Abstract Perovskite-type LaMnO 3 powders and coatings have been prepared by a novel technique, the reactive suspension plasma spraying (SPS) using an inductively coupled plasma of about 40 kW plate power and an oxygen plasma sheath gas. Suitable precursor mixtures were found on the basis of solid state reactions, solubility and the phases obtained during the spray process. Best results were achieved by spraying a suspension of fine MnO 2 powder in a saturated ethanol solution of LaCl 3 with a 1:1 molar ratio of La and Mn. Low reactor pressure was helpful in order to diminish the amount of corrosive chlorine compounds in the reactor. As-sprayed coatings and collected powders showed perovskite contents of 70-90%. After a post-treatment with an 80% oxygen plasma an almost pure LaMnO 3 deposit was achieved in the center of the incident plasma jet.

Abstract Suspensions of cobalt spinel (Co3O4) powders were rf plasma sprayed to form electrocatalytically active anode layers. Stable cobalt oxide suspensions of low viscosity exceeding 50 wt% solid phase have been processed. A spheroidization study revealed the formation of large spherical powder particles (- 30 + 80 µm). Cobalt oxide coatings were produced by rf suspension plasma spraying. The porosity was controlled by optimizing spray distance and reactor pressure. The main disadvantage of the thermal plasma processing of cobalt spinel is that the decomposition of the spinel phase into CoO could not be prevented, not even with the application of an 80% oxygen plasma. However, with a relatively low power oxygen plasma post-treatment, the deposited CoO layers can be oxidized to Co3O4, greatly improving the electrochemical performance of the anode layers.

Abstract Fine (median size 6 μm and 0.3 μm) cobalt spinel (Co 3 O 4 ) powders were processed suspended in a suitable liquid phase. Suspensions exceeding 50 wt.% solid phase content were successfully injected into an inductively coupled plasma. Spheroidized powders with large particle size (up to 80 μm) were prepared, and cobalt oxide coatings were produced by this novel RF-SPS method. The microstructural features of the coatings can be controlled by parameter optimization similarly to plasma spraying of dry powders. Numerous variations of the physical and chemical conditions of the process were performed in an attempt to overcome the main disadvantage of the process, i.e. the decomposition of the spinel phase to CoO. So far, the spinel phase could be reestablished only by a post-treatment of the deposited coatings with atomic oxygen in the RF plasma.

Abstract LaMnO 3 powders and coatings have been prepared by reactive suspension plasma spraying (SPS) of MnO 2 powders and LaCl 3 solutions. A 40 kW inductively coupled plasma with an oxygen plasma sheath gas has been used. Water and ethanol have been tested as the liquid phase in the SPS process. High perovskite content (70-90%) has been achieved for both powders and coatings when spraying a suspension of fine MnO 2 powder in a saturated ethanol solution of LaCl3 with a 1:1 molar ratio of La and Mn. Materials obtained by a 1100 °C oven treatment have been used as reference during the study. The reactor pressure was varied from 30 to 80 kPa. Low pressure was found to be necessary to suppress the formation of undesired phases in the powders and coatings obtained. A plasma post treatment of the coatings results in an increase of the perovskite content.

Abstract Suspension Plasma Spraying (SPS) is a thermal spray process based on a suspension of fine (<10 μm) or even ultrafine (<100 nm) powders which is axially fed into the induction plasma through an atomization probe. The atomization of the suspension results in microdroplets (20 μm in size). They are flash dried in the plasma, melted and finally can impact a substrate to build a coating or be cooled down and collected as a spheroidized powder. The large industrial potential of this technology results first from the use of fine powder or even sol-gel which is one of the starting step for many ceramic processes, and second from the various side benefits of the liquid phase in the SPS. Indeed, the liquid phase can be simply a carrier for ultrafine powder, or a protection against oxidation in the case of metals, or a protection for health in the case of whiskers, for instance. It can also take a part in chemical reactions when the liquid phase is a solution of chloride, nitrates... or it can be an organic liquid for the synthesis of carbide, where CO is a strong reducer. Furthermore the liquid phase can also release some energy because of its combustion at the very end of the process. It can also change the local atmosphere surrounding the in flight droplets in the plasma where it is possible to use H 2 O 2 as a carrier in order to increase the oxygen partial pressure around sensitive to oxygen decomposition materials. The applications of SPS are in the powder synthesis (in R&D or production), in the spraying of metals, ceramics or composites directly synthesized, or in production of very reactive with air materials. Applications of SPS will be presented for hydroxyapatite (HA) and NiAlMo. Induction plasma SPS coatings and/or powders properties will be discussed as a function of the SPS process variables.

