Microstructure and Electrochemical Behavior of a Structured Electrolyte/LSM-Cathode Interface Modified by Flame Spraying for Solid Oxide Fuel Cell Application

Plasma-sprayed yttria-stabilized zirconia (YSZ) can be potentially employed as electrolyte layers in solid oxide fuel cells (SOFCs). The formation of a structured electrolyte surface characterized by convex micro deposits generated by only partially molten particles at spraying will increase the specific surface area and subsequently improve the output performance of SOFCs. However, using completely molten YSZ particles during plasma spraying leads to the formation of locally flat surface. In this study, flame spraying was employed to deposit YSZ particles on YSZ substrate using surface-melted particles. The deposition was carried out at different spray distances on YSZ substrate preheated to 650 °C. The surface and cross-section morphology of YSZ particles were characterized by SEM. The electrochemical behavior of single cell with the structured cathode was characterized by the electrochemical impedance spectroscopy. The results show that spray distance exhibits significant influence on the morphology of deposited YSZ particles. The cathode polarization of a structured cathode was decreased by about 30-43% compared to a flat cathode at different temperatures.     

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.     

Higher Temperature Thermal Barrier Coatings with the Combined Use of Yttrium Aluminum Garnet and the Solution Precursor Plasma Spray Process

Gas-turbine engines are widely used in transportation, energy and defense industries. The increasing demand for more efficient gas turbines requires higher turbine operating temperatures. For more than 40 years, yttria-stabilized zirconia (YSZ) has been the dominant thermal barrier coating (TBC) due to its outstanding material properties. However, the practical use of YSZ-based TBCs is limited to approximately 1200 °C. Developing new, higher temperature TBCs has proven challenging to satisfy the multiple property requirements of a durable TBC. In this study, an advanced TBC has been developed by using the solution precursor plasma spray (SPPS) process that generates unique engineered microstructures with the higher temperature yttrium aluminum garnet (YAG) to produce a TBC that can meet and exceed the major performance standards of state-of-the-art air plasma sprayed YSZ, including: phase stability, sintering resistance, CMAS resistance, thermal cycle durability, thermal conductivity and erosion resistance. The temperature improvement for hot section gas turbine materials (superalloys & TBCs) has been at the rate of about 50 °C per decade over the last 50 years. In contrast, SPPS YAG TBCs offer the near-term potential of a > 200 °C improvement in temperature capability.     

Radiation Spectral Analysis and Particle Temperature/Velocity Measurement in Plasma Spray with One-Color Camera

A color camera optical diagnostic imaging system has been developed for the measurement of temperature and velocity of individual in-flight particles in thermal plasma spray, based on the principle of particle streak velocimetry and two-color thermometry. Radiation spectral analysis of the characteristic behavior of a particle-laden plasma plume was performed to identify an optimal spectral range for accurate temperature measurements over which the powder particles and the interfering thermal plasma gas are discernable. Calibration of the thermal imaging system was carried out using a blackbody furnace with uncertainties less than 1.8%. Extensive experimental measurements were taken with the optical imaging system to obtain the temperature and velocity distributions of YSZ particles in practical plasma spraying applications. The uncertainties of the measured temperature and velocity with a color camera system mostly fluctuate around ±10% in comparison with data obtained from a commercially available measuring system.     

Warm Spray Forming of Ti-6Al-4V

Warm spray (WS) is a modification of high-velocity oxy-fuel spraying, in which the temperature of the supersonic gas flow generated by the combustion of kerosene and oxygen is controlled by diluting the combustion flame with an inert gas such as nitrogen. The inert gas is injected into the mixing chamber placed between the combustion chamber and the powder feed ports, thus the temperature of the propellant gas can be controlled from ~700 to 2,000 K. Since WS allows for higher particle temperatures in comparison to cold spray, warm sprayed particles are more softened upon impact, thus resulting in greater deformation facilitating the formation of shear instability for bonding. Recently, the combustion pressure of WS has been increased from 1 (low-pressure warm spray) to 4 MPa (high-pressure warm spray) in order to increase the velocity of sprayed particles. Effects of spray parameters on microstructure, mechanical properties, and splats formation of Ti-6Al-4V were systematically studied. Obtained coatings were examined by analyzing the coating cross-section images, microhardness as well as oxygen content. In addition, flattening ratio of splats was calculated as a function of nitrogen flow rate. It was found that the increased particle velocity caused by the increased combustion pressure had significant beneficial effects in terms of improving density and controlling the oxygen level in the sprayed Ti-6Al-4V coatings.     

