Liquid Precursor Plasma Spraying of Functional Materials: A Case Study for Yttrium Aluminum Garnet (YAG)

RF precursor plasma spray synthesis (RFPPS) is an innovative and rapid technique to deposit functional oxide coatings by starting from liquid inorganic precursors and directly producing ceramic coatings. RFPPS offers excellent opportunities in exploring the nonequilibrium phase evolution during plasma spraying of molecularly mixed precursors to form multicomponent oxides. A detailed discussion of progress, critical issues and consideration in precursor development, RF plasma spraying, coating development, and phase evolution of yttrium aluminum garnet (YAG) is presented as a case study. Appropriate selection of precursors and proper tuning of spray parameters resulted in amorphous or crystalline coatings in the as-sprayed condition. YAG phase selection has also been investigated using a discrete, low-density combinatorial synthesis approach.     

Comparison of the photocatalytic behavior of TiO2 coatings elaborated by different thermal spraying processes

This paper proposes a comparative study on the microstructure and photocatalytic performances of titanium dioxide coatings elaborated by various thermal spraying methods (plasma spraying in atmospheric conditions, suspension plasma spraying, and high-velocity oxyfuel spraying). Agglomerated spray dried anatase TiO₂ powder was used as feedstock material for spraying. Morphology and microstructural characteristics of the coatings were studied mainly by scanning electron microscopy and x-ray diffraction. The photocatalytic behavior of the TiO₂-base surfaces was evaluated from the conversion rate of gaseous nitrogen oxides (NOx). It was found that the crystalline structure depended strongly on the technique of thermal spraying deposition. Moreover, a high amount of anatase was suitable for the photocatalytic degradation of the pollutants. Suspension plasma spraying has allowed retention of the original anatase phase and for very reactive TiO₂ surfaces to be obtained for the removal of nitrogen oxides. This article was originally published inBuilding on 100 Years of Success, Proceedings of the 2006 International Thermal Spray Conference (Seattle, WA), May 15–18, 2006, B.R. Marple, M.M. Hyland, Y.-Ch. Lau, R.S. Lima, and J. Voyer, Ed., ASM International, Materials Park, OH, 2006.     

Preparation of perovskite powders and coatings by radio frequency suspension plasma spraying

Perovskite-type LaMnO₃ powders and coatings have been prepared by a novel technique: reactive suspension plasma spraying (SPS) using an inductively coupled plasma of approximately 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 MnO₂ powder in a saturated ethanol solution of LaCl₃ with a 1 to 1 molar ratio of lanthanum and manganese. A low reactor pressure was helpful in diminishing the amount of corrosive chlorine compounds in the reactor. As-sprayed coatings and collected powders showed perovskite contents of 70 to 90%. After a posttreatment with an 80% oxygen plasma, an almost pure LaMnO₃ deposit was achieved in the center of the incident plasma jet. This paper originally appeared in Thermal Spray: Meeting the Challenges of the 21st Century; Proceedings of the 15th International Thermal Spray Conference, C. Coddet, Ed., ASM International, Materials Park, OH, 1998. This proceedings paper has been extensively reviewed according to the editorial policy of the Journal of Thermal Spray Technology.     

Cold gas dynamic spraying of iron-base amorphous alloy

This paper describes recent efforts to synthesize iron-base amorphous alloys coatings using cold gas dynamic spraying. Characterization of the gas-atomized iron-base (Fe-Cr-Mo-W-C-Mn-Si-Zr-B) powder shows that the powder is fully amorphous when the particle diameter is below 20 μm. The coatings produced were composed of the same microstructure as the one observed in the feedstock powder. The overall deformation suggests the occurrence of a localized deformation process at the particle/particle boundary and a possible adiabatic deformation softening inside the powder particles during splat formation. The synthesis of fully amorphous, porous-free coatings using cold gas dynamic spraying was demonstrated in this work. This article was originally published inBuilding on 100 Years of Success, Proceedings of the 2006 International Thermal Spray Conference (Seattle, WA), May 15–18, 2006, B.R. Marple, M.M. Hyland, Y.-Ch. Lau, R.S. Lima, and J. Voyer, Ed., ASM International, Materials Park, OH, 2006.     

