Finely grained nanometric and submicrometric coatings by thermal spraying: A review

Technology, microstructure and properties of nanostructured coatings obtained using different feedstock including: (i) powders composed of agglomerated nanocrystals; (ii) solutions; and (iii) suspensions are discussed. The methods of nanostructured coarse powders manufacturing are reviewed together with the problems related to formulation of solutions and suspensions. A particular attention is paid to the key problem at liquid feedstock spraying, namely to their delivery and injection into jets or flames. The physical and chemical phenomena occurring at flight of injected liquid droplet of solution and suspension are shown and related to the formation of coatings and their microstructure. Some microstructural, chemical, mechanical and electrical properties of coatings are collected and related to the operational processing parameters by regression equations derived from the design of spray experiments. Finally, the possible applications of nanostructured coatings are briefly discussed.     

Parameters Controlling Liquid Plasma Spraying: Solutions, Sols, or Suspensions

This article presents what is our present knowledge in plasma spraying of suspension, sol, and solution in order to achieve finely or nano-structured coatings. First, it describes the different plasma torches used, the way liquid jet is injected, and the different measurements techniques. Then, drops or jet fragmentation is discussed with especially the influence of arc root fluctuations for direct current plasma jets. The heat treatment of drops and droplets is described successively for suspensions, sols, and solutions both in direct current or radio-frequency plasmas, with a special emphasize on the heat treatment, during spraying, of beads and passes deposited. The resulting coating morphologies are commented and finally examples of applications presented: Solid Oxide Fuel Cells, Thermal Barrier coatings, photocatalytic titania, hydroxyapatite, WC-Co, complex oxides or metastable phases, and functional materials coatings.     

Comparative study on the photocatalytic behaviour of titanium oxide thermal sprayed coatings from powders and suspensions

This work presents a study of the microstructures and photocatalytic behaviour of titanium oxide coatings obtained by thermal spraying of agglomerated nanopowders and suspensions. Fine TiO₂ Degussa P25 nanopowder, generally considered as the reference material in photocatalytic applications, was used as the material feedstock. HVOF process and suspension thermal spraying were used to prepare photocatalytic titania coatings. The coatings were mainly characterised by means of SEM and X-ray diffraction. The photocatalytic performance was evaluated based on decolouration of the pink dye Rhodamine B and degradation of gaseous acetaldehyde. A lower degree of pollutant degradation was found for deposits prepared by HVOF spraying of granules due principally to the low content of the photocatalytically active phase, i.e. anatase. Complete photocatalytic degradation of the organic compounds was recorded for the suspension-sprayed coatings. Based on the current results, suspension thermal spraying appears to be the better choice for preparing photocatalytically active titanium oxide surfaces for the removal of organic pollutants.     

Nanoindentation study of the mechanical and damage behaviour of suspension plasma sprayed TiO2 coatings

TiO₂ coatings can be used as self-cleaning surfaces owing to their photocatalytic and hydrophilic properties. Suspension plasma spray (SPS) has proven to be a feasible and cheap technique for producing self-cleaning surfaces with acceptable photo-activity. This paper presents a nanoindentation study of the mechanical properties (hardness, Young's modulus and scratch resistance) of photoactive layers of suspension plasma sprayed TiO₂ coatings applied on to glass substrates. Microstructure observation showed that the rutile grains were surrounded by fine anatase crystals. Under the same spraying conditions, the resulting anatase/rutile concentrations varied depending on the cooling rate (the substrate being either cooled with water or in air). The results showed that higher concentrations of anatase, which is softer than rutile, reduced the scratch damage and increased the friction coefficient.     

Life cycle assessment of using powder and liquid precursors in plasma spraying: The case of yttria-stabilized zirconia

Plasma spraying using liquid precursors makes possible the production of finely-structured coatings and thin coatings. This technology has been investigated for nearly ten years in many laboratories and applications are now emerging, using conventional plasma equipment except for the feedstock injection system. While superior quality is expected from the nano-structured coatings, the question remains as to the impacts of using liquid precursors on the environment. In this study, we used the life cycle assessment (LCA) methodology to compare the conventional plasma spray process using powder feedstock, with injection of the precursor in the form of a liquid solution or suspension. The LCA methodology consists of identifying and comparing the environmental impacts of feedstock, energy inputs, products and emissions (solid, liquid and gaseous) of these two alternatives. The LCA study was carried out using the SimaPro program developed in the Netherlands and a peer-reviewed database of upstream materials and energy (EcoInvent v.2). The specific application studied was the plasma spraying of yttria-stabilized zirconia.     

