Water-stabilized Plasma Torch Research Articles

Suspension Spraying Tip: High Molecular Weight Solvent

In suspension spraying, two most frequently used solvents are water and ethanol. In this study, we test the potential of using alternative, high molecular weight solvent and demonstrate the associated advantages. For that, two organic solvents are directly compared: ethanol (serving as a benchmark, suspension formulated at 10 wt.% solid load) and di-propylene glycol methyl ether (two suspensions at 10 wt.% and 20 wt.% solid load). As a model material, $$\hbox {Al}_{2}\hbox {O}_3$$ is selected, a frequently sprayed ceramics employed in many industrial sectors. Sub-micron 100% alpha-alumina powder is used to formulate the suspensions. Identical spray conditions are then used to deposit the coatings using hybrid water-stabilized plasma torch. Shadowgraphy monitoring of the suspension fragmentation as well as in situ measurement of the particle in-flight properties is employed, showing no significant differences between the three series. Further, it is shown that the ethanol- and ether-based-feedstock coatings are fully comparable in terms of their microstructure, porosity content, surface roughness as well as hardness and adhesion to the substrates. Importantly, the ether-based coatings exhibit slightly higher levels of $$\alpha$$ - $$\hbox {Al}_{2}\hbox {O}_3$$ phase when compared to their ethanol-based counterpart (17 wt.% vs. 6 wt.%). The use of 20 wt.% solid load in the ether solvent leads to twofold increase in the deposition rate while (as opposed to ethanol) successfully retaining a dense microstructure. Lastly, the ether is significantly cheaper and safer to handle than ethanol.

Dielectric properties of Ce-doped YAG coatings produced by two techniques of plasma spraying

Yttrium aluminum garnet (YAG) with cerium admixture (Ce:YAG) was plasma sprayed using two different devices – gas-stabilized plasma (GSP) torch and water-stabilized plasma (WSP) torch. Coatings on stainless steel as well as self-standing plates were produced. Besides microstructure and crystallographic characterizations, dielectric tests were performed on these coatings. They included capacitance (i.e. relative permittivity), loss tangent and volume resistivity measurements. After spraying, the YAG crystal phase was preserved without any decomposition, but an amorphous fraction was detected in the as-sprayed coatings deposited by both processes. The dielectric behavior of the coatings was influenced by imperfections like splat boundaries, pores and thin cracks. The Ce:YAG samples were successfully plasma sprayed by both spray techniques. Selected aspects of wear were measured and compared with a single-crystal. The dielectric properties are comparable with the single-crystal and highly promising, particularly the loss tangent with values so low that they were not found in any other as-sprayed ceramic coating.

Microstructures and Thermal Cycling Properties of Thermal Barrier Coatings Deposited by Hybrid Water-Stabilized Plasma Torch

Hybrid water-stabilized plasma (WSP-H) torches provide high-enthalpy plasma which may be utilized for high-throughput and yet economical spraying of coatings from powders, suspensions, and solutions. It was previously demonstrated that microstructures and functional properties of the WSP-H coatings may be tailored to a wide extent for new applications, namely those requiring high coating thickness and/or coating of large components. In this study, applicability potential of WSP-H technology for spraying of novel thermal barrier coatings (TBCs) is demonstrated. WSP-H technology was used for spraying of yttria-stabilized zirconia (YSZ) top-coats from powder, suspension, and solution. Yttria content in the top-coat feedstock was 7-8 wt.%. In addition, gadolinium zirconate (Gd2Zr2O7-GZO) was sprayed from suspension for comparison. NiCrAlY bond-coat was also deposited by WSP-H, and Hastelloy-X alloy was used as substrate material. Microstructure, phase composition, and endurance of the deposited coatings in thermal cycling fatigue (TCF) test and during high-temperature short-term annealing were evaluated. All coatings showed excellent high-temperature stability and TCF resistance withstanding more than 650 cycles, surpassing some of the currently commercially used TBCs. Lifetime of the TBC with columnar top-coat deposited from YSZ suspension exceeded even more than 900 cycles.

