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.     

A Fitting Formula for Predicting Droplet Mean Diameter for Various Liquid in Effervescent Atomization Spray

The outflow of the effervescent atomization spray is simulated by a comprehensive numerical model based on the Navier-Stokes equation and the particle tracking method. The droplet mean diameter under different operating conditions and liquid properties were calculated. Based on the extensive computations, a formula relating droplet Sauter mean diameter to the operating conditions and liquid physical parameters were obtained with curve fitting technique. The results calculated from the formulae were compared with the experimental data and a good agreement was obtained. The formulae can be used to predict the droplet mean diameter for various Newtonian liquid in axisymmetric effervescent atomization spray conveniently and effectively.     

Microstructure of Suspension Plasma Spray and Air Plasma Spray Al2O3-ZrO2 Composite Coatings

Al₂O₃-ZrO₂ coatings were deposited by the suspension plasma spray (SPS) molecularly mixed amorphous powder and the conventional air plasma spray (APS) Al₂O₃-ZrO₂ crystalline powder. The amorphous powder was produced by heat treatment of molecularly mixed chemical solution precursors below their crystallization temperatures. Phase composition and microstructure of the as-synthesized and heat-treated SPS and APS coatings were characterized by XRD and SEM. XRD analysis shows that the as-sprayed SPS coating is composed of α-Al₂O₃ and tetragonal ZrO₂ phases, while the as-sprayed APS coating consists of tetragonal ZrO₂, α-Al₂O₃, and γ-Al₂O₃ phases. Microstructure characterization revealed that the Al₂O₃ and ZrO₂ phase distribution in SPS coatings is much more homogeneous than that of APS coatings.     

An Insight into Suspension Plasma Spray: Injection of the Suspension and Its Interaction with the Plasma Flow

Yttria Stabilized Zirconia (YSZ) suspensions were injected in an atmospheric plasma jet using two designs of a home-made two-fluid atomizing nozzle. The sprays of drops were visualized and the behavior of the suspension in the plasma jet was investigated by implementing the Particle Image Velocimetry (PIV) method. The effects of the suspension formulation (surface tension, liquid viscosity, and relative gas-to-liquid mass ratio, GLR) on the distribution and median value of the drop size as well as on the velocity maximum value were evaluated. The interactions between the sprays and the plasma jet were studied. The differences in the behavior of the particle velocity along and radial to the torch axis were pointed out. The validity of PIV measurements was finally demonstrated by the relation established between the in-flight particle velocity and the coating structure.     

Microstructural Characteristics of Y2O3-MgO Composite Coatings Deposited by Suspension Plasma Spray

Dense composite Y₂O₃-MgO coatings have been deposited by suspension plasma spray. Ethanol-based suspensions of powders synthesized by thermal decomposition of precursor solutions containing yttrium nitrate (Y[n]) and magnesium nitrate (Mg[n]) or magnesium acetate (Mg[a]) were selected as the feedstock; this gave powders with both phases in each particle, to inhibit phase segregation during solvent evaporation. The influence of powder characteristics on the microstructures of the coatings was investigated. The Y[n]Mg[a] suspension was more stable, with a better dispersion of the component phases than the Y[n]Mg[n] suspension. The coatings deposited using each suspension type exhibited lamellar structures comprising Y₂O₃ and MgO phases in wavy alternating streaks, with unmelted/semi-melted particles entrapped in the lamellae; this indicates that phase segregation still occurred in the molten state. Eutectic structures were formed in the coating generated using the Y[n]Mg[a] suspension, resulting from improved mixing of the component phases in the suspension powder.     