Modeling of motion and heating of powder particles in laser, plasma, and hybrid spraying

Mathematical models for simulation of motion and heating of fine ceramic particles in plasma and laser spraying, as well as under conditions of a new technological process, that is, hybrid laser plasma spraying, are proposed. Trajectories, velocities, and temperature fields of fine SiO₂ particles being sprayed using the argon plasma jet, CO₂ laser beam, and their combination have been calculated. It is shown that the space-time distribution of temperature in spray particles greatly depends on the spraying method. This article was originally published inBuilding on 100 Years of Success, Proceedings of the 2006 International Thermal Spray Conference (Seattle, WA), May 15–18, 2006, B.R. Marple, M.M. Hyland, Y.-Ch. Lau, R.S. Lima, and J. Voyer, Ed., ASM International, Materials Park, OH, 2006.     

Thermomechanical behavior of nanostructured plasma sprayed zirconia coatings

Retaining nonmelted nanoparticles of zirconia in nanostructured coatings has been a challenge in the past. Recently an air plasma spray process was developed to produce coatings that retain up to 30–35% by volume nonmelted particles, resulting in a unique structure. The creep/sintering behavior of such thermal barrier coatings deposited from nanostructured feedstock has been measured and compared with deposits produced from hot oven spherical particles (HOSP). Both feedstocks contain 6–8 wt.% Y₂O₃ as a stabilizer. Flexure and compression creep testing were conducted under several different loads and temperatures to obtain creep exponents and parameters. This article was originally published inBuilding on 100 Years of Success, Proceedings of the 2006 International Thermal Spray Conference (Seattle, WA), May 15–18, 2006, B.R. Marple, M.M. Hyland, Y.-Ch. Lau, R.S. Lima, and J. Voyer, Ed., ASM International, Materials Park, OH, 2006.     

Alumina coatings by plasma spraying of monosize sapphire particles

A series of plasma sprayed coatings of controlled microstructure was obtained by spraying three monosize sapphire powders using an axial injection torch in which the plasma gas composition and nozzle diameter were the only processing parameters varied. The effects of changes in these parameters on the coating splat morphology, porosity, angular crack distribution, and hardness are reported. The uniform, dense microstructure and the high hardness of 14 GPa (a level usually only associated with chromia thermal spray coatings) of the best alumina coatings resulted from using tightly controlled processing conditions and monodispersed precursor powders. The microstructural quality of plasma sprayed coatings and, hence, the coating properties can be improved significantly by minimizing variations in processing and raw material parameters. This paper originally appeared in Thermal Spray: Meeting the Challenges of the 21st Century; Proceedings of the 15th International Thermal Spray Conference, C. Coddet, Ed., ASM International, Materials Park, OH, 1998. This proceedings paper has been extensively reviewed according to the editorial policy of the Journal of Thermal Spray Technology.     

Biocompatible nanostructured high-velocity oxyfuel sprayed titania coating: Deposition, characterization, and mechanical properties

Nanostructured titania (TiO₂) coatings were produced by high-velocity oxyfuel (HVOF) spraying. They were engineered as a possible candidate to replace hydroxyapatite (HA) coatings produced by thermal spray on implants. The HVOF sprayed nanostructured titania coatings exhibited mechanical properties, such as hardness and bond strength, much superior to those of HA thermal spray coatings. In addition to these characteristics, the surface of the nanostructured coatings exhibited regions with nanotextured features originating from the semimolten nanostructured feedstock particles. It is hypothesized that these regions may enhance osteoblast adhesion on the coating by creating a better interaction with adhesion proteins, such as fibronectin, which exhibit dimensions in the order of nanometers. Preliminary osteoblast cell culture demonstrated that this type of HVOF sprayed nanostructured titania coating supported osteoblast cell growth and did not negatively affect cell viability. This article was originally published inBuilding on 100 Years of Success, Proceedings of the 2006 International Thermal Spray Conference (Seattle, WA), May 15–18, 2006, B.R. Marple, M.M. Hyland, Y.-Ch. Lau, R.S. Lima, and J. Voyer, Ed., ASM International, Materials Park, OH, 2006.     