Toward Highly Sintering-Resistant Nanostructured ZrO2-7wt.%Y2O3 Coatings for TBC Applications by Employing Differential Sintering

There are still concerns in the scientific community about the stability of nanostructured YSZ coatings at high temperatures. Questions have been raised about the possibility of accelerated sintering of these ultrafine materials and the associated changes in properties that could accompany this sintering. In this work, nanostructured YSZ coatings were engineered to counteract sintering effects by tailoring the coatings to exhibit a bimodal microstructure formed by (i) a matrix of dense YSZ zones (produced from molten YSZ particles) and (ii) large porous nanostructured YSZ zones (produced from semimolten nanostructured YSZ particles) that were embedded in the coating microstructure during thermal spraying. These coatings were subjected to heat treatment in air at 1400 °C for 1, 5, and 20 h. The superior driving force for sintering exhibited by the porous nanozones, when compared to that of the dense zones, caused the nanozones to shrink at much faster rates than those exhibited by the denser matrix zones (i.e., differential sintering), thereby creating a significant network of voids in the coating microstructure. Due to these effects, after 20 h exposure at 1400 °C, the thermal conductivity and elastic modulus values of the conventional coatings were approximately two times higher than those of the nanostructured ones.     

Effects of Purity and Phase Content of Feedstock Powder on Thermal Durability of Zirconia-Based Thermal Barrier Coatings

The thermal durability of thermal barrier coatings (TBCs) obtained using feedstock powders with different purity and phase content was investigated by cyclic thermal testing, including the effects on the sintering and phase transformation behaviors. Three kinds of 8 wt.% yttria-stabilized zirconia, namely regular purity (8YSZ), high purity (HP), and no monoclinic phase (nMP), were employed to prepare top coats by atmospheric plasma spraying on a NiCoCrAlY bond coat using a high-velocity oxy-fuel system. Use of 8YSZ, HP, and nMP for plasma spraying affected the microstructure and lifetime of the TBC in furnace cyclic testing (FCT) at 1100 °C and the sintering rate during annealing at 1400 °C for 50, 100, 200, and 400 h. In FCT, the TBC formed from nMP showed the longest durability, while that formed from HP showed lifetime performance similar to that obtained with regular-purity 8YSZ. The TBC obtained with nMP also exhibited the lowest monoclinic phase transition rate, followed by those obtained using HP and 8YSZ.     

Low Thermal Conductivity Yttria-Stabilized Zirconia Thermal Barrier Coatings Using the Solution Precursor Plasma Spray Process

The primary function of thermal barrier coatings (TBCs) is to insulate the underlying metal from high temperature gases in gas turbine engines. As a consequence, low thermal conductivity and high durability are the primary properties of interest. In this work, the solution precursor plasma spray (SPPS) process was used to create layered porosity, called inter-pass boundaries, in yttria-stabilized zirconia (YSZ) TBCs. IPBs have been shown to be effective in reducing thermal conductivity. Optimization of the IPB microstructure by the SPPS process produced YSZ TBCs with a thermal conductivity of 0.6 W/mK, an approximately 50% reduction compared to standard air plasma sprayed (APS) coatings. In preliminary tests, SPPS YSZ with IPBs exhibited equal or greater furnace thermal cycles and erosion resistance compared to regular SPPS and commercially made APS YSZ TBCs.     

