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.     

Kinetic sprayed rare earth iron alloy composite coatings

One unique advantage of the kinetic spray process is its ability to mix constituents that would normally react with each other to form coatings. This attribute was used to produce composite coatings with different rare earth iron alloys (REFe₂) and several ductile matrices. Composite coatings of Terfenol-D [(Tb_0.3Dy_0.7)Fe_1.9] and SmFe₂ were combined with ductile matrices of aluminum, copper, iron, and molybdenum. Evidence of an induced magnetic coercivity was measured for the REFe₂-Mo and Fe composite coatings. Coatings were produced on flat substrates and shafts. Coating morphology as well as the physical, magnetostrictive, and magnetic properties of these coatings are discussed. 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.     

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.     

Liquid plasma sprayed coatings of yttria-stabilized zirconia for SOFC electrolytes

To achieve solid oxide fuel cells (SOFC) at reduced costs, the atmospheric plasma spray (APS) process could be an attractive technique. However, to make dense and thin layers as needed for electrolytes, a suspension is preferably implemented as a feedstock material instead of a conventional powder. Suspensions of yttria-stabilized zirconia particles in methanol have been prepared with various solid loadings and states of dispersion. An external injection system was used to ensure the atomization and radial injection of the suspension into the Ar-H₂ plasma under atmospheric conditions. The coatings morphologies were characterized by scanning electron microscopy, and their porosity was evaluated by the Archimedes method. Differences in the microstructure of the deposits were observed depending on the APS operating conditions. Special attention has been dedicated to assess the influence of the suspension as well as the injection on the layer morphology. For this purpose, the atomization has been investigated and efforts have been made to understand relationships among suspension properties, atomization, and coating microstructure. 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.     

New developments in cold spray based on higher gas and particle temperatures

In cold spraying, bonding is associated with shear instabilities caused by high strain rate deformation during the impact. It is well known that bonding occurs when the impact velocity of an impacting particle exceeds a critical value. This critical velocity depends not only on the type of spray material, but also on the powder quality, the particle size, and the particle impact temperature. Up to now, optimization of cold spraying mainly focused on increasing the particle velocity. The new approach presented in this contribution demonstrates capabilities to reduce critical velocities by well-tuned powder sizes and particle impact temperatures. A newly designed temperature control unit was implemented to a conventional cold spray system and various spray experiments with different powder size cuts were performed to verify results from calculations. Microstructures and mechanical strength of coatings demonstrate that the coating quality can be significantly improved by using well-tuned powder sizes and higher process gas temperatures. The presented optimization strategy, using copper as an example, can be transferred to a variety of spray materials and thus, should boost the development of the cold spray technology with respect to the coating quality. 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.     

Plasma Electrolytic Oxidation of Arc-Sprayed Aluminum Coatings

Different posttreatment methods, such as heat treatment, mechanical processing, sealing, etc., are known to be capable to improve microstructure and exploitation properties of thermal spray coatings. In this work, a plasma electrolytic oxidation of aluminum coatings obtained by arc spraying on aluminum and carbon steel substrates is carried out. Microstructure and properties of oxidized layers formed on sprayed coating as well as on bulk material are investigated. Oxidation is performed in electrolyte containing KOH and liquid glass under different process parameters. It is shown that thick uniform oxidized layers can be formed on arc-sprayed aluminum coatings as well as on solid material. Distribution of alloying elements and phase composition of obtained layers are investigated. A significant improvement of wear resistance of treated layers in two types of abrasive wear conditions is observed. 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.     

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.     

A new high-velocity oxygen fuel process for making finely structured and highly bonded inconel alloy layers from liquid feedstock

High-velocity oxygen fuel (HVOF) thermal spray processes are used in applications requiring the highest density and adhesion strength, which are not achievable in most other thermal spray processes. Similar to other thermal spray processes, however, a normal HVOF process is unable to apply fine powders less than 10 μm via a powder feeder. The advantages of using smaller and even nanosized particles in a HVOF process include uniform microstructure, higher cohesion and adhesion, full density, lower internal stress, and higher deposition efficiency. In this work, a new process has been developed for HVOF forming of fine-grained Inconel 625 alloy layers using a liquid feedstock containing small alloy particles. Process investigations have shown the benefits of making single and duplex layered coatings with full density and high bond strength, which are attributed to the very high kinetic energy of particles striking on the substrates and the better melting of the small particles. 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.     