Abstract The focus of this study is the formation of a solid solution and metallic nickel in the cobalt-nickel mixed oxide coatings during suspension plasma spray (SPS) deposition. The (Co,Ni)O solid solution is a potential material for inert anode applications in aluminum production. SPS coatings and in-flight collected particles are studied to gain further insight into the melting and mixing phenomena of the NiO and CoO powders as well as phase formation in the deposited coatings. Moreover, the role of suspension feedstock particle sizes on the microstructure of coatings is discussed. SEM, EDS and X-ray diffraction studies helped better understanding the formation of different crystalline phases within the as-sprayed coatings. It was found that the formation of metallic nickel is possible in the coatings. The results support the importance of substrate temperature on the formation of metallic Ni, so that keeping the substrate at low temperature results in an increase of the Ni content in the coatings. In this study, possible causes for the formation of metallic Ni during spraying are discussed.

Abstract Ceria (CeO2) based electrolytes have been considered for use in solid oxide fuel cells (SOFC) for more than 20 years. There are however some limitations to this usage that this study has tried to address, indeed the study objective has been that of synthesizing and thermal spraying thin layers (50 - 100 µm) of doped CeO2 by the technique of suspension plasma spraying, using radio frequency (RF) plasma technology. Various dopant combinations and concentrations have been selected for this work in order to increase the useful partial oxygen pressure range for satisfactory ionic conductivity development, thereby increasing the anionic conductivity and preventing CeO2 reduction in fuel cell service. Ceria possesses the fluorite crystal structure at low temperatures but does not have enough oxygen vacancies to be a good ionic conductor. In ceria the cerium have 4+ oxidation state within the fluorite structure, and by substituting a certain amount of Ce4+ ions by trivalent dopant ions, oxygen vacancies are induced into the structure. Recent studies have demonstrated that at low temperatures doped ceria seems to be a better electrolyte than doped zirconia. Also, it seems that dopants with ionic radii close to Ce4+ ions give rise to better ionic conductivities. The doped ceria conductivity increases with the dopant concentration because more oxygen vacancies are created, but at higher concentrations vacancy ordering occurs which results in decreased ionic conductivity.

Abstract Thermal plasma spraying is a suitable technique for hydroxyapatite [HA, Ca 10 (P0 4 ) 6 (OH) 2 ] coating preparation. Suspension Plasma Spraying (SPS) is a newly developed process based on a suspension of fine (<10 μm) or even ultrafine (<100 μm) powders, axially fed into the RF plasma through an atomization probe. The atomization of the suspension results in microdroplets (20 μm in size). They are flash dried, melted and finally impacted onto the substrate to solidify and build the coating. The aqueous suspension of HA is chemically synthesized. Our experiments included variations of the plasma gas composition (Ar/O 2 , Ar/H 2 ), the plasma deposition reactor pressure. Characterizations techniques (e.g. X-ray diffraction, scanning electron microscope and transmission electron microscope) were applied to resultant SPS HA coatings which possessed good crystallinity and about 3% weight α-TCP and lime. The texture examination has shown that preferential crystal orientation followed the (001) Miller's plane family. SPS by RF induction plasma has proved to be a reliable process for the production of thick (200 μm) HA coatings with high deposition rate (>150 μm/min).

Abstract The porous architecture of coatings has a significant influence on the coating performances and thus should be properly designed for the intended applications. For simulating the coating properties, it is necessary to determine the numerical representation of the coating microstructure. In this study, YSZ coatings were manufactured by suspension plasma spray (SPS). Afterwards, the porous architecture of as-prepared coatings was investigated by the combination of three techniques, imaging analysis, Ultra Small Angle X-ray Scattering (USAXS), and X-ray transmission. A microstructural model for reconstructing the porous architecture of the SPS coating was subsequently computed according to the collected experimental results. Finally, the coating thermal properties were simulated based on the model and were compared with the experimental results.

Abstract This study investigates the effect of composition on the antibacterial and antiviral properties of hydroxyapatite/titania composite coatings deposited by suspension plasma spraying. Hydroxyapatite is a bioceramic material used as a plasma-sprayed coating to promote osseointegration of femoral stems. TiO2 has promising photocatalytic activity and good efficiency in destroying bacteria, viral species, and parasites. Prior to coating, substrates were grit blasted, ultrasonically cleaned, and heated to enhance adhesion strength. The microstructure of the resulting coatings was then characterized using XRD and Raman spectroscopy. Test results indicated that SPS transformed Ti2O3 into TiO2 with mixed phases. Ti4O7 and Ti3O5 phases were also identified, which show photocatalytic activity due to oxygen vacancies. Antibacterial and antiviral tests were conducted as well.