Improvement of Mechanical Properties of Plasma Sprayed Al2O3-ZrO2-SiO2 Amorphous Coatings by Surface Crystallization.

Ceramic Al2O3−ZrO2−SiO2 coatings with near eutectic composition were plasma sprayed using hybrid water stabilized plasma torch (WSP-H). The as-sprayed coatings possessed fully amorphous microstructure which can be transformed to nanocrystalline by further heat treatment. The amorphous/crystalline content ratio and the crystallite sizes can be controlled by a specific choice of heat treatment conditions, subsequently leading to significant changes in the microstructure and mechanical properties of the coatings, such as hardness or wear resistance. In this study, two advanced methods of surface heat treatment were realized by plasma jet or by high energy laser heating. As opposed to the traditional furnace treatments, inducing homogeneous changes throughout the material, both approaches lead to a formation of gradient microstructure within the coatings; from dominantly amorphous at the substrate–coating interface vicinity to fully nanocrystalline near its surface. The processes can also be applied for large-scale applications and do not induce detrimental changes to the underlying substrate materials. The respective mechanical response was evaluated by measuring coating hardness profile and wear resistance. For some of the heat treatment conditions, an increase in the coating microhardness by factor up to 1.8 was observed, as well as improvement of wear resistance behaviour up to 6.5 times. The phase composition changes were analysed by X-ray diffraction and the microstructure was investigated by scanning electron microscopy.

Lignite Gasification in Thermal Steam Plasma

Recycling of organic waste is an increasingly hot topic in recent years. This issue becomes even more interesting if such processing leads to a source of hydrogen or syngas for fuel production. A process of high-temperature decomposition of lignite was studied on the plasma gasification reactor PLASGAS, where water-stabilized plasma torch was used as a source of high-enthalpy plasma. The plasma torch power was 120 kW and allowed heating of the reactor to more than 1000 °C. The material feeding rate in the gasification reactor was 30 or 60 kg per hour that is comparable to a small industrial production process. The efficiency evaluation of the thermal decomposition process was performed. Energy balance of the process was carried out as well as an influence of the lignite particle size and the addition of methane (CH4) on the synthesis gas composition. The ratio H2/CO was in the range of 1.5–2.5 depending on the experimental conditions.

Barium Titanate Dielectrics Sprayed by a High Feed-Rate Water-Stabilized Plasma Torch

Barium titanate coatings were first time sprayed by a high feed-rate plasma torch with water stabilization. Two power levels of the torch were applied. Two substrate materials were used—stainless steel and carbon steel. Various substrate preheating levels from 125 to 450 °C were applied to change the cooling conditions. Microstructure, phase composition including crystallinity quantification, surface roughness and microhardness were evaluated. Dielectric measurements proved that coatings with medium-level relative permittivity and with stable loss factor course versus frequency of the AC electric field were fabricated by spraying. The cold substrates provided coatings with low reflectivity and visibly darker surface compare to the hot substrates. The coatings exhibited good dielectric properties—on the top of an expectable range for plasma-sprayed BaTiO3. This study is targeted to coatings prospective for electrical industry, namely via optimization of conditions at the high feed-rate spraying.

After-glow luminescence of SrZrO3 prepared by plasma spraying

Strontium zirconate SrZrO3 is a multifunctional material studied in literature as a luminescent material, proton-conductor, thermal barrier coating, and dielectric ceramics. In our study this material was sprayed by a high feed-rate water-stabilized plasma torch WSP 500 at its standard electric power 150kW. The as-deposited coatings exhibited lamellar microstructure with relatively high porosity over 13%. Archimedean (water immersion) specific weight was 4.54g/cm3. Annealing was done in air at 1350°C. Annealed coating exhibited an interesting response to UV light, including after-glow luminescence. After excitation by 225nm light the sample exhibited after-glow exponential luminescence decay with 5s characteristic lifetime. Diffused reflectance of the coatings was measured as well. The infrared reflectance is slightly lower after annealing, whereas in the ultraviolet band it is higher.

