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.     

Influence of Plasma Instabilities in Ceramic Suspension Plasma Spraying

Direct current Suspension Plasma Spraying (SPS) allows depositing finely structured coatings. This article presents an analysis of the influence of plasma instabilities on the yttria-stabilized suspension drops fragmentation. A particular attention is paid to the treatment of suspension jet or drops according to the importance of voltage fluctuations (linked to those of the arc root) and depending on the different spray parameters such as the plasma forming gas mixture composition and mass flow rate and the suspension momentum. By observing the suspension drops injection with a fast shutter camera and a laser flash sheet triggered by a defined transient voltage level of the plasma torch, the influence of plasma fluctuations on jet or drops fragmentation is studied through the deviation and dispersion trajectories of droplets within the plasma jet. 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.     

悬浮液等离子喷涂与常规等离子喷涂纳米结构陶瓷涂层的研究

以蛇纹石,矿物质羟基硅酸镁Mg6(Si4O10)(OH)8,为主成分的自修复剂对金属磨损表面的修复作用,在我国已得到较为广泛关注和认同。文中以在内燃机车柴油机缸套内表面生成的自修复层为例,通过SEM,XRD,XPS,AES,Laser Raman,HRTEM,STEM和纳米硬度计等表面分析和测量手段,深入观察和分析了磨损表面自修复层的生成机理。结果表明:蛇纹石的高化学活性使氧原子、氧离子和自由水从表面向内部强扩散,铁基金属的合金成分渗碳体(Fe3C)被氧化。这是有别于高温内氧化的一种特殊的内氧化过程,对磨损表面生成自修复层有决定性的作用。进而,摩擦副的相对往复运动诱发内氧化组织的形变细化和形变强化,形成性能优异的自修复保护层。     

Suspension Plasma Spraying of YPSZ Coatings: Suspension Atomization and Injection

Among processes evaluated to produce some parts of or the whole solid-oxide fuel cell, Suspension Plasma Spraying (SPS) is of prime interest. Aqueous suspensions of yttria partially stabilized zirconia atomized into a spray by an internal-mixing co-axial twin-fluid atomizer were injected into a DC plasma jet. The dispersion and stability of the suspensions were enhanced by adjusting the amount of dispersant (ammonium salt of polyacrylic acid, PAA). A polyvinyl alcohol (PVA) was further added to the suspension to tailor its viscosity. The PVA also improved the dispersion and stability of the suspensions. The atomization of optimized formulations is described implementing Weber and Ohnesorge dimensionless numbers as well as gas-to-liquid mass ratio (ALR) value. Drop size distributions changed from monomodal distributions at low We to multimodal distributions when We number increases. The viscosity of the suspensions has a clear influence on the drop size distribution and suspension spray pattern. The secondary fragmentation of the drops due to the plasma jet was evidenced and the final size of the sheared drops was shown to depend on the characteristics of the suspension. Rather dense zirconia coatings have been prepared, which is a promising way to produce electrolyte.     

Silver-Doped Hydroxyapatite Coatings Deposited by Suspension Plasma Spraying

Pure hydroxyapatite suspension was produced by wet chemical synthesis. Using a hybrid water-stabilized torch, a series of HA coatings were produced on SS304 and Ti6Al4V substrates and their properties were characterized by SEM, EDX and XRD techniques. After deposition, the amorphous phase content reached 6-10% and the coatings retained 75-82% of crystalline HA phase. Their thickness reached 145 μm. To understand the wear behavior of the coatings, pin-on-disc tribology evaluation was performed. Additionally, a set of HA coatings was prepared with pure metallic Ag content. This formed by in situ chemical decomposition of AgNO₃ added into the HA suspension. The Ag was dispersed evenly within the coatings in the form of submicron-sized particles situated predominantly along the HA splats boundaries with a total Ag content of 8 wt.%. Given the antibacterial properties of Ag, such result presents a promising step forward in the hard tissue replacement research.     

Suspension Plasma Spraying: Process Characteristics and Applications

Suspension plasma spraying (SPS) offers the manufacture of unique microstructures which are not possible with conventional powdery feedstock. Due to the considerably smaller size of the droplets and also the further fragmentation of these in the plasma jet, the attainable microstructural features like splat and pore sizes can be downsized to the nanometer range. Our present understanding of the deposition process including injection, suspension plasma plume interaction, and deposition will be outlined. The drawn conclusions are based on analysis of the coating microstructures in combination with particle temperature and velocity measurements as well as enthalpy probe investigations. The last measurements with the water cooled stagnation probe gives valuable information on the interaction of the carrier fluid with the plasma plume. Meanwhile, different areas of application of SPS coatings are known. In this paper, the focus will be on coatings for energy systems. Thermal barrier coatings (TBCs) for modern gas turbines are one important application field. SPS coatings offer the manufacture of strain-tolerant, segmented TBCs with low thermal conductivity. In addition, highly reflective coatings, which reduce the thermal load of the parts from radiation, can be produced. Further applications of SPS coatings as cathode layers in solid oxide fuel cells (SOFC) and for photovoltaic (PV) applications will be presented.     