Suspension plasma spraying of nanostructured WC-12Co coatings

Nanostructured WC-12% Co coatings were deposited by suspension plasma spraying of submicron feedstock powders, using an internal injection plasma torch. The liquid carrier used in this approach allows for controlled injection of much finer particles than in conventional thermal spraying, leading to thin coatings with a fine surface finish. A polyethylene-imine (PEI) dispersant was used to stabilize the colloidal suspension in an ethanol carrier. In-flight particle states were measured for a number of operating conditions of varying plasma gas flow rates, feed rates, and standoff distances and were related to the resulting microstructure, phase composition (EDS, SEM, XRD), and Vickers hardness. High in-flight particle velocities (>800 m/s) were generated, leading to dense coatings. It was observed that the coating quality was generally compromised by the high temperature and reactivity of the small particles. To compensate for this shortcoming, the suspension feed rate was adjusted, thereby varying the thermal load on the plasma. Results showed that a slightly larger agglomerate size, in conjunction with low particle jet temperatures, could somewhat limit the decomposition of WC into brittle W₂C/W₃C and amorphous cobalt containing binder phases. This article was originally published inBuilding on 100 Years of Success, Proceedings of the 2006 International Thermal Spray Conference (Seattle, WA), May 15–18, 2006, B.R. Marple, M.M. Hyland, Y.-Ch. Lau, R.S. Lima, and J. Voyer, Ed., ASM International, Materials Park, OH, 2006.     

Microstructures and characterization of zirconia-yttria coatings formed in laser and hybrid spray process

Hybrid plasma spraying combined with yttrium-aluminum-garnet laser irradiation was studied to obtain optimum zirconia coatings for thermal barrier use. Zirconia coatings of approximately 150 μm thickness were formed on NiCrAlY bond coated steel substrates both by means of conventional plasma spraying and hybrid plasma spraying under a variety of conditions. Post-laser irradiation was also conducted on the plasma as-sprayed coating. The microstructure of each coating was studied and, for some representative coatings, thermal barrier properties were evaluated by hot erosion and hot oxidation tests. With hybrid spraying, performed under optimum conditions, it was found that a microstructure with appropriate partial densification and without connected porosity was formed and that cracks, which are generally produced in the post-laser irradiation treatment, were completely inhibited. In addition, hybrid spraying formed a smooth coating surface. These microstructural changes resulted in improved coating properties with regard to hardness, high temperature erosion resistance, and oxidation resistance. This paper originally appeared in Thermal Spray: Meeting the Challenges of the 21st Century; Proceedings of the 15th International Thermal Spray Conference, C. Coddet, Ed., ASM International, Materials Park, OH, 1998. This proceedings paper has been extensively reviewed according to the editorial policy of the Journal of Thermal Spray Technology.     

Microstructure and properties of tungsten carbide coatings sprayed with various high-velocity oxygen fuel spray systems

This article reports on a series of experiments with various high-velocity oxygen fuel spray systems (Jet Kote, Top Gun, Diamond Jet (DJ) Standard, DJ 2600 and 2700, JP-5000, Top Gun-K) using different WC-Co and WC-Co-Cr powders. The microstructure and phase composition of powders and coatings were analyzed by optical and scanning electron microscopy and x-ray diffraction. Carbon and oxygen content of the coatings were determined to study the decarburization and oxidation of the material during the spray process. Coatings were also characterized by their hardness, bond strength, abrasive wear, and corrosion resistance. The results demonstrate that the powders exhibit various degrees of phase transformation during the spray process depending on type of powder, spray system, and spray parameters. Within a relatively wide range, the extent of phase transformation has only little effect on coating properties. Therefore, coatings of high hardness and wear resistance can be produced with all HVOF spray systems when the proper spray powder and process parameters are chosen. This paper originally appeared in Thermal Spray: Meeting the Challenges of the 21st Century; Proceedings of the 15th International Thermal Spray Conference, C. Coddet, Ed., ASM International, Materials Park, OH, 1998. This proceedings paper has been extensively reviewed according to the editorial policy of the Journal of Thermal Spray Technology.     

Nanostructured photocatalytic titania coatings formed by suspension plasma spraying

This paper describes formation of titanium dioxide coatings designed for photocatalytic applications, obtained by suspension plasma spraying (SPS), an alternative of the atmospheric plasma spraying (APS) technique in which the material feedstock is a suspension of the material to be sprayed. Two different TiO₂ powders were dispersed in distilled water and ethanol and injected in Ar-H₂ or Ar-H₂-He plasma under atmospheric conditions. Scanning electron microscopy (SEM) and x-ray diffraction (XRD) analyses were performed to study the microstructure of the titania coatings. Photocatalytic efficiency of the elaborated samples was evaluated from the conversion ratio of different air pollutants: nitrogen oxides (NOx) and sulfur dioxide (SO₂). The morphology and crystalline structure of the deposits depended mainly on the nature of the solvent (water or alcohol) used in the preparation of the slurries. Dense coatings were obtained starting from aqueous suspensions and porous deposits were elaborated by plasma spraying of a PC105 alcoholic suspension. A significant phase transformation from anatase to rutile occurred when ethanol was used as a solvent. Different photocatalytic performances were observed as a function of the nature of the liquid material feed-stock, the spraying parameters, and the nature of the pollutant. This article was originally published inBuilding on 100 Years of Success, Proceedings of the 2006 International Thermal Spray Conference (Seattle, WA), May 15–18, 2006, B.R. Marple, M.M. Hyland, Y.-Ch. Lau, R.S. Lima, and J. Voyer, Ed., ASM International, Materials Park, OH, 2006.     