Strontium Zirconate TBC Sprayed by a High Feed-Rate Water-Stabilized Plasma Torch

A novel thermal barrier coating (TBC) material, strontium zirconate SrZrO3, was sprayed by a high feed-rate water-stabilized plasma torch WSP 500. Stainless steel coupons were used as substrates. Coatings with a thickness of about 1.2 mm were produced, whereas the substrates were preheated over 450 °C. The torch worked at 150 kW power and was able to spray SrZrO3 with a high spray rate over 10 kg per hour. Microstructure and microhardness, phase composition, adhesion, thermal conductivity and thermal expansion were evaluated. The coating has low thermal conductivity under 1 W/m K in the interval from room temperature up to 1200 °C. Its crystallite size is slightly over 400 nm and thermal expansion 12.3 µm K−1 in the similar temperature range.

Controlling Microstructure of Yttria-Stabilized Zirconia Prepared from Suspensions and Solutions by Plasma Spraying with High Feed Rates

Introduction of suspension and solution plasma spraying led to a breakthrough in the deposition of yttria-stabilized zirconia (YSZ) coatings and enabled preparation of new types of layers. However, their deposition with high feed rates needed, for example, for the deposition of thermal barrier coatings (TBCs) on large-scale components, is still challenging. In this study, possibility of high-throughput plasma spraying of YSZ coatings is demonstrated for the latest generation of high-enthalpy hybrid water-stabilized plasma (WSP-H) torch technology. The results show that microstructure of the coatings prepared by WSP-H may be tailored for specific applications by the choice of deposition conditions, in particular formulation of the liquid feedstock. Porous and columnar coatings with low thermal conductivity (0.5-0.6 W/mK) were prepared from commercial ethanol-based suspension. Dense vertically cracked coatings with higher thermal conductivity but also higher internal cohesion were deposited from suspension containing ethanol/water mixture and coarser YSZ particles. Spraying of solution formulated from diluted zirconium acetate and yttrium nitrate hexahydrate led also to the successful deposition of YSZ coating combining regions of porous and denser microstructure and providing both low thermal conductivity and improved cohesion of the coating. Enthalpy content, liquid-plasma interaction and coating buildup mechanisms are also discussed.

Development of suspension plasma sprayed alumina coatings with high enthalpy plasma torch

Deposition of aluminium oxide (Al2O3) coatings from liquid feedstocks using a high enthalpy hybrid water-stabilized plasma torch was investigated. The entire process included the optimization of spraying parameters using a commercial ready-to-spray suspension, optimization and deposition of custom-made suspensions and one solution and evaluation of mechanical properties of the most durable coatings. Acquired coating microstructures varied from porous with typical columnar morphology to well-sintered dense structures with low porosity. The microstructural features were clearly linked to the feedstock formulation. The most durable coating with the highest density microstructure prepared from ethanol-based suspension showed outstanding mechanical properties, e.g. high values of hardness (up to 1211HV0.3), tensile adhesion strength (up to 51MPa) and wear resistance (material removal rate as low as 1.94·10−5mm3·N−1·m−1 as measured by pin-on-disc test). Moreover, deposition from a water-based solution of aluminium nitrate resulted in deposition of highly porous coating composed predominantly of stable α-alumina phase.

The microstructural studies of suspension plasma sprayed zirconia coatings with the use of high-energy plasma torches