Numerical Study on Plasma Jet and Particle Behavior in Multi-arc Plasma Spraying

Plasma jet and particle behavior in conventional single-arc plasma spraying has been subject to intensive numerical research. However, multi-arc plasma spraying is a different case which has yet to be investigated more closely. Numerical models developed to investigate the characteristics of multi-arc plasma spraying (plasma generator, plasma jet, and plasma–particle interaction models) were introduced in previous publications by the authors. The plasma generator and plasma jet models were already validated by comparing calculated plasma temperatures with results of emission spectroscopic computed tomography. In this study, the above-mentioned models were subjected to further validation effort. Calculated particle in-flight characteristics were compared with those determined by means of particle diagnostics and high-speed videography. The results show very good agreement. The main aim of the current publication is to derive conclusions regarding the general characteristics of plasma jet and particle in-flight behavior in multi-arc plasma spraying. For this purpose, a numerical parameter study is conducted in which the validated models are used to allow variations in the process parameters. Results regarding plasma jet/particle in-flight temperatures and velocities are presented. Furthermore, the general characteristics of plasma jet and particle behavior in multi-arc plasma spraying are discussed and explained. This contributes to better understanding of the multi-arc plasma spraying process, in particular regarding the injection behavior of particles into hot regions of the plasma jet. Finally, an example test case showing a possible practical application area of the models is introduced.     

Numerical Investigation of High Velocity Suspension Flame Spraying

High-velocity suspension flame spraying (HVSFS) has recently developed as a possible alternative to conventional HVOF-spraying employing liquid suspensions instead of dry powder feedstock enables the use of nanoparticles. From the fluid dynamics point of view, the HVSFS system is complex and involves three-phase (gas, liquid and solid particles) turbulent flow, heat transfer, evaporation of the suspension solvent, chemical reactions of main fuel (propane) and suspension solvent (ethanol) and supersonic/subsonic flow transitions. Computational fluid dynamic techniques were carried out to solve the mass, momentum, and energy conservation equations. The realizable k-?? turbulence model was used to account for the effect of turbulence. The HVSFS process involves two combustion reactions. A primary combustion process is the premixed oxygen-propane reaction and secondary process is the non-premixed oxygen-gaseous ethanol reaction. For each reaction, one step global reaction, which takes dissociations and intermediate reactions into account, was derived from the equilibrium chemistry code developed by Gordon and McBride and eddy dissipation model was used to calculate the rate of reactions based on the transport equations for all species (10 species) mass fractions. Droplets were tracked in the continuum in a Lagrangian approach. In this paper, flow field inside and outside the gun simulated to provide clear and complete insight about the HVSFS processes. Moreover, the effect of some operative parameters (oxy-fuel flow rate, ethanol flow rate, droplets injection velocity and droplets size) on the gas flow field along the centerline and droplets evaporation behavior was discussed.     

Induction Plasma Synthesis of Nano-Structured SOFCs Electrolyte Using Solution and Suspension Plasma Spraying: A Comparative Study

In this paper, two plasma spraying technologies: solution plasma spraying (SolPS) and suspension plasma spraying (SPS) were used to produce nano-structured solid oxide fuel cells (SOFCs) electrolytes. Both plasma spraying processes were optimized in order to achieve the thin gas-tight electrolytes. The comparison of the two plasma spraying processes is based on electrolyte phase, microstructure, morphology, as well as on plasma deposition rate. The results show that nano-structured thin electrolytes (~5 μm thick) have been successfully SPS deposited on porous anodes with a high deposition rate. Compared to the electrolytes produced by SolPS, the SPS-deposited electrolyte layer is much denser. During the SPS process, fine droplets of 0.5-1 μm in diameter impact on the surface of the coating and penetrate into the pores of the anode. As the stresses are reduced on the resulting 0.5-2 μm splats, there is no apparent microcracks network on the splats, this resulting in highly gas-tight coatings. It is demonstrated that the SPS process is beneficial for the improvement of the performance of the films to be used as SOFC electrolytes.     