离心雾化等离子喷涂粒子的形成及其分布研究

介绍了离心雾化等离子喷涂技术的工作原理和喷涂粒子的雾化机理，分析了雾化粒子的形成过程。通过试验收集喷涂粒子，使用扫描电镜观察雾化粒子的表面形貌，统计分析了在不同转速的情况下粒子的粒度及其分布，并与理论计算值进行了比较。研究表明，离心雾化等离子喷涂中粒子球形度较好，随着电极转速的提高，粒子的粒度减小，和电弧喷涂的粒子相比，离心雾化等离子喷涂的粒子粒度较大，且分布较均匀。分析了粒子粒度及其分布的影响因素，结果表明粒子粒度与消耗电极的转速、半径、熔融液滴的密度成反比，与熔融液滴的表面张力成正比。     

Pressure-Based Liquid Feed System for Suspension Plasma Spray Coatings

Thermal spraying with liquid-based feedstocks demonstrated a potential to produce coatings with new and enhanced characteristics. A liquid delivery system prototype was developed and tested in this study. The feeder is based on the 5MPE platform and uses a pressure setup to optimally inject and atomize liquid feedstock into a plasma plume. A novel self-cleaning apparatus is incorporated into the system to greatly reduce problems associated with clogging and agglomeration of liquid suspensions. This approach also allows the liquid feedstock line to the gun to remain charged for quick on-off operation. Experiments on aqueous and ethanol-based suspensions of titania, alumina, and YSZ were performed through this liquid delivery system using a 9MB plasma gun. Coatings with ultrafine splat microstructures were obtained by plasma spraying of those suspensions. Phase composition and microstructure of the as-sprayed coatings were investigated.     

Synchronization of Suspension Plasma Spray Injection with the Arc Fluctuations

Poorly controlled heat and momentum transfers between plasma and material, plasma instabilities are some of the difficulties encountered in suspension plasma spraying. The improvement of this method is usually attempted by means of the reduction of arc fluctuations. This paper presents a new approach to the injection of reactive material in an arc jet. The principle is to produce a pulsed laminar plasma jet combined with phased injection of liquid droplets. This is achieved by the particular design of the plasma torch that works at moderate power and following a resonant mode. The droplets are injected using a piezoelectric device, based on drop-on-demand method, triggered by the voltage signal sampled at the torch connections. The results are evaluated by time-resolved imaging technique that shows how the trajectories are influenced by the moment at which the droplets penetrate the plasma jet.     

静电雾化喷射成形装置设计及流场模拟

喷射成形是快速凝固技术的重要发展方向之一,近年来,静电雾化技术应用到喷射成形过程中,使该技术更加完善,而静电雾化喷射成形装置是该技术的关键技术.本文设计了静电雾化装置,并对喷射成形工艺中静电作用下气体流场进行了模拟,结果表明,静电作用改善了雾化效果,提高了喷射成形产品的质量.     

Nanoparticles Modeling in Axially Injection Suspension Plasma Spray of Zirconia and Alumina Ceramics

Suspension plasma spray (SPS) is a thermal spray method in which nanoparticles are injected into the plasma jet with the help of suspension droplets to achieve thin and finely structured nanocoatings. The nanoparticles experience three in-flight stages: injection within the suspension droplets, discharge of the nanoparticle agglomerates after the evaporation of the suspension solvent, and tracking of the nanoparticle or agglomerates during the momentum and heat transfer with the plasma jet before coating. A numerical model is proposed in this paper for nanoparticle injection, discharge, acceleration, heating, melting, and evaporation. Initial values of suspension droplet size and agglomerate size are selected according to typical experimental data. Noncontinuum effects on particle acceleration and heating, known as Knudsen effects, are considered, as well as the influence of evaporation on the heat transfer. After a comparison with the experimental data, this nanoparticle model is applied for zirconia and alumina axially injected into the suspension plasma spray. Trajectory, velocity, and temperature of the in-flight nanoparticles are predicted for different initial sizes ranging from 30 nm to 1.5 μm; the distributions of the particle characteristics for multiple particles in the spray are also presented. The effects of powder size and material, power input, plasma gas flow rate, and standoff distance on the nanoparticle characteristics have been investigated and discussed.     