The presented studies are focused on the microstructure characterization of zirconia-based coatings deposited by two types of high-energy plasma torches: (i) Axial III; and, (ii) hybrid version of Water-Stabilized Plasma (WSP) torch. The suspensions were formulated using solid dispersed phase of: (i) zirconia stabilized with 14wt% of Y2O3 and (ii) zirconia stabilized with 24wt% of CeO2+2.5wt% of Y2O3 and continuous phase of water with ethanol. The spray process parameters were optimized for each plasma set-up individually. The in-flight observations (shadowgraphy) were performed to optimize the injection of the liquid feedstock into the plasma jet. Then the coating's morphology and coating/substrate interface were characterized using conventional light microscopy and scanning electron microscopy (SEM). The results showed that through the change of deposition parameters various coatings microstructures could be obtained, in particular columnar and two-zones structures. The EDS/EDX and XRD studies showed that there was no significant change in chemical/phase composition of zirconia material before and after spraying. Electron backscatter diffraction (EBSD) method allowed to analyze the grain size in the coating microstructure as well as crystallographic orientation of individual grains. The results showed that coatings were characterized by submicrometric microstructure what corresponded to the size of powder particles used to formulate suspension. No texture was observed in the coatings microstructure. The surface topography analysis which was performed by confocal scanning laser microscopy (CSLM) and Shape From Shading (SFS) technique proved the great influence of suspension concentration on the coating structure.

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.

Metallurgical bond between magnesium AZ91 alloy and aluminium plasma sprayed coatings

We report on creation of metallurgic bond between AZ91 magnesium alloy and aluminium plasma sprayed coatings which has been so far observed only after additional surface treatments. High-enthalpy plasma spray process employing water-stabilized plasma torch was used to spray commercially pure aluminium and AlCr6Fe2 alloy and, thus, creating around 200 and 450μm thick coatings, respectively, with presence of aluminium oxides. For both coatings, metallurgical bond layers with thickness of around 100μm and notable for their eutectic morphology were obtained. Analyses of microstructure, elemental and phase compositions revealed that the bond layer with the commercially pure aluminium coating is dominantly Al12Mg17 while the bonding with AlCr6Fe2 alloy comprises both Al12Mg17 and Al3Mg2. Despite the presence of porosity, the coatings' polarization resistance measurements showed increased values as compared with the bare substrate. Results of adhesion tests did not confirm the deterioration of adhesion strength due to the presence of intermetallics in the bond, and more important factor was the phase composition and microstructure of the coatings. The thickness of the metallurgic bond can be thermally controlled via the substrate preheating and/or its thickness.

Study on the plasma sprayed amorphous diopside and annealed fine-grained crystalline diopside

Natural diopside CaMgSi2O6 was processed by plasma spray technique into self-supporting plates. The experimental powder for spraying came from as-mined natural diopside and was crushed and sieved to the proper size for plasma spraying with a water-stabilized plasma torch (WSP). By removing the substrates after cooling, self-supporting plates (SSP) were obtained. These deposits were further studied with optical microscopy, SEM, X-ray diffraction, thermal analysis, mechanical tests and dielectric spectroscopy. Microhardness was measured on cross-sections prepared for microstructure observation. Wear resistance in wet conditions was tested as well. Dielectric properties of capacitor samples prepared from the self-supporting sprayed deposits were measured at low voltage. The results showed that diopside is an interesting candidate for various electrical applications as it has similar dielectric behavior as alumina or silicates. Thermal annealing of the SSP was done. Despite crystallization of the amorphous fraction (present after spraying) into a fine-grained structure, annealing worsened slightly dielectric responses of diopside. Differences between diopside and other silicates sprayed by the authors in the past are discussed.

Post-treatment of Plasma-Sprayed Amorphous Ceramic Coatings by Spark Plasma Sintering

Alumina-zirconia ceramic material has been plasma sprayed using a water-stabilized plasma torch to produce free standing coatings. The as-sprayed coatings have very low porosity and are mostly amorphous. The amorphous material crystallizes at temperatures above 900 °C. A spark plasma sintering apparatus has been used to heat the as-sprayed samples to temperatures above 900 °C to induce crystallization, while at the same time, a uniaxial pressure of 80 MPa has been applied to their surface. After such post-treatment, the ceramic samples are crystalline and have very low open porosity. The post-treated material exhibits high hardness and significantly increased flexural strength. The post-treated samples have a microstructure that is best described as nanocomposite with the very small crystallites embedded in an amorphous matrix.