Three-Dimensional Modeling of Suspension Plasma Spraying with Arc Voltage Fluctuations

In this study, a three-dimensional DC plasma torch is modeled using Joule effect method to simulate the plasma jet and its voltage fluctuations. The plasma gas is a mixture of argon/hydrogen, and the arc voltage fluctuation is used as an input data in the model. Reynolds stress model is used for time-dependent simulation of the oscillating flow of the plasma gas interacting with the ambient air. The results are used to investigate the plasma oscillation effects on the trajectory, temperature, and velocity of suspension droplets. Suspensions are formed of ethanol and yttria-stabilized zirconia submicron particles and modeled as multicomponent droplets. To track the droplets/particles, a two-way coupled Eulerian–Lagrangian method is employed. In addition, in order to simulate the droplet breakup, Kelvin–Helmholtz/Rayleigh–Taylor (KH–RT) breakup model is used. After the completion of suspension breakup and evaporation, the sprayed particles are tracked to obtain the in-flight particle conditions including trajectory, size, velocity, and temperature. The arc voltage fluctuations were found to cause more than two times wider particle trajectories resulting in wider particle temperature, velocity, and size distributions compared with the case of constant voltage.     

Manufacturing Process of Nanostructured Alumina Coatings by Suspension Plasma Spraying

This paper describes the formation process of nanostructured alumina coatings and the injection system obtained by suspension plasma spraying (SPS), an alternative to the atmospheric plasma spraying technique in which the material feedstock is a suspension of the nanopowder to be sprayed. The nanoscale alumina powders (d ≈ 20 nm) were dispersed in distilled water or ethanol and injected by a peristaltic pump into plasma under atmospheric conditions. Optical microscopy (OM), scanning electron microscopy (SEM), and x-ray diffraction (XRD) analyses were performed to study the microstructure of the nanostructured alumina coatings. The results showed that the nanoscale alumina powders in suspension were very easily adsorbed at the inner surface of injection, which caused the needle to jam. The rotation of the pump had a great effect on the suspension injection in the plasma. The very small resistance of the thin plasma boundary layer near the substrate can drastically decrease the impacting velocity of nanosize droplets. The concentration of suspension also has a significant influence on the distribution of the size of the droplet, the enthalpy needed for spraying suspension, and the roughness of the coating surface. The phase structures of alumina suspension coatings strongly depend on the plasma spraying distance. A significant nanostructured fine alumina coating was obtained in some areas when ethanol was used as a solvent. The microstructures of the coating were observed as a function of the solvent and the spraying parameters.     

Synthesis and Preliminary Tests of Suspension Plasma Spraying of Fine Hydroxyapatite Powder

The synthetic hydroxyapatite (HA, Ca₁₀(PO₄)₆(OH)₂) is a very useful biomaterial for numerous applications in medicine, such as e.g., fine powder for suspension plasma spraying. The powder was synthesized using aqueous solution of ammonium phosphate (H₂(PO₄)NH₄) and calcium nitrate (Ca(NO₃) · 4H₂O) in the carefully controlled experiments. The synthesized fine powder was characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The powder was formulated into water and alcohol based suspension and used to carry out the initial tests of plasma spraying onto titanium substrate. The phase analysis of sprayed coating was made with the XRD.     

In Situ Particle Behavior of Cast Iron Powder by Suspension Plasma Spraying

An important issue for atmospheric plasma sprayed metal coatings is the oxidation involved during processing that significantly affects its phase composition and microstructure and thus the overall coating properties. In this study, suspension thermal spraying was used to manufacture cast iron coatings with high amounts of graphite carbon as solid-lubricant, because graphite structure is considerably diminished in molten droplets of the spray material due to the dissolution into molten iron and/or the oxidation. Additional graphite formation based on the soot reaction of liquid hydrocarbon was observed. Oxidation strongly affects the soot reaction during suspension thermal spraying. Therefore, setting-up of a shroud around the plasma plume is quite effective to prevent the oxidation of hydrocarbon.     

Deposition and Characteristics of Submicrometer-Structured Thermal Barrier Coatings by Suspension Plasma Spraying

In the field of thermal barrier coatings (TBCs) for gas turbines, suspension plasma sprayed (SPS) submicrometer-structured coatings often show unique mechanical, thermal, and optical properties compared to conventional atmospheric plasma sprayed ones. They have thus the potential of providing increased TBC performances under severe thermo-mechanical loading. Experimental results showed the capability of SPS to obtain yttria stabilized zirconia coatings with very fine porosity and high density of vertical segmentation cracks, yielding high strain tolerance, and low Young??s modulus. The evolution of the coating microstructure and properties during thermal cycling test at very high surface temperature (1400?°C) in our burner rigs and under isothermal annealing was investigated. Results showed that, while segmentation cracks survive, sintering occurs quickly during the first hours of exposure, leading to pore coarsening and stiffening of the coating. In-situ measurements at 1400?°C of the elastic modulus were performed to investigate in more detail the sintering-related stiffening.     