On the Role of Spraying Process on Microstructural, Mechanical, and Thermal Response of Alumina Coatings

Thermal spraying is a widely used technology for industrial applications to provide coatings that improve the surface characteristics. According to the specificities of processes (APS, VPS, flame, electric arc), any kind of material can be sprayed. Among materials, ceramic coatings present several interesting aspects such as wear resistance, corrosion protection as well as thermal or electrical insulation; particularly alumina coatings which appear as the most commonly used. From all spraying processes, atmospheric plasma spraying (APS) is a rather well-established process but some others can also be used with a lower economical impact such as the flame technology. The aim of this study was to analyze the alumina coating properties according to the technology employed such as APS or wire flame spraying using the Rokide™ and the Master Jet^? guns. After micrographic analyses by SEM, physical and mechanical properties were measured considering the thermal conductivity and the hardness. 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.     

Characterization of YSZ solid oxide fuel cells electrolyte deposited by atmospheric plasma spraying and low pressure plasma spraying

Yttria doped zirconia has been widely used as electrolyte materials for solid oxide fuel cells (SOFC). Plasma spraying is a cost-effective process to deposit YSZ electrolyte. In this study, the 8 mol% Y₂O₃ stabilized ZrO₂ (YSZ) layer was deposited by low pressure plasma spraying (LPPS) and atmospheric plasma spraying (APS) with fused-crushed and agglomerated powders to examine the effect of spray method and particle size on the electrical conductivity and gas permeability of YSZ coating. The microstructure of YSZ coating was characterized by scanning electron microscopy and x-ray diffraction analysis. The results showed that the gas permeability was significantly influenced by powder structure. The gas permeability of YSZ coating deposited by fused-crushed powder is one order lower in magnitude than that by agglomerated powder. Moreover, the gas permeability of YSZ deposited by LPPS is lower than that of APS YSZ. The electrical conductivity of the deposits through thickness direction was measured by potentiostat/galvanostat based on three-electrode assembly approach. The electrical conductivity of YSZ coating deposited by low pressure plasma spraying with fused-crushed powder of small particle size was 0.043 S cm⁻¹ at 100 °C, which is about 20% higher than that of atmospheric plasma spraying YSZ with the same powder. This article was originally published inBuilding on 100 Years of Success, Proceedings of the 2006 International Thermal Spray Conference (Seattle, WA), May 15–18, 2006, B.R. Marple, M.M. Hyland, Y.-Ch. Lau, R.S. Lima, and J. Voyer, Ed., ASM International, Materials Park, OH, 2006.     

Suspensions Plasma Spraying of Ceramics with Hybrid Water-Stabilized Plasma Technology

Technology of water-stabilized plasma torch was recently substantially updated through introduction of a so-called hybrid concept that combines benefits of water stabilization and gas stabilization principles. The high-enthalpy plasma provided by the WSP-H (“hybrid”) torch may be used for thermal spraying of powders as well as liquid feedstocks with high feed rates. In this study, results from three selected experiments with suspension plasma spraying with WSP-H technology are presented. Possibility of deposition of coatings with controlled microstructures was demonstrated for three different ceramics (YSZ—yttria-stabilized zirconia, YAG—yttrium aluminum garnet and Al₂O₃) introduced into ethanol-based suspensions. Shadowgraphy was used for optimization of suspension injection and visualization of the liquid fragmentation in the plasma jet. Coatings were deposited onto substrates attached to the rotating carousel with integrated temperature monitoring and air cooling, which provided an excellent reproducibility of the deposition process. Deposition of columnar-like YSZ and dense YAG and Al₂O₃ coatings was successfully achieved. Deposition efficiency reached more than 50%, as evaluated according to EN ISO 17 836 standard.     