Processing Parameter Effects and Thermal Properties of Y<Subscript>2</Subscript>Si<Subscript>2</Subscript>O<Subscript>7</Subscript> Nanostructured Environmental Barrier Coatings Synthesized by Solution Precursor Induction Plasma Spraying

The solution precursor plasma spray process, in which a solution of metal salts is axially injected into an induction thermal plasma, is suitable for deposition of nanostructured environmental barrier coatings. The effects of main processing parameters, namely the solution precursor concentration, spraying distance, reactor pressure, and atomization gas flow rate, have been analyzed using D-optimal design of experiments regarding the deposition rate and coating porosity responses. Among these four parameters, the solution precursor concentration had the greatest influent on the coating structure, followed by the spraying distance and reactor pressure, and finally the atomization gas flow rate with a small contribution. It is pointed out that the species that impact on the substrate are agglomerates of nanoparticles. The equivalent thermal conductivity of selected coatings was computed from experimental temperature evolution curves obtained by laser flash thermal diffusivity analysis, using two methods: a multilayer finite-element model with optimization, and a multilayer thermal diffusion model. The results of the two models agree, with coatings exhibiting low thermal conductivity between 0.7 and 1 W/(m K) at 800 °C.     

Development of Holistic Three-Dimensional Models for Cold Spray Supersonic Jet

A three-dimensional, computational fluid dynamics (CFD) model is developed to estimate cold spray gas conditions. This model is calibrated and validated with respect to thermal history of a substrate exposed to the cold spray supersonic jet. The proposed holistic model is important to track state of gas and particles from injection point to the substrate surface with significant benefits for optimization of very rapid "nanoseconds" cold spray deposition. The three-dimensional model is developed with careful attention with respect to computation time to benefit broader cold spray industry with limited access to supercomputers. The k-ε-type CFD model is evaluated using measured temperature for a titanium substrate exposed to cold spray nitrogen at 800 °C and 3 MPa. The model important parameters are detailed including domain meshing method with turbulence, and dissipation coefficients during spraying. Heat transfer and radiation are considered for the de Laval nozzle used in experiments. The calibrated holistic model successfully estimated state of the gas for chosen high temperature and high pressure cold spray parameters used in this study. Further to this, the holistic model predictions with respect to the substrate maximum temperature had a good agreement with earlier findings in the literature.     

Impact of Impurity Content on the Sintering Resistance and Phase Stability of Dysprosia- and Yttria-Stabilized Zirconia Thermal Barrier Coatings

Dysprosia-stabilized zirconia (DySZ) is a promising candidate to replace yttria-stabilized zirconia (YSZ) as a thermal barrier coating due to its lower inherent thermal conductivity. It is also suggested in studies that DySZ may show greater stability to high temperature phase changes compared to YSZ, possibly allowing for coatings with extended lifetimes. Separately, the impurity content of YSZ powders has been proven to influence high-temperature sintering behavior. By lowering the impurity oxides within the spray powder, a coating more resistant to sintering can be produced. This study presents both high purity and standard purity dysprosia and YSZ coatings and their performance after a long heat treatment. Coatings were produced using powder with the same morphology and grain size; only the dopant and impurity content were varied. Samples have been heat treated for exposure times up to 400 h at a temperature of 1150 °C. Samples were measured for thermal conductivity to plot the evolution of coating thermal properties with respect to exposure time. Thermal conductivity has been compared to microstructure analysis and porosity measurement to track structural changes. Phase analysis utilizing x-ray diffraction was used to determine differences in phase degradation of the coatings after heat treatment.     

Effect of Suspension Plasma-Sprayed YSZ Columnar Microstructure and Bond Coat Surface Preparation on Thermal Barrier Coating Properties

Suspension plasma spraying (SPS) is identified as promising for the enhancement of thermal barrier coating (TBC) systems used in gas turbines. Particularly, the emerging columnar microstructure enabled by the SPS process is likely to bring about an interesting TBC lifetime. At the same time, the SPS process opens the way to a decrease in thermal conductivity, one of the main issues for the next generation of gas turbines, compared to the state-of-the-art deposition technique, so-called electron beam physical vapor deposition (EB-PVD). In this paper, yttria-stabilized zirconia (YSZ) coatings presenting columnar structures, performed using both SPS and EB-PVD processes, were studied. Depending on the columnar microstructure readily adaptable in the SPS process, low thermal conductivities can be obtained. At 1100 °C, a decrease from 1.3 W m^?1 K^?1 for EB-PVD YSZ coatings to about 0.7 W m^?1 K^?1 for SPS coatings was shown. The higher content of porosity in the case of SPS coatings increases the thermal resistance through the thickness and decreases thermal conductivity. The lifetime of SPS YSZ coatings was studied by isothermal cyclic tests, showing equivalent or even higher performances compared to EB-PVD ones. Tests were performed using classical bond coats used for EB-PVD TBC coatings. Thermal cyclic fatigue performance of the best SPS coating reached 1000 cycles to failure on AM1 substrates with a β-(Ni,Pt)Al bond coat. Tests were also performed on AM1 substrates with a Pt-diffused γ-Ni/γ′-Ni₃Al bond coat for which more than 2000 cycles to failure were observed for columnar SPS YSZ coatings. The high thermal compliance offered by both the columnar structure and the porosity allowed the reaching of a high lifetime, promising for a TBC application.     

