraulic cylinders used in marine environments. Thermal spray coating appears to be a promising technique for replacing electroplated coating in many applications, but the performance of thermal spray coatings in highly corrosive environments must be improved. In the present work, a new sealing method for HVOF WC-CoCr coatings for their application on hydraulic cylinders for marine environments has been tested. The method consists of applying sol-gel solution that can penetrate, fill, and thus seal the pores and cracks in the coating. The sealed coatings have been tested with and without posttreatment and compared with as-sprayed coatings. Open-circuit potential (OCP) and tribocorrosion tests in 3.4% NaCl were performed to evaluate the performance of the sealing method. Both tests showed that the sealed coatings had the best performance.     

Quantitative Topographical Characterization of Thermally Sprayed Coatings by Optical Microscopy

Topography measurements and roughness calculations for different rough surfaces (Rugotest surface comparator and thermally sprayed coatings) are presented. The surfaces are measured with a novel quantitative topography measurement technique based on optical stereomicroscopy and a comparison is made with established scanning stylus and optical profilometers. The results show that for most cases the different methods yield similar results. Stereomicroscopy is therefore a valuable method for topographical investigations in both quality control and research. On the other hand, the method based on optical microscopy demands a careful optimization of the experimental settings like the magnification and the illumination to achieve satisfactory results.     

Modeling Thermal Conductivity of Thermally Sprayed Coatings with Intrasplat Cracks

Thermal spraying is one of the most important approaches for depositing thermally insulating ceramic top coatings for advanced gas turbines due to the low thermal conductivity of the coating resulting from its lamellar structure. The thermal conductivity of the coating has been explained based on the concept of thermal contact resistance and correlated to microstructural aspects such as splat bonding ratio, splat thickness, and the size of the bonded areas. However, the effect of intrasplat cracks on the thermal conductivity was usually neglected, despite the fact that intrasplat cracking is an intrinsic characteristic of thermally sprayed ceramic coatings. In this study, a model for the thermal conductivity of a thermally sprayed coating taking account of the effect of intrasplat cracks besides intersplat thermal contact resistance is proposed for further understanding of the thermal conduction behavior of thermally sprayed coatings. The effect of the intersplat bonding ratio on the thermal conductivity of the coating is examined by using the model. Results show that intrasplat cracks significantly decrease the thermal conductivity by cutting off some heat flux paths within individual splats. This leads to a deviation from the typical ideal thermal contact resistance model which presents cylindrical symmetry. Based on the modified model proposed in this study, the contribution of intrasplat cracks to the thermal resistivity can be estimated to be 42–57 % for a typical thermally sprayed ceramic coating. The results provide an additional approach to tailor the thermal conductivity of thermally sprayed coatings by controlling the coating microstructure.     

Corrosion Behavior of Arc Sprayed Nickel-Base Coatings

In this study, nickel-base cored wires were prepared by using NiCr strip to wrap metal powders of nickel (Ni), chromium (Cr), molybdenum (Mo), and chromium boron (CrB). Nickel-base coatings were prepared by electric arc spraying. Microstructures of Ni-Cr-Mo and Ni-Cr-B coatings were investigated using scanning electron microscopy (SEM), energy-dispersive analysis (EDAX), and x-ray diffraction (XRD) analysis. The coatings have a compact surface and presented a bonding strength higher than 40 MPa. Potentiodynamic polarization measurements and salt-spray test were carried out to determine the corrosion behavior of the coatings. The results showed that Ni-base coatings containing Mo (5%) or B (2-4%) had better antichlorine ion corrosion performance than that of Ni-base coatings without Mo element, and PS45 (Ni-Cr-Ti) coating. The antichlorine ion corrosion coatings could be used for resolving the corrosion protection problem of the equipment and piping contacting sour, alkali, salt liquid in petrochemical engineering applications. 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.     

