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.     

Mechanical and Thermal Transport Properties of Suspension Thermal-Sprayed Alumina-Zirconia Composite Coatings

Micro-laminates and nanocomposites of Al₂O₃ and ZrO₂ can potentially exhibit higher hardness and fracture toughness and lower thermal conductivity than alumina or zirconia alone. The potential of these improvements for abrasion protection and thermal barrier coatings is generating considerable interest in developing techniques for producing these functional coatings with optimized microstructures. Al₂O₃-ZrO₂ composite coatings were deposited by suspension thermal spraying (APS and HVOF) of submicron feedstock powders. The liquid carrier employed in this approach allows for controlled injection of much finer particles than in conventional thermal spraying, leading to unique and novel fine-scaled microstructures. The suspensions were injected internally using a Mettech Axial III plasma torch and a Sulzer-Metco DJ-2700 HVOF gun. The different spray processes induced a variety of structures ranging from finely segregated ceramic laminates to highly alloyed amorphous composites. Mechanisms leading to these structures are related to the feedstock size and in-flight particle states upon their impact. Mechanical and thermal transport properties of the coatings were compared. Compositionally segregated crystalline coatings, obtained by plasma spraying, showed the highest hardness of up to 1125 VHN_{3 N}, as well as the highest abrasion wear resistance (following ASTM G65). The HVOF coating exhibited the highest erosion wear resistance (following ASTM G75), which was related to the toughening effect of small dispersed zirconia particles in the alumina-zirconia-alloyed matrix. This microstructure also exhibited the lowest thermal diffusivity, which is explained by the amorphous phase content and limited particle bonding, generating local thermal resistances within the structure.     

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.     

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.     

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.     

Measurement and numerical simulation of particle velocity in cold spraying

The velocity of cold spray particles was measured by a diagnostic system designed for thermal spray particles that is based on thermal radiation. A laser beam was used to illuminate the cold spray particles in cold spraying to obtain a sufficient radiant energy intensity for detection. The measurement was carried out for copper particles of different mean particle sizes. The particle velocity was also estimated using a two-dimensional axisymmetric model developed previously. The simulated velocity agreed well with the measured result. This fact indicates that particle velocity in cold spraying can be predicted reasonably by simulation. Therefore, it is possible to optimize the cold spray process with the aid of the simulation results. 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.     

Comparison Between High-Velocity Suspension Flame Spraying and Suspension Plasma Spraying of Alumina

Two different spray processes??suspension plasma spraying (SPS) and high-velocity suspension flame spraying (HVSFS)??are under focus in the field of suspension spraying. Both techniques are suitable for manufacturing finely structured coatings. The differences in the particle velocity and temperature of these two processes cause varying coating characteristics. The high particle velocity of the HVSFS process leads to more dense coatings with low porosity values. Coatings with a higher and also homogeneous porosity, which can be generated by SPS, have also high potential, for example, for thermal barrier coatings. In this study, both the processes??SPS and HVSFS??were compared using alumina as feedstock material mixed with different solvents. Besides the characterization of the microstructure and phase composition of the applied coatings, the focus of this study was the investigation of the melting behavior of the particles in-flight and of single splat characteristics.     

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.     

Process diagnostics in suspension plasma spraying

Benefits and limitations of process diagnostics are investigated for the suspension plasma spraying of yttria-stabilized zirconia thermal barrier coatings. The methods applied were enthalpy probe measurements, optical emission spectroscopy, and in-flight particle diagnostic.It was proved that the plasma characteristics are not affected negatively by the injection of the ethanol based suspension since the combustion of species resulting from ethanol decomposition achieves a gain of plasma enthalpy. Furthermore, the conditions of the suspension injection into the plasma were found to be optimum as a significant content of evaporated powder material could be detected. Regarding the void content and segmentation crack density of the coatings, the in-flight particle diagnostic showed that the spray distance should be dimensioned in a way that the molten particles reach the substrates just before solidification starts.     

From DC Time-Dependent Thermal Plasma Generation to Suspension Plasma-Spraying Interactions

This paper proposes an original route for modeling the time-dependent behavior of a plasma jet issued from a DC plasma-spraying torch operating with various kinds of gas mixtures. The hydrodynamic interactions between this jet and a liquid jet for suspension plasma-spraying or a classical particle injection for the deposition of coatings are studied. In a first step, the classical plasma spraying process was explored using the FLUENT CFD code. Zirconia particles, defined as Lagrangian particles, were injected in an Ar/H₂ flow and their positions, kinetic and thermal states were compared with experimental results. The trend and intensity of the values demonstrated a rather good agreement. In a second step, the suspension plasma spraying was investigated with the AQUILON CFD to simulate interactions between the plasma and aqueous jets. An Ar/H₂ plasma flow was simulated with the Large Eddy Scale turbulence model assumption, in which a liquid jet had been introduced. The behavior observed during the first stage of the interactions between the two fluids corresponded to expectations.     