Effect of steam treatment during plasma spraying on the microstructure of hydroxyapatite splats and coatings

The major problems with plasma sprayed hydroxyapatite (HA) coatings for hard tissue replacement are severe HA decomposition and insufficient mechanical properties of the coatings. Loss of crystalline HA after the high-temperature spraying is due mainly to the loss of OH⁻ in terms of water. The current study used steam to treat HA droplets and coatings during both in-flight and flattening stages during plasma spraying. The microstructure of the HA coatings and splats was characterized using scanning electron microscope, Raman spectroscopy, Fourier transform IR spectroscopy, and x-ray diffraction. Results showed that a significant increase in crystallinity of the HA coating was achieved through the steam treatment (e.g., from 58 to 79%). In addition, the effects were dependent on particle sizes of the HA feedstock, more increase in crystallinity of the coatings made from smaller powders was revealed. The Raman spectroscopy analyses on the individual splats and coatings indicate that the mechanism involves entrapping of water molecules by the individual HA droplets upon their impingement. It further suggests that the HA decomposition has already taken place before the impingement of the droplets on precoating or substrate. The improvement in crystallinity and phases, for example, from tricalcium phosphate and amorphous calcium phosphate to HA, was achieved by reversing the HA decomposition through providing extra OH⁻. Furthermore, the steam treatment during the spraying also accounts for remarkably increased adhesion strength from 9.09 to 23.13 MPa. The in vitro testing through immersing the HA coatings in simulated body fluid gives further evidence that the economic and simple steam treatment is promising in improving HA coating structure. 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.     

Investigation of Al-Al2O3 Cold Spray Coating Formation and Properties

Coating build-up mechanisms and properties of cold-sprayed aluminum-alumina cermets were investigated using two spherical aluminum powders having average diameters of 36 and 81 μm. Those powders were blended with alumina at several concentrations. Coatings were produced using a commercial low-pressure cold spray system. Powders and coatings were characterized by electronic microscopy and microhardness measurements. In-flight particle velocities were monitored for all powders. The deposition efficiency was measured for all experimental conditions. Coating performance and properties were investigated by performing bond strength test, abrasion test, and corrosion tests, namely, salt spray and alternated immersion in saltwater tests. These coating properties were correlated to the alumina fraction either in the starting powder or in the coating. 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.     

Numerical Simulation of Droplet Breakup and Collision in the Solution Precursor Plasma Spraying

Finely structured ceramic coatings can be obtained by solution precursor plasma spraying. The final structure of the coating highly depends on the droplet size and velocity distribution at the injection, the evolution of the spray in the jet, and droplet breakup and collision within the spray. This article describes a 3D model to simulate the transport phenomena and the trajectory and heating of the solution spray in the process. O’Rourke’s droplet collision model is used to take into account the influence of droplet collision. The influence of droplet breakup is also considered by implementing TAB droplet breakup models into the plasma jet model. The effects of droplet collisions and breakup on the droplet size, velocity, and temperature distribution of the solution spray are investigated. The results indicate that droplet breakup and collision play an important role in determining the final particle size and velocity distributions on the substrate. 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.     

Modeling thermal conductivity of thermal spray coatings: comparing predictions to experiments

Thermal conductivity plays a critical role in the thermal transport of thermal-sprayed coatings. In this article, a combined image analysis and finite-element method approach is developed to assess thermal conductivity from high-resolution scanning electron microscopy images of the coating microstructure. Images are analyzed with a collection of image-processing algorithms to reveal the microscopic coating morphology. The processed digital image is used to generate a two-dimensional finite-element mesh in which pores, cracks, and the bulk coating material are identified. The effective thermal conductivity is then simulated using a commercial finite-element code. Results are presented for three coating material systems [yttriastabilized zirconia (YSZ), molybdenum, and NiAl], and the results are found to be in good agreement with the experimental values obtained using the laser flash method. The YSZ coatings are also annealed, and the analysis procedure was repeated to determine whether the technique can accurately assess changes in coating morphology. 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, 2006.     

Numerical simulation of the cold gas dynamic spray process

A computational fluid dynamic (CFD) model of the cold gas dynamic spray process is presented. The gas dynamic flow field and particle trajectories within an oval-shaped supersonic nozzle as well as in the immediate surroundings of the nozzle exit, before and after the impact with the target plane, are simulated. Predicted nozzle wall pressure values compare well with experimental data. In addition, predicted particle velocity results at the nozzle exit are in qualitative agreement with those obtained using a side-scatter laser Doppler anemometer (LDA). Details of the pattern of the particle release into the surroundings are visualized in a convenient manner. 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.     