Thermophysical and Microstructural Studies on Thermally Sprayed Tungsten Carbide-Cobalt Coatings

The development of new hardmetal coating applications such as fatigue-loaded parts, structural components, and tools for metal forming is connected with improvement of their performance and reliability. For modelling purposes, the knowledge of thermophysical, mechanical, and other material data is required. However, this information is still missing today. In this study, the thermophysical data of a WC-17Co coating sprayed with a liquid-fuelled HVOF-process from a commercial agglomerated and sintered feedstock powder from room temperature up to 700 °C was determined as an example. The dependence of the heat conductivity on temperature was obtained through measurement of the coefficient of thermal expansion, the specific heat capacity, and the thermal diffusivity. Heat conductivities ranging from 29.2 W/(mK) at 50 °C to 35.4 W/(mK) at 700 °C were determined. All measurements were performed twice (as-sprayed and after the first thermal cycle) to take into account the structural and compositional changes. Extensive XRD and FESEM studies were performed to characterize the phase compositions and microstructures in the as-sprayed and heat-treated states. Bulk samples obtained by spark plasma sintering from the feedstock powder were studied for comparison.     

Thermally Sprayed SiC Coatings for Offshore Wind Turbine Bearing Applications

Tribological tests were conducted on thermally sprayed silicon carbide (SiC) coatings to investigate its potential on reducing wear in offshore wind turbine bearings. The tests were carried out under dry conditions, 3.5 wt.% NaCl solution, and polyalfaolefin (PAO)-lubricated conditions. In order to obtain good quality SiC coatings, it is compulsory to modify the feedstock to limit SiC decomposition during atmospheric spraying process. The SiC feedstock used in this research has been modified with yttrium aluminum garnet (Y₃Al₅O₁₂) oxide additives that originated from its metal salt precursors. High-frequency pulse detonation (HFPD) technique has been utilized to produce coatings of around 100 μm in thickness. The sliding tests have recorded the lowest coefficient of friction (COF) of 0.15 in PAO condition and the highest COF of 0.50 in dry sliding. The wear tracks morphology show that during dry sliding test, the coatings experience abrasive wear accompanied by tribo-oxidation reaction that initiates crack formation along the splat boundaries. On the other two sliding test conditions (NaCl and PAO), polishing of asperities and some grain plowing from the splats were observed in the wear tracks. Tribochemical wear was found to be the main mechanism producing smooth surfaces. Nevertheless, in all cases, the wear losses were negligible.     

Microstructural Analysis and Transport Properties of Thermally Sprayed Multiple-Layer Ceramic Coatings

Multilayer, graded ceramic/metal coatings were prepared by an air plasma spray method on Ti-6Al-4V, 4140 steel and graphite substrates. The coatings were designed to provide thermal barriers for diesel engine pistons to operate at higher temperatures with improved thermal efficiency and cleaner emissions. A systematic, progressive variation in the mixture of yttria-stabilized zirconia and bondcoat alloys (NiCoCrAlYHfSi) was designed to provide better thermal expansion match with the substrate and to improve thermal shock resistance and cycle life. Heat transfer through the layers was evaluated by a flash diffusivity technique based on a model of one-dimensional heat flow. The aging effect of the as-sprayed coatings was captured during diffusivity measurements, which included one heating and cooling cycle. The hysteresis of thermal diffusivity due to aging was not observed after 100-h annealing at 800 °C. The measurements of coatings on substrate and freestanding coatings allowed the influence of interface resistance to be evaluated. The microstructure of the multilayer coating was examined using scanning electron microscope and electron probe microanalysis.     

Finite Element Simulation of Residual Stress Development in Thermally Sprayed Coatings

The coating buildup process of Al₂O₃/TiO₂ ceramic powder deposited on stainless-steel substrate by atmospheric plasma spraying has been simulated by creating thermomechanical finite element models that utilize element death and birth techniques in ANSYS commercial software and self-developed codes. The simulation process starts with side-by-side deposition of coarse subparts of the ceramic layer until the entire coating is created. Simultaneously, the heat flow into the material, thermal deformation, and initial quenching stress are computed. The aim is to be able to predict—for the considered spray powder and substrate material—the development of residual stresses and to assess the risk of coating failure. The model allows the prediction of the heat flow, temperature profile, and residual stress development over time and position in the coating and substrate. The proposed models were successfully run and the results compared with actual residual stresses measured by the hole drilling method.     