Influence of Suspension Plasma Spraying Process Parameters on TiO2 Coatings Microstructure

The study aimed at optimizing the suspension plasma spraying of TiO₂ coatings obtained using different suspensions of fine rutile particles in water solution onto aluminum substrates. The experiments of spraying were designed using a 2³ full factorial plan. The plan enabled to find the effects of three principal parameters, i.e. electric power input to plasma, spray distance, and suspension feed rate onto microstructure of coatings, content of anatase phase and size of anatase crystals in the coatings. The microstructure of deposits was observed with scanning electron microscope (SEM) and optical microscope and their composition was characterized using energy dispersive spectrometry (EDS). The observations were made on the coatings surface and their cross-sections. The latter made it possible to determine the coatings thicknesses to be in the range from 8 to 33 μm.

Temperature Measurement Challenges and Limitations for In-Flight Particles in Suspension Plasma Spraying

Suspension plasma spraying (SPS) acquires a significant interest from the industry. The deposited coatings using this technique were proved to have unique microstructural features compared to those built by conventional plasma spraying techniques. In order to optimize this process, in-flight particle diagnostics is considered a very useful tool that helps to control various spraying parameters and permits better coating reproducibility. In that context, the temperature of in-flight particles is one of the most important key elements that helps to optimize and control the SPS process. However, the limitations and challenges associated with this process have a significant effect on the accuracy of two-color pyrometric techniques used to measure the in-flight particle temperature. In this work, the influence of several nonthermal radiation sources on the particle temperature measurement is studied. The plasma radiation scattered by in-flight particles was found to have no significant influence on temperature measurement. Moreover, the detection of the two-color signals at two different locations was found to induce a significant error on temperature measurement. Finally, the plasma radiation surrounding the in-flight particles was identified as the main source of error on the temperature measurement of in-flight particles.     

Electrocatalytically Active Nickel-Based Electrode Coatings Formed by Atmospheric and Suspension Plasma Spraying

Ni-based electrode coatings with enhanced surface areas, for hydrogen production, were developed using atmospheric plasma spray (APS) and suspension plasma spray (SPS) processes. The results revealed a larger electrochemical active surface area for the coatings produced by SPS compared to those produced by APS process. SEM micrographs showed that the surface microstructure of the sample with the largest surface area was composed of a large number of small cauliflower-like aggregates with an average diameter of 10 μm.     

Application of Suspension Plasma Spraying (SPS) for Manufacture of Ceramic Coatings

Conventional thermal spray processes as atmospheric plasma spraying (APS) have to use easily flowable powders with a size up to 100 μm. This leads to certain limitations in the achievable microstructural features. Suspension plasma spraying (SPS) is a new promising processing method which employs suspensions of sub-micrometer particles as feedstock. Therefore much finer grain and pore sizes as well as dense and also thin ceramic coatings can be achieved. Highly porous coatings with fine pore sizes are needed as electrodes in solid-oxide fuel cells. Cathodes made of LaSrMn perovskites have been produced by the SPS process. Their microstructural and electrochemical properties will be presented. Another interesting application is thermal barrier coating (TBC). SPS allows the manufacture of high-segmented TBCs with still relatively high porosity levels. In addition to these specific applications also the manufactures of new microstructures like nano-multilayers and columnar structures are presented.     

Mechanical Properties of Yttria- and Ceria-Stabilized Zirconia Coatings Obtained by Suspension Plasma Spraying

Plasma generated by the SG-100 torch was applied to spray suspension formulated with the use of ZrO₂ + 8 wt.% Y₂O₃ (8YSZ) and ZrO₂ + 24 wt.% CeO₂ + 2.5 wt.% Y₂O₃ (24CeYSZ) as solid phases. The suspensions were formulated with the use of 20 wt.% solid phase, 40 wt.% water, and 40 wt.% ethanol. The plasma spray parameters were optimized by keeping constant: (a) the electric power of 40 kW and (b) the working gas compositions of 45 slpm for Ar and 5 slpm for H₂. On the other hand, the spray distance was varied from 40 to 60 mm and the torch linear speed was varied from 300 to 500 mm/s. The coatings were sprayed onto stainless steel substrates, and their thicknesses were in the range from 70 to 110 μm. The coating microstructures were analyzed with a scanning electron microscope. Mechanical properties were tested with the different methods including the indentation and scratch tests. The indentation test, carried out with various loads ranging from 100 to 10,000 mN, enabled to determine elastic modulus and Martens microhardness. Young’s modulus of the coatings was in the range of 71-107 GPa for 8YSZ and 68-130 GPa for 24CeYSZ coatings. The scratch test enabled the authors to find the scratch macrohardness.