Effective Parameters in Axial Injection Suspension Plasma Spray Process of Alumina-Zirconia Ceramics

Suspension plasma spray (SPS) is a novel process for producing nano-structured coatings with metastable phases using significantly smaller particles as compared to conventional thermal spraying. Considering the complexity of the system there is an extensive need to better understand the relationship between plasma spray conditions and resulting coating microstructure and defects. In this study, an alumina/8 wt.% yttria-stabilized zirconia was deposited by axial injection SPS process. The effects of principal deposition parameters on the microstructural features are evaluated using the Taguchi design of experiment. The microstructural features include microcracks, porosities, and deposition rate. To better understand the role of the spray parameters, in-flight particle characteristics, i.e., temperature and velocity were also measured. The role of the porosity in this multicomponent structure is studied as well. The results indicate that thermal diffusivity of the coatings, an important property for potential thermal barrier applications, is barely affected by the changes in porosity content.     

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.     

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.     

Nanocomposite Lanthanum Zirconate Thermal Barrier Coating Deposited by Suspension Plasma Spray Process

This work seeks to develop an innovative nanocomposite thermal barrier coating (TBC) exhibiting low thermal conductivity and high durability compared with that of current TBCs. To achieve this objective, nanosized lanthanum zirconate particles were selected for the topcoat of the TBC system, and a new process—suspension plasma spray—was employed to produce desirable microstructural features: the nanocomposite lanthanum zirconate TBC contains ultrafine splats and high volume porosity, for lower thermal conductivity, and better durability. The parameters of plasma spray experiment included two main variables: (i) spray distance varying from 40 to 80 mm and (ii) the concentration of suspension 20, 25, and 30 wt.%, respectively. The microstructure of obtained coatings was characterized with scanning electron microscope and x-ray diffraction. The porosity of coatings is in the range of 6-10%, and the single phase in the as-sprayed coatings was pyrochlore lanthanum zirconate.     

Mathematical Modeling and Numerical Simulation of Splat Cooling in Plasma Spray Coatings

Particle deformation and cooling significantly affect the characteristics of thermally sprayed coatings, such as the adhesion and cohesion strength between a splat and a substrate and between splats, as well as the internal stresses of deposits. It is essential to understand these processes for the successful industrial application of thermal spray technology. However, to date, the microstructure of the boundary of a splat and the substrate has not been clarified, although much research has been conducted on splat formation and the cooling process. We have developed a microstructure model of the boundary between the splat and the substrate, based on splat morphology obtained from experiments. In the model, it is assumed that gaps, or voids, and contact areas are arranged on the splat boundary with the substrate in an orderly fashion. The model includes phase changes and heat resistance simulating the function of the microstructure during splat cooling. Assumptions in the model are that ambient gas trapped in the gaps, or voids, transfers heat only by conduction and not by convection or radiation. The results of the simulation indicated that the extent of gaps, or voids, significantly affects the rate of decrease of the average temperature of the splat surface, as well as the temperature distribution inside the splat.     

Erosion Performance of Gadolinium Zirconate-Based Thermal Barrier Coatings Processed by Suspension Plasma Spray

7-8 wt.% Yttria-stabilized zirconia (YSZ) is the standard thermal barrier coating (TBC) material used by the gas turbines industry due to its excellent thermal and thermo-mechanical properties up to 1200 °C. The need for improvement in gas turbine efficiency has led to an increase in the turbine inlet gas temperature. However, above 1200 °C, YSZ has issues such as poor sintering resistance, poor phase stability and susceptibility to calcium magnesium alumino silicates (CMAS) degradation. Gadolinium zirconate (GZ) is considered as one of the promising top coat candidates for TBC applications at high temperatures (>1200 °C) due to its low thermal conductivity, good sintering resistance and CMAS attack resistance. Single-layer 8YSZ, double-layer GZ/YSZ and triple-layer GZdense/GZ/YSZ TBCs were deposited by suspension plasma spray (SPS) process. Microstructural analysis was carried out by scanning electron microscopy (SEM). A columnar microstructure was observed in the single-, double- and triple-layer TBCs. Phase analysis of the as-sprayed TBCs was carried out using XRD (x-ray diffraction) where a tetragonal prime phase of zirconia in the single-layer YSZ TBC and a cubic defect fluorite phase of GZ in the double and triple-layer TBCs was observed. Porosity measurements of the as-sprayed TBCs were made by water intrusion method and image analysis method. The as-sprayed GZ-based multi-layered TBCs were subjected to erosion test at room temperature, and their erosion resistance was compared with single-layer 8YSZ. It was shown that the erosion resistance of 8YSZ single-layer TBC was higher than GZ-based multi-layered TBCs. Among the multi-layered TBCs, triple-layer TBC was slightly better than double layer in terms of erosion resistance. The eroded TBCs were cold-mounted and analyzed by SEM.     