Synthesis and oxidation behavior of nanocrystalline MCrAlY bond coatings

Thermal barrier coating systems protect turbine blades against high-temperature corrosion and oxidation. They consist of a metal bond coat (MCrAlY, M = Ni, Co) and a ceramic top layer (ZrO₂/Y₂O₃). In this work, the oxidation behavior of conventional and nanostructured high-velocity oxyfuel (HVOF) NiCrAlY coatings has been compared. Commercially available NiCrAlY powder was mechanically cryomilled and HVOF sprayed on a nickel alloy foil to form a nanocrystalline coating. Freestanding bodies of conventional and nanostructured HVOF NiCrAlY coatings were oxidized at 1000 °C for different time periods to form the thermally grown oxide layer. The experiments show an improvement in oxidation resistance in the nanostructured coating when compared with that of the conventional one. The observed behavior is a result of the formation of a continuous Al₂O₃ layer on the surface of the nanostructured HVOF NiCrAlY coating. This layer protects the coating from further oxidation and avoids the formation of mixed oxide protrusions present in the conventional coating. The original version of this article was published as part of the ASM Proceedings, Thermal Spray 2003: Advancing the Science and Applying the Technology, International Thermal Spray Conference (Orlando, FL), May 5–8 2003, Basil R. Marple and Christian Moreau, Ed., ASM International, 2003.     

High-speed visualization and plume characterization of the hybrid spray process

The hybrid spray process that combines arc spray with a high-velocity oxyfuel (HVOF)/plasma jet has recently demonstrated its effectiveness in deposition of functionally gradient coatings. This approach aims at exploiting the combined attributes of the arc-spray technique and the HVOF/air plasma spraying (APS) technique. This paper presents high-speed visualization and plume characterization of an arc/HVOF hybrid spray gun as well as a twin-wire arc-spray gun. The physics of atomization in the hybrid spray process is examined using a high-speed camera. A DPV/CPS-2000 (Tecnar, St-Bruno, QC, Canada) particle diagnostics sensor is used to measure particle velocity, temperature, size, and distribution. The influence of feed material, arc parameters, and HVOF parameters on the particle characteristics is presented. Differences in the in-flight characteristics between the hybrid and the twin-wire arc process are discussed aided by the observed atomization phenomena with the high-speed camera. This article was originally published inBuilding on 100 Years of Success, Proceedings of the 2006 International Thermal Spray Conference (Seattle, WA), May 15–18, 2006, B.R. Marple, M.M. Hyland, Y.-Ch. Lau, R.S. Lima, and J. Voyer, Ed., ASM International, Materials Park, OH, 2006.     

Wear characteristics of plasma-sprayed nanostructured yttria partially stabilized zirconia coatings

Reconstituted nanostructured and conventional yttria partially stabilized zirconia coatings were deposited by atmospheric plasma spray. The tribologic properties of the coatings against 100C6 steel were evaluated with a ball-on-disc configuration under dry friction conditions at room temperature. Microstructure and the phase composition of the powders and the coatings were examined using a scanning electron microscope, optical microscope, and x-ray diffraction. Microhardness and the Young’s modulus of coatings were measured by indentation testing. Results showed that the wear resistance of the coatings produced using the nanostructured powder is improved compared with the coating produced using the conventional powder. The wear rates of nanostructured zirconia coatings are about four-fifths of those of conventional counterparts under a load of 5 N. The wear mechanism is also discussed. The original version of this paper was published as part of the DVS Proceedings: “Thermal Spray Solutions: Advances in Technology and Application,” International Thermal Spray Conference, Osaka, Japan, 10–12 May 2004, CD-Rom, DVS-Verlag GmbH, Düsseldorf, Germany.     

Relation Between the Arc-Root Fluctuations, the Cold Boundary Layer Thickness and the Particle Thermal Treatment

In plasma spraying, the arc-root fluctuations, modifying the length and characteristics of the plasma jet, have an important influence on particle thermal treatment. These voltage fluctuations are strongly linked to the thickness of the cold boundary layer (CBL), surrounding the arc column. This thickness depends on the plasma spray parameters (composition and plasma forming gas mass flow rate, arc current, etc.) and the plasma torch design (anode-nozzle internal diameter and shape, etc.). In order to determine the influence of these different spray parameters on the CBL properties and voltage fluctuations, experiments were performed with two different plasma torches from Sulzer Metco. The first one is a PTF4 torch with a cylindrical anode-nozzle, working with Ar-H₂ plasma gas mixtures and the second one is a 3MB torch with either a conical or a cylindrical anode-nozzle, working with N₂-H₂ plasma gas mixtures. Moreover, arc voltage fluctuations influence on particle thermal treatment was studied through the measurements of transient temperature and velocity of particles, issued from an yttria partially stabilized zirconia powder with a size distribution between 5 and 25 μm. 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.