The Use of Acoustic Emission to Characterize Fracture Behavior During Vickers Indentation of HVOF Thermally Sprayed WC-Co Coatings

This paper describes how acoustic emission (AE) measurements can be used to supplement the mechanical information available from an indentation test. It examines the extent to which AE data can be used to replace time-consuming surface crack measurement data for the assessment of fracture toughness of brittle materials. AE is known to be sensitive to fracture events and so it was expected that features derived from the AE data may provide information on the processes (microscale and macroscale fracture events and densification) occurring during indentation. AE data were acquired during indentation tests on samples of a WC-12%Co coating of nominal thickness 300 μm at a variety of indentation loads. The raw AE signals were reduced to three stages and three features per stage, giving nine possible indicators per indentation. Each indicator was compared with the crack profile, measured both conventionally and using a profiling method which gives the total surface crack length around the indent. A selection of the indents was also sectioned in order to make some observations on the subsurface damage. It has been found that reproducible AE signals are generated during indentation involving three distinct stages, associated, respectively, with nonradial cracking, commencement of radial cracking, and continued descent of the indenter. It has been shown that AE can give at least as good a measure of cracking processes during indentation as is possible using crack measurement after indentation.     

Microstructure Control of Thermally Sprayed Co-Based Self-Fluxing Alloy Coatings by Diffusion Treatment

This article describes microstructure control aimed for wear-resistance improvement of Co-based (Co-Cr-W-B-Si) self-fluxing alloy coating by diffusion treatment. The diffusion treatments of thermally sprayed Co-based self-fluxing alloy coating on steel substrate were carried out at 1370-1450 K for 600-6000 s under an Ar gas atmosphere. Microstructural variations of the coating and the interface between the substrate and the coating were investigated in detail. A proper diffusion treatment precipitates two kinds of fine compounds in Co-based matrix. X-ray diffractometer (XRD) and electron probe microanalyzer (EPMA) analysis revealed these precipitates to be a chromium boride dissolving cobalt and a tungsten boride containing cobalt and chromium. The size of each precipitate became larger with increasing treatment temperature and time. A coating with the proper size borides showed a superior wear-resistance. 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.     

Fast Regime Fluidized Bed Machining (FR-FBM) of Thermally Sprayed Coatings

Finishing of thermally sprayed metallic, ceramic, and cermet coatings is required to meet tolerances and requirements on surface roughness in most industrial applications. Conventional machining is a costly and time-consuming process, and is difficult to automate. Therefore, this study investigates and develops a new technique highly amenable for automation: fast regime—fluidized bed machining (FR-FBM). Atmospheric plasma sprayed TiO₂, Cr₂O₃, and HVOF-sprayed WC-17%Co and Tribaloy-800 coatings, deposited on AISI 1040 steel substrates, were subjected to FR-FBM treatment. The effects of the leading operational parameters, namely, abrasive size, jet pressure, and processing time, were evaluated on all coatings by using a two/three-levels full factorial design of experiments. The FR-FBM treated surfaces were observed by FE-SEM and their surface finishing was evaluated by contact profilometry. Significant improvements in surface finishing of all the machined thermally sprayed coatings can always be detected, with FR-FBM being able to guarantee the precision and to ensure the closest geometrical tolerances.     

Modeling of Thickness and Profile Uniformity of Thermally Sprayed Coatings Deposited on Cylinders

In thermal spraying processes, kinematic parameters of the robot play a decisive role in the coating thickness and profile. In this regard, some achievements have been made to optimize the spray trajectory on flat surfaces. However, few reports have focused on nonholonomic or variable-curvature cylindrical surfaces. The aim of this study is to investigate the correlation between the coating profile, coating thickness, and scanning step, which is determined by the radius of curvature and scanning angle. A mathematical simulation model was developed to predict the thickness of thermally sprayed coatings. Experiments were performed on cylinders with different radiuses of curvature to evaluate the predictive ability of the model.     

Fatigue Behavior of Bodies with Thermally Sprayed Metallic and Ceramic Deposits

This paper summarizes the basic results of fatigue testing of bodies with both metallic and ceramic thermally sprayed coatings. Three kinds of ceramic coatings (Al₂O₃, Cr₂O₃, and olivine) sprayed with DC plasma under identical conditions were investigated together with metallic Ni-5wt.%Al coatings sprayed by wire arc, DC plasma, and HVOF. The elastic modulus of the deposited coatings was investigated using four point bending and resonance method. Bending fatigue tests at resonance frequency were performed with cantilever beam specimens. The processes taking place during the fatigue test are identified and discussed. The morphology of the fracture surfaces was investigated together with microstructure and porosity of the coatings.