Microstructural characterization of plasma sprayed Al2O3-40 wt.% TiO2 coatings on high density graphite with different post-treatments

Graphite is one of the candidate materials proposed for application in pyrochemical reprocessing plants involving aggressive molten chloride environment. Post treatments are promising techniques for the improvement of properties of thermal spray coatings for different industrial applications. In the present work, the effect of post treatments like vacuum annealing (VA) and laser melting (LM) on the microstructure and chemical modification of plasma sprayed Al₂O₃-40 wt.% TiO₂ coatings over high density (HD) graphite substrates has been investigated. When compared with sprayed coatings (SC), VA coatings showed cluster morphology and LM coatings exhibited homogenous microstructure. On laser melted surfaces networks of cracks were observed. XRD studies showed that the metastable γ-Al₂O₃ phase present in the SC is transformed to stable α-Al₂O₃ after post treatments. In LM coatings Al₂TiO₅ phase was more predominant in contrast to SC and VA coatings. The microhardness enhancement was observed in case of LM coating compared to the VA and SC. Due to elimination of coating defects in LM samples, there is a considerable reduction in the surface roughness.     

Microstructural and Tribological Investigation of High-Velocity Suspension Flame Sprayed (HVSFS) Al2O3 Coatings

Al₂O₃ coatings were manufactured by the high-velocity suspension flame spraying (HVSFS) technique using a nanopowder suspension. Their structural and microstructural characteristics, micromechanical behavior, and tribological properties were studied and compared to conventional atmospheric plasma sprayed and high-velocity oxygen-fuel-sprayed Al₂O₃ coatings manufactured using commercially available feedstock. The HVSFS process enables near full melting of the nanopowder particles, resulting in very small and well flattened lamellae (thickness range 100 nm to 1 μm), almost free of transverse microcracking, with very few unmelted inclusions. Thus, porosity is much lower and pores are smaller than in conventional coatings. Moreover, few interlamellar or intralamellar cracks exist, resulting in reduced pore interconnectivity (evaluated by electrochemical impedance spectroscopy). Such strong interlamellar cohesion favors much better dry sliding wear resistance at room temperature and at 400 °C.     

Characterization of mechanical properties of suspension plasma sprayed TiO2 coatings using scratch test

The study aimed at characterizing mechanical properties of TiO₂ coatings obtained by the use of aqueous suspensions of fine rutile and anatase particles onto metal substrates. Thickness of the coatings was found with the use of optical microscope observations of metallographical cross-sections. The coatings morphology was found with scanning electron microscope (SEM) and their phase composition was determined by X-ray diffraction method. The mechanical properties were characterized using scratch test. The test enabled to characterize the adhesion of coatings by determination of critical force necessary to peel off the coatings from the substrate and, on the other hand, to estimate their cohesion by the measurement of the scratch hardness. The hardness was calculated using the width of the scratch and the value of force applied. The design of experiments (DOE) of spraying with the use of a 2³ full factorial plan was applied to rutile powder. The coatings were sprayed onto aluminium substrate. The DOE enabled to find the effects of three principal parameters, i.e. electric power input to plasma, spray distance and suspension feed rate onto coating adhesion expressed by critical force. A preliminary data for anatase powder sprayed with one set of operational parameters onto stainless steel substrate are also shown.     

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

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

Hot corrosion behavior of detonation gun sprayed Cr3C2–NiCr coatings on Ni and Fe-based superalloys in Na2SO4–60% V2O5 environment at 900 °C

The present work investigates the hot corrosion resistance of detonation gun sprayed (D-gun) Cr₃C₂–NiCr coatings on Superni 75, Superni 718 and Superfer 800 H superalloys. The deposited coatings on these superalloy substrates exhibit nearly uniform, adherent and dense microstructure with porosity less than 0.8%. Thermogravimetry technique is used to study the high temperature hot corrosion behavior of bare and Cr₃C₂–NiCr coated superalloys in molten salt environment (Na₂SO₄–60% V₂O₅) at high temperature 900 °C for 100 cycles. The corrosion products of the detonation gun sprayed Cr₃C₂–NiCr coatings on superalloys are analyzed by using XRD, SEM, and FE-SEM/EDAX to reveal their microstructural and compositional features for elucidating the corrosion mechanisms. It is shown that the Cr₃C₂–NiCr coatings on Ni- and Fe-based superalloy substrates are found to be very effective in decreasing the corrosion rate in the given molten salt environment at 900 °C. Particularly, the coating deposited on Superfer 800 H showed a better hot corrosion protection as compared to Superni 75 and Superni 718. The coatings serve as an effective diffusion barrier to preclude the diffusion of oxygen from the environment into the substrate superalloys. It is concluded that the hot corrosion resistance of the D-gun sprayed Cr₃C₂–NiCr coating is due to the formation of desirable microstructural features such as very low porosity, uniform fine grains, and the flat splat structures in the coating.