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

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

Lanthanum hexaaluminate—a new material for atmospheric plasma spraying of advanced thermal barrier coatings

One of the main application fields of the thermal spraying process is thermal barrier coatings (TBCs). Today, partially stabilized zirconia (YSZ or MSZ) is mainly used as a TBC material. At temperatures above 1000 °C, zirconia layers age distinctively, including phenomena shrinkage and microcrack formation. Therefore, there is a considerable interest in TBCs for higher temperature applications. In this paper, lanthanum hexaaluminate, a newly developed TBC material with long-term stability up to 1400 °C, is presented. It ages significantly more slowly at these high temperatures than commercial zirconia-based TBCs. Its composition favors the formation of platelets, which prevent a densification of the coating by postsintering. It consists of La₂O₃, Al₂O₃, and MgO. Its crystal structure corresponds to a magnetoplumbite phase. Lanthanum hexaaluminate powders were produced using two different fabrication routes, one based on salts and the other one based on oxides. To optimize the granulate, various raw materials and additives were tested. The slurry was spray dried in a laboratory spray drier and calcined at 1650 °C. Using these two powders, coatings were produced by atmospheric plasma spraying (APS). The residual stresses of the coatings were measured by the hole drilling method, and the deposition process was optimized with respect to the residual stresses in the TBC. The coatings were extensively analyzed regarding phase composition, thermal expansion, and long-term stability, as well as microstructural properties.     

Microstructure and Thermal Cycling Behavior of Air Plasma-Sprayed YSZ/LaMgAl11O19 Composite Coatings

Yttria-stabilized zirconia (YSZ) based composite coatings with the addition of LaMgAl₁₁O₁₉ (LaMA) as the secondary phase, were prepared by air plasma spraying in order to improve the performances of the traditional YSZ coating. Results indicate that the newly developed composite coating shows increased vertical crack density with the enhancement of the LaMA content during thermal cycling process, which results in increased strain tolerance and service lifetime. However, such composite coatings about 200 ??m thick, exhibit inferior thermal cycling lifetimes with respect to the typical YSZ coating for surface temperatures above 1400 °C. The presence of amorphous LaMA phase in the composite coating results in increased thermal conductivity and a relative thin top coat leading to a reduced thermal insulation efficiency. These are believed to be responsible for the premature degradation of bond coat and final top coat spallation failure. Such an investigation gives useful guidelines to develop advanced composite coatings based on YSZ/LaMA systems.     

Effect of Substrate Preheating on Bonding Strength of Cold-Sprayed Mg Coatings

A poor bonding strength between the magnesium coating and substrate limits magnesium coating’s application. This paper aims at improving the bonding strength between the coating and substrate using substrate preheating. Aluminum substrates were heated to 100, 200 and 300 °C by a flame nozzle prior to cold spraying. The effects of substrate preheating on the microstructure and bonding strength were studied. The deformation behavior of single particles was simulated by a commercial software ABAQUS, and observed using SEM. The results show that substrate preheating can increase the bonding strength significantly. The bonding strength increased from 3.3 ± 0.8 to 11.6 ± 0.5 MPa when the substrate temperature increased from room-temperature to 200 °C. The fracture analyses show that the coating fracture occurred within the coating when the substrate was preheated at 200 °C.     