Plasma spraying of cerium-doped YAG

Abstract

Feasibility of suspension spraying of yttria-stabilized zirconia with water-stabilized plasma torch

Thermal spraying of suspensions allows preparation of coatings from submicron-sized powders but demands a source of heat with a high enthalpy in order to provide an appropriate thermal treatment of the liquid feedstock during the in-flight stage so that the solvent may be evaporated, dispersed particles melted and accelerated towards the substrate to form a coating. Water-stabilized plasma (WSP) torch developed at the Institute of Plasma Physics AS CR, v.v.i. provides such a heat source with high enthalpy, high velocity of the plasma and, when compared to high-enthalpy gas-stabilized plasma (GSP) torches, relatively cheap operation. In this study, results of our experiments with suspension spraying of yttria-stabilized zirconia (YSZ) with WSP torch are presented and demonstrate that coating deposition with a high feed rate is possible with WSP technology. Formation of both columnar “cauliflower” microstructure and segmentation cracks was achieved. Variation of the deposition conditions was observed to modify coating microstructure in terms of splat morphology, porosity and thickness per pass, which is promising for further coating development.

Influence of Preheating Temperature on the Quality of the Interface between Plasma Sprayed Coatings and Substrate

This study was aimed to investigate the effect of the substrate preheating temperature on the overall quality of the coating/substrate interface. The coatings (stainless steel) were deposited using a water stabilized plasma torch (Institute of Plasma Physics, Prague, i.e. IPP, Czech Republic) on steel substrates. Three sets of samples were prepared under identical spraying and grit blasting condition; substrate preheating temperature was the only parameter which was varied, i.e. preheating to 150°C, 250°C and 350°C. Higher preheating temperature led to a significant increase in the coating adhesion.

The Influence of Interface Characteristics on the Adhesion/Cohesion of Plasma Sprayed Tungsten Coatings

Tungsten is the prime candidate material for plasma facing components of future fusion devices. Plasma spraying, with its ability to coat large areas, including non-planar surfaces, with a significant thickness, is a prospective fabrication technology for components subject to moderate heat loads, e.g., the first wall of the Demonstration Reactor (DEMO). The functionality of such coatings is critically dependent on their adhesion to the underlying material. This in turn, is influenced by a variety of processing-related factors, chief among them being the state of the interface. In this study, the effects of two factors—surface roughness and the presence of thin interlayers—were investigated. Two different levels of roughness of steel substrates were induced by grit blasting, and two thin interlayers—titanium (Ti) and tungsten (W)—were applied by physical vapor deposition prior to plasma spraying of W by a Water Stabilized Plasma (WSP) torch. Coating adhesion was determined by a shear adhesion test. The structures of the coatings and the interfaces, as well as the characteristics of the fractured surfaces, were observed by SEM.

Preparation and Properties of Ultra-High Temperature Ceramics Based on ZrC and HfC

Successful preparation of massive compact bodies from ultra-high temperature ceramics like zirconium carbide, hafnium carbide and their cermets with tungsten matrix with high values of mechanical parameters is difficult. Only limited number of techniques is able to perform it because of their absolutely highest melting points. In our contribution the preparation of these materials by both - hot pressing and plasma spraying techniques is described and chemical processes taking part at the fabrication are studied. Hot-pressed products fabricated at 2000°C and 6 GPa partly react with the internal surface of the BELT-type apparatus. Melting and solidification is taking place at plasma spraying. This process, carried out by water stabilized plasma torch with centerline temperature up to 30 000°C, is joined with undesirable reactions with plasma-forming medium, with oxidation in a turbulent plasma flow and nitridation of free-flight particles. All these chemical processes depend on variety of parameters, such as particle size of the feedstock powders or electric power of the arc. The mentioned parameters are easily controlled. Other, less controllable, factors include trajectory of powder particles in the plasma jet, important for the melting degree as well as for oxidation or nitridation of the powder surface. New knowledge concerning properties of compact ZrC and HfC were obtained.