Fabrication of finely structured silicon-supported SOFC with anode deposited by multi-phase plasma spraying

The mechanically mixed NiO/YSZ powder was usually used as the anode material of atmospheric plasma sprayed (APS) solid oxide fuel cells (SOFC). Big particles and the non-uniform distribution of the pores were observed in the resultant anode layer. To overcome the limitations, a method of fabricating anode layer by multi-phase plasma spraying (MPS) was proposed in this paper. The NiO and YSZ powders were delivered into plasma jet by a separate injection, where nitrogen carrier was employed to feed micrometer-sized NiO powder and liquid carrier was to feed submicrometer-sized YSZ powder. Suspension plasma spraying (SPS) was applied to fabricate dense electrolyte layer. The microstructure and composition of coatings were characterized by SEM and EDS. The results showed that finely structured anode layer with small particle size (d ∼ 2 μm) was achieved by the MPS method. The MPS anode layer was porous with the porosity of 32.1% while the APS anode layer was 22.6%. Three kinds of elements (Ni, Y, Zr) were observed in the MPS anode layer and the NiO content was calculated to be 49.6 wt%. In the SPS process, the suspension flow rate was matched to the plasma gas flow rate to obtain proper injection condition.     

Application of multiscale modeling in the coating formation simulation of APS PYSZ TBCs

The process parameters of atmospheric plasma spraying (APS) influence the coating formation and properties of partially yttria stabilized zirconia (PYSZ) thermal barrier coatings (TBC). Simulations can be used to investigate this dependency and to design the coating process for a targeted production of TBCs. A whole process simulation was realized by modeling the linked subprocesses: plasma torch, plasma free jet, powder particles characteristics, and coating formation. The coating formation can be described by model approaches with different physical assumptions and geometric scales. One approach is the simulation of single powder particles hitting the substrate surface. An alternative macroscale finite element model (FEM) model approach is applied in the coating formation simulation. A group of particles is pooled in a splash that is dependent on the precalculated particle distribution in front of the substrate. A third modeling approach is applied to calculate effective mechanical and thermodynamical properties of coatings dependent on the experimentally obtained or calculated microstructure of the PYSZ TBC, which is based on different homogenization methods. The application of three simulation approaches in the whole process simulation of APS is discussed; advantages and disadvantages are elucidated. Results based on simulation and experiments are presented for a variation of process parameters. Missing links in the multiscale approach are detected to make suggestions for future modeling and simulation 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.     

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.     

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.     

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.     

Highly Segmented Thermal Barrier Coatings Deposited by Suspension Plasma Spray: Effects of Spray Process on Microstructure

Effects of the ceramic powder size used for suspension as well as several processing parameters in suspension plasma spraying of YSZ were investigated experimentally, aiming to fabricate highly segmented microstructures for thermal barrier coating (TBC) applications. Particle image velocimetry (PIV) was used to observe the atomization process and the velocity distribution of atomized droplets and ceramic particles travelling toward the substrates. The tested parameters included the secondary plasma gas (He versus H₂), suspension injection flow rate, and substrate surface roughness. Results indicated that a plasma jet with a relatively higher content of He or H₂ as the secondary plasma gas was critical to produce highly segmented YSZ TBCs with a crack density up to ~12 cracks/mm. The optimized suspension flow rate played an important role to realize coatings with a reduced porosity level and improved adhesion. An increased powder size and higher operation power level were beneficial for the formation of highly segmented coatings onto substrates with a wider range of surface roughness.     

Effect of Powder Injection Location on Ceramic Coatings Properties When Using Plasma Spray

The effect of powder injecting location of the plasma spraying on spraying properties was studied. Three different powder-injecting methods were applied in the experiment. In the first method, the particles were axially injected into the plasma flow from the cathode tip. In the second method, the particles were radially injected into the plasma flow just downstream of the anode arc root inside the anode nozzle. In the third method, the particles were radially injected into the plasma jet at the nozzle exit. The alumina particles with a mean diameter of 20 μm were used to deposit coatings. Spraying properties, such as the deposition efficiency, the melting rate of the powder particles, and the coating quality were investigated. The results show that the spraying with axial particle injecting can heat and melt the powder particles more effectively, produce coatings with better quality, and have higher deposition efficiency. 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.     

Process map for plasma sprayed aluminum oxide-carbon nanotube nanocomposite coatings

Process map has been developed for plasma sprayed aluminum oxide (Al₂O₃) ceramic nanocomposite coatings with carbon nanotube (CNT) reinforcement in varying content and spatial distribution. The process map was constructed using the temperature and velocity data of the in-flight powder particles exiting from the plasma plume. Process map elucidates the interdependence of powder feedstock pre-treatment, CNT content and dispersion behavior on the in-flight particle thermal history and subsequently evolving microstructure and coating properties. High thermal conductivity of CNTs alters the heat transfer characteristic during the splat formation. Microstructure of the coatings consists of fully melted zone (FM), partially melted or solid-state sintered zone (PM) and porosity. Process map provides a processing control tool for plasma spraying of Al₂O₃-CNT nanocomposite coatings.     

Ambient and high-temperature thermal conductivity of thermal sprayed coatings

Aside from its importance as a design parameter for thermal barrier coatings, measuring thermal conductivity of thermal sprayed coatings itself provides a unique method to critically characterize the nature, quantity, and anisotropy of the defect morphologies in these splat-based coatings. In this paper, the authors present a systematic assessment of thermal conductivity of wide range using the flash diffusivity technique. For the case of plasma sprayed yttria-stabilized zirconia (YSZ), coatings obtained from wide-ranging initial powder morphologies as well as those fabricated under different particle states were characterized. Both in-plane and through-thickness properties were obtained. Other material systems that were considered include: metallic alloys and semiconductors of interests. Issues such as reproducibility and reliability in measurements were also considered and assessed. Finally, work in collaboration with the Oak Ridge National Laboratory (ORNL) for alternate approaches to characterization of thermal conductivity as well as high-temperature measurements was performed. 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.