Investigation about the Chrome Steel Wire Arc Spray Process and the Resulting Coating Properties

Nowadays, wire-arc spraying of chromium steel has gained an important market share for corrosion and wear protection applications. However, detailed studies are the basis for further process optimization. In order to optimize the process parameters and to evaluate the effects of the spray parameters DoE-based experiments had been carried out with high-speed camera shoots. In this article, the effects of spray current, voltage, and atomizing gas pressure on the particle jet properties, mean particle velocity and mean particle temperature and plume width on X46Cr13 wire are presented using an online process monitoring device. Moreover, the properties of the coatings concerning the morphology, composition and phase formation were subject of the investigations using SEM, EDX, and XRD-analysis. These deep investigations allow a defined verification of the influence of process parameters on spray plume and coating properties and are the basis for further process optimization. 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.     

Optimization of a Rotating Twin Wire-Arc Spray Gun

This paper presents a CFD (Computational Fluid Dynamic) study and experimental results concerning a rotating twin wire-arc spray process for the production of coatings on engine cylinder bores. In this process, the wire atomization is performed using a gas injection coaxially with the cylinder axis. The thermal spray tool is equipped with a deviation head rotating around the cylinder axis and allowing deflecting the droplet spray perpendicularly to the cylinder surface. The initial deviation head was found to be not sufficiently efficient so that a new deviation head incorporating an inclined slot was designed and used. Both CFD results and experiments showed that this new deviation head is more efficient. Moreover, it allowed increasing the coating bond-strength up to the specifications imposed by PSA Peugeot-Citroen. The present article shows that the wire-arc spray technology may replace efficiently the Atmospheric Plasma Spray (APS) for the thermal spray of coatings on engine cylinder bores. Moreover, it shows how CFD may help in solving industrial problems. In particular, the FLUENT CFD code was used in order to perform improvements of the deviation head design. This article was originally 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, 2007.     

Solution Precursor Plasma Spray of Nickel-Yittia Stabilized Zirconia Anodes for Solid Oxide Fuel Cell Application

In conventional plasma spray of SOFC components, the large NiO and YSZ particles used, about 50-150 microns for high porosity coating, reduce the density of three-phase sites for electrode reaction. In this article, the SPPS process was used to synthesize and deposit Ni-YSZ anodes. The results show that several process parameters have significant effects on the microstructure and phase composition of the deposited material. The deposits were composed of tower-like, irregularly shaped agglomerates and smooth surface deposits. The sizes of the agglomerates increase with the decrease of the plasma-torch power and most are not completely molten during the impact. After heat treatment to reduce the NiO present in the as deposited coatings, the coatings were found to contain spherical YSZ particles about 0.5 μm in diameter distributed in a continuous Ni matrix, which is verified by both SEM observation and electrical resistance measurement. The coatings have 30-50% porosity. 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.     

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.     

3D Modeling of Transport Phenomena and the Injection of the Solution Droplets in the Solution Precursor Plasma Spraying

Solution precursor plasma spraying has been used to produce finely structured ceramic coatings with nano- and sub-micrometric features. This process involves the injection of a solution spray of ceramic salts into a DC plasma jet under atmospheric condition. During the process, the solvent vaporizes as the droplet travel downstream. Solid particles are finally formed due to the precipitation of the solute, and the particle are heated up and accelerated to the substrate to generate the coating. This article describes a 3D model to simulate the transport phenomena and the trajectory and heating of the solution spray in the process. The jet-spray two-way interactions are considered. A simplified model is employed to simulate the evolution process and the formation of the solid particle from the solution droplet in the plasma jet. The temperature and velocity fields of the jet are obtained and validated. The particle size, velocity, temperature, and position distribution on the substrate are predicted. 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.     

Plasma spray synthesis from precursors: Progress, issues, and considerations

Precursor plasma spray synthesis is an innovative and rapid method for making functional oxide ceramic coatings by starting from solution precursors and directly producing inorganic films. This emerging method utilizes molecularly mixed precursor liquids, which essentially avoids the handling and selection of powders, opening up new avenues for developing compositionally complex functional oxide coatings. Precursor plasma spray also offers excellent opportunities for exploring the nonequilibrium phase evolution during plasma spraying of multicomponent oxides from inorganic precursors. Although there have been efforts in this area since the 1980s and early 1990s with the goal of synthesizing nanoparticles, only recently has the work progressed in the area of functional systems. At the Center for Thermal Spray Research an integrated investigative strategy has been used to explore the benefits and limits of this synthesis strategy. Water- and alcohol-based sol/solution precursors derived from various chemical synthesis methods were used as feedstocks to deposit thin/thick films of spherical and nanostructured coatings of yttrium aluminum garnet (YAG), yttrium iron garnet, lanthanum strontium manganate and Zr-substituted yttrium titanates, and compositions of Y₂O₃-Al₂O₃ and their microstructural space centered around stoichiometric YAG. A detailed discussion of the salient features of the radiofrequency induction plasma spraying approach, the results obtained in the investigations to develop various functional oxide coatings, and process issues and challenges are presented. 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.