Phase Formation and Transformation in Alumina/YSZ Nanocomposite Coating Deposited by Suspension Plasma Spray Process

Suspension Plasma Spray process was used for deposition of pseudo-eutectic composition of alumina-yttria-stabilized zirconia as a potential thermal barrier coating using Mettech axial III torch. Process variables including feed and plasma parameters were altered to find their effects on the formation of phases in the composite coating. The in-flight particle velocity was found to be the crucial parameter on phase formation in the resulting coatings. Low particle velocities below 650 m/s result in the formation of stable phases i.e., α-alumina and tetragonal zirconia. In contrast, high particle velocities more than 750 m/s favor the metastable γ-alumina and cubic zirconia phases as dominant structures in as-deposited coatings. Accordingly, the plasma auxiliary gas and plasma power as influential parameters on the particle velocity were found to be reliable tools in controlling the resulting coating structure thus, the consequent properties. The noncrystalline portion of the coatings was also studied. It was revealed that upon heating, the amorphous phase prefers to crystallize into pre-existing crystalline phases in the as-deposited coating. Thus, the ultimate crystalline structure can be designed using the parameters that control the particle velocity during plasma spray coating.     

等离子喷涂陶瓷粒子加热加速行为的数值模拟

通过数值模拟研究了等离子喷涂陶瓷粒子的加热加速行为。用SprayWatch-2i粒子测速仪测定的典型工艺条件下等离子喷涂陶瓷粒子的状态参量进行验证,结果表明:测量结果与计算结果吻合较好。系统地研究了气体参数和粒子参数对粒子加热加速行为的影响,为提高等离子喷涂效率和获得高质量涂层提供理论依据。     

等离子喷涂陶瓷粒子加热加速行为的数值模拟

通过数值模拟研究了等离子喷涂陶瓷粒子的加热加速行为。用SprayWatch-2i粒子测速仪测定的典型工艺条件下等离子喷涂陶瓷粒子的状态参量进行验证，结果表明：测量结果与计算结果吻合较好。系统地研究了气体参数和粒子参数对粒子加热加速行为的影响，为提高等离子喷涂效率和获得高质量涂层提供理论依据。     

Suspension Plasma Spray and Performance Characterization of Half Cells with NiO/YSZ Anode and YSZ Electrolyte

The use of a liquid feedstock carrier in suspension plasma spray (SPS) permits injection of fine powders, providing the possibility of producing sprayed coatings that are both thin and dense and have fine microstructures. These characteristics make SPS an attractive process for depositing highly efficient electrodes and electrolytes for solid oxide fuel cell (SOFC) applications. In this study, NiO-yttria stabilized zirconia (YSZ) anode and YSZ electrolyte half cells were successfully deposited on porous Hastelloy X substrates by SPS. The NiO-YSZ anode deposition process was optimized by design of experiment. The YSZ electrolyte spray process was examined by changing one parameter at a time. The results from the design-of-experiment trials indicated that the porosity of the as-deposited coatings increased with an increase of suspension feed rate while it decreased with an increase of total plasma gas flow rate and standoff distance. The deposition rate increased with an increase of total plasma gas flow rate, suspension feed rate, and standoff distance. The microstructure examination by SEM showed that the NiO and YSZ phases were homogeneously distributed and that the YSZ phase had a lamellar structure. It was observed that the density of the YSZ electrolyte layer increased as input power of the plasma torch increased. Electrochemical characterization of the fabricated cells indicated that an open cell voltage of 0.989 V at 500 °C and a peak power of 0.610 W/cm² at 750 °C were reached.