Abstract Thermal spray is a versatile process that produces high-quality coatings possessing diverse properties such as superhydrophobicity, wear resistance, corrosion resistance, dielectric properties etc. Conventionally, powder feedstock is used in thermal spray, and this process is commercialised in numerous industrial processes. However, liquid feedstock based thermal spray is still in its development phases, due to limited information available on process parameters. Various parameters such as plasma/fuel gas, plasma current, feedrate, feeding angle, type of feedstock (suspension or solution precursor), feedstock concentration, feedstock viscosity, solvent, etc. significantly influence the thermal and kinetic energy exchange between plasma/flame and feedstock material. Suspension plasma spray (SPS) and suspension high velocity oxy-fuel spray (SHVOF), once optimised, can give rise to coatings with multiscale features. An in-depth understanding of the complex interaction between feedstock solution/suspension chemical-physical properties and plasma/flame jet characteristics is essential to understand its specific impact on coating properties and their application. This paper presents comparisons between two different TiO2 coatings, deposited by SPS and S-HVOF, and obtained by varying some of the fundamental spray deposition parameters. The surface morphology and cross-sections of the as-deposited coatings were compared through SEM/EDX. Further, surface wetting properties were analysed through measuring the static and dynamic contact angles.

Abstract Intensive R&D work of more than one decade has demonstrated many unique coating properties, particularly for oxide ceramic coatings fabricated by suspension thermal spraying technology. Suspension spraying allows producing yttria-stabilized zirconia (YSZ) thermal barrier coatings (TBC) with columnar microstructure, similar to those produced by electron-beam physical vapor deposition (EB-PVD), and vertically cracked morphologies, with a generally low thermal conductivity. Therefore, suspension sprayed YSZ TBCs are seen as an alternative to EB-PVD coatings and those produced by conventional air plasma spray (APS) processes. Nonetheless, the microstructure of the YSZ topcoat is strongly influenced by the properties of the metallic bondcoat. In this work, direct laser interference patterning (DLIP) was applied to texture the surface topography of Ni-alloy based plasma sprayed bondcoat. Suspension plasma spraying (SPS) was applied to produce YSZ coatings on top of as-sprayed and laser-patterned bondcoat. The samples were characterized in terms of microstructure, phase composition and thermal cycling performance. The influence of the bondcoat topography on the properties of suspension sprayed YSZ coatings is presented and discussed.

Abstract In this paper a process based on both Thermal Plasma Chemical Vapor Deposition (TPCVD) and Suspension Plasma Spraying (SPS) is applied on r.f. induction thermal plasma for α/β-SiC ceramic synthesis and deposition. The starting materials are low-cost liquid disilanes. The resulting coatings are investigated by means of SEM and XRD. Results on the influence of the processing parameters (i.e. pressure, spray distance, substrate temperature, plasma gas nature and composition, precursor composition, atomization parameters) on the coating phase and microstructure are shown. Control of the microstructure (or nanostructure) as well as of the phase content, namely the ratio α/β can be achieved. A processing route presenting the elementary steps of SiC TPCVD is also proposed.

Abstract The aim of this work is to better understand the build-up of thermal barrier coatings (TBC) on microtextured substrates, particularly the influence of geometry on the behavior of plasma jets in substrate boundary layers. Coatings produced by suspension plasma spraying served as an experimental reference for numerical analysis, which involved advanced turbulent flow and volumetric heat source modeling along with the use of commercial fluid flow software. Geometric and numerical models were used to simulate the generation of plasma inside the torch and the resulting plasma flow with its highly nonlinear thermophysical characteristics. This work opens the possibility of predicting feedstock particle movement and deposition, which is essential in understanding coating build-up mechanisms in general and the flow of fine particles on substrate surfaces in particular.