Cold Spray Coating of Submicronic Ceramic Particles on Poly(vinyl alcohol) in Dry and Hydrogel States

We report an approach using cold spray technology to coat poly(vinyl alcohol) (PVA) in polymer and hydrogel states with hydroxyapatite (HA). Using porous aggregated HA powder, we hypothesized that fragmentation of the powder upon cold spray could lead to formation of a ceramic coating on the surface of the PVA substrate. However, direct spraying of this powder led to complete destruction of the swollen PVA hydrogel substrate. As an alternative, HA coatings were successfully produced by spraying onto dry PVA substrates prior to swelling in water. Dense homogeneous HA coatings composed of submicron particles were obtained using rather low-energy spraying parameters (temperature 200-250 °C, pressure 1-3 MPa). Coated PVA substrates could swell in water without removal of the ceramic layer to form HA-coated hydrogels. Microscopic observations and in situ measurements were used to explain how local heating and impact of sprayed aggregates induced surface roughening and strong binding of HA particles to the molten PVA substrate. Such an approach could lead to design of ceramic coatings whose roughness and crystallinity can be finely adjusted to improve interfacing with biological tissues.     

Ni-Al Nanoscale Energetic Materials: Phenomena Involved During the Manufacturing of Bulk Samples by Cold Spray

It has been shown that the cold-gas dynamic spraying process, or simply cold spray, is a suitable technique to manufacture nanoscale energetic materials with high reactivity and low porosity. The current study focuses on the Ni-Al system, for which the reactivity has been increased by an initial mechanical activation achieved by the ball-milling technique, leading to lamellar nanostructured composite particles. The consolidation of this nanoscale energetic material using the cold-gas dynamic spray technique permits to retain the feedstock powder nanoscale structure in the coatings, which in turn retain the high reactivity features of the powder. However, it has been noticed that the stagnation temperature during the spray can lead to partial reaction of the highly reactive feedstock powder, which directly influences the reactivity of the coatings. In this study, different stages of the spray process were investigated: (i) the in-flight behavior of the nanoscale energetic material (powder) at different stagnation temperatures (from 300 to 800 °C); (ii) the substrate-temperature evolution as the function of gas temperature; and (iii) the impact of the powder on the substrate, related to particle’s velocity and its influence on the nanostructure of the particles.     

Impedance Analysis of 7YSZ Thermal Barrier Coatings During High-Temperature Oxidation

ZrO₂-7 wt.%Y₂O₃ (7YSZ) thermal barrier coatings (TBCs) were prepared by atmospheric plasma spraying. High-temperature oxidation of 7YSZ TBCs was accomplished at 950 °C and characterized by impedance spectroscopy and scanning electron microscopy with energy-dispersive spectrometry. The results indicated that the thermally grown oxide (TGO) mainly contained alumina. The increase of the thickness of the TGO layer appeared to follow a parabolic law. Impedance analysis demonstrated that the resistance of the TGO increased with increasing oxidation time, also following a parabolic law, and that characterization of the TGO thickness based on fitting an equivalent circuit to its measured resistance is feasible. The YSZ grain-boundary resistance increased due to increasing cracks within the coating for oxidation time less than 50 h. However, beyond 150 h, the YSZ grain-boundary resistance slightly decreased, mainly due to sintering of the coating during the oxidation process.     

Diagnostics of Cold-Sprayed Particle Velocities Approaching Critical Deposition Conditions

In cold spraying, the impact particle velocity plays a key role for successful deposition. It is well known that only those particles can achieve successful bonding which have an impact velocity exceeding a particular threshold. This critical velocity depends on the thermomechanical properties of the impacting particles at impacting temperature. The latter depends on the gas temperature in the torch but also on stand-off distance and gas pressure. In the past, some semiempirical approaches have been proposed to estimate particle impact and critical velocities. Besides that, there are a limited number of available studies on particle velocity measurements in cold spraying. In the present work, particle velocity measurements were performed using a cold spray meter, where a laser beam is used to illuminate the particles ensuring sufficiently detectable radiant signal intensities. Measurements were carried out for INCONEL^® alloy 718-type powders with different particle sizes. These experimental investigations comprised mainly subcritical spray parameters for this material to have a closer look at the conditions of initial deposition. The critical velocities were identified by evaluating the deposition efficiencies and correlating them to the measured particle velocity distributions. In addition, the experimental results were compared with some values estimated by model calculations.