Abstract In suspension spraying, the two most frequently used solvents are water and ethanol. In this study, we test a potential alternative, a high-molecular weight solvent. Two organic solvents are compared: ethanol (serving as a benchmark, suspension formulated at 10 wt.% solid load) and di-propylene glycol methyl ether (two suspensions at 10 wt.% and 20 wt.%). Submicron alpha-alumina powder is used as a model material to formulate the suspensions. It is shown that ethanol- and ether-based-feedstock coatings are fully comparable in terms of their microstructure, porosity content, surface roughness, and hardness. However, the ether-based coatings exhibit slightly higher levels of α-Al2O3 phase than their ethanol-based counterpart (17 wt.% vs. 6 wt.%). The use of 20 wt.% solid load in the ether solvent leads to a twofold increase in the deposition rate while, as opposed to ethanol, successfully retaining a dense microstructure. Ether also costs less than ethanol and is safer to handle.

Abstract Solid oxide fuel cells (SOFC) are expected to gain a high importance as direct converters for transforming chemical into electrical energy. They have the potential of working with considerably higher efficiency and much less environmental problems compared to systems used so far. SOFCs of present technology operate at temperatures in the range of 950 °C. Besides an increase in performance and stability, a main precondition for a technical breakthrough of SOFCs is a drastic reduction of their production costs. Approaches are the use of less-expensive materials, new SOFC designs with thinner components and the improvement of presently applied production routes, or their replacement by other techniques such as thermal spray methods. DC- and RF-VPS show very attractive properties particularly if the cell will be manufactured in one consecutive combined process. The state of SOFC spray design will be described together with results of the process adaptation and the SOFC components development.

Abstract This study presents the results of thermal cycling experiments on thermal barrier coatings deposited using hybrid water/argon-stabilized plasma (WSP-H) torches. Topcoats produced from YSZ suspensions and powders were successfully prepared and evaluated by thermal fatigue testing. Quad-layer coatings with topcoats consisting of yttria stabilized zirconia, gadolinium zirconate, and yttrium aluminum garnet were also prepared and tested at high temperatures and thermal gradients. The results obtained show the potential of WSP-H technology for applications where protection of large components or deposition of thick coatings are required.

Abstract As a critical technology, thermal barrier coatings (TBC) have been used in both aero engines and industrial gas turbines for a few decades, however, the most commonly used MCrAlY bond coats which control air plasma sprayed (APS) TBC lifetime are still deposited by the powders developed in 1980s. This motivates a reconsideration of development of MCrAlY at a fundamental level to understand why the huge efforts in the past three decades has so little impact on industrial application of MCrAlY alloys. Detailed examination of crack trajectories of thermally cycled samples and statistic image analyses of fracture surface of APS TBCs confirmed that APS TBCs predominately fails in top coat. Cracks initiate and propagate along splat boundaries next to interface area. TBC lifetime can be increased by either increasing top coat fracture strength (strain tolerance) or reducing the tensile stress in top coat or both. By focusing on the reduction of tensile stress in top coats, three new bond coat alloys have been designed and developed, and the significant progress in TBC lifetime have been achieved by using new alloys. Extremely high thermal cycle lifetime is attributed to the unique properties of new alloys, such as remarkably lower coefficient of thermal expansion (CTE) and weight fraction of β phase, absence of mixed / spinel oxides, and TGO self repair ability, which cannot be achieved by the existed MCrAlY alloys.

Abstract Thermally sprayed WC-Co coatings provide excellent wear resistance and corrosion protection under heavy loads, but their application usually involves additional grinding and polishing steps, which can be 3-4 times costlier than the spraying process itself. There is thus the motivation to develop a process that produces smooth, near-net-shape carbide coatings. This contribution is an investigation of WC-12Co coatings obtained by suspension HVOF spraying. Significant work was devoted to the development and characterization of water-based hardmetal suspensions synthesized from commercially available WC and Co powders. The suspensions produced were sprayed using the HVOF process, and the resulting coatings were evaluated based on microstructure, hardness, and phase composition.

Abstract An experimental study of the spheroidization efficiency of induction plasma processes was completed. The main objective being to obtain models which could be subsequently used for the prediction of the spheroidization efficiency for various powders and plasma operating conditions. Silica, alumina, chromium oxide and zirconia powders were treated during the experimentation. For the plasma treatment of the powders the installation used had a maximum available power of 50 kW with an operating frequency of 3 MHz. Operating conditions were varied such to minimize side reactions and the evaporation of powders. The resulting powders did show the presence of cavities and a slight change in the mean diameters. The maximum energy efficiency based semi-empirical model did predict the spheroidization efficiency of the particles beyond a defined critical point known as the maximum energy efficiency point. For the model, the maximum energy efficiency is distinct for the individual powders but remain within a defined range which is reflected in the small variations in the Z constant.