Titanium dioxide coatings were sprayed by a water stabilized plasma gun (WSP) to form robust self-supporting bodies with a photocatalytically active surface. Agglomerated nanometric powder was used as a feedstock. In one case argon was used as a powder-feeding as well as coating-cooling gas whereas in the other case nitrogen was used. Stainless steel was used as a substrate and the coatings were released after the cooling. Over one millimeter thick self-supporting bodies were studied by XRD, HR-TEM, XPS, Raman spectroscopy, UV-VIS spectrophotometry and photocatalytic tests. Majority of the tests was done at the surface as well as at the bottom side representing the contact surface with the substrate during the spray process. Porosity was studied by image analysis on polished cross sections where also microhardness was measured. Dominant phase present in the sprayed samples was rutile whereas anatase was the main minor component. Hydrogen content in the nitrogen assisted coating was higher, but the character of the optical absorption edge remained the same for both samples. Photoelectron spectroscopy revealed differences in the character of O 1s peak between both samples. The photocatalytic activity was tested by decomposition of acetone at UV illumination, whereas also the end products - CO and CO 2 - were monitored. The nitrogen-assisted coating was revealed as more efficient photocatalyst.

An alternative method to produce bulk nanocrystalline materials and avoid the powder compaction step is to produce amorphous material by rapid solidification followed by controlled heat treatment to introduce nanocrystalline structure. The extremely high cooling rates in plasma sprayed particles give rise to formation of nonequilibrium phases, which may become amorphous for certain materials. Five different materials studied in this work are based on near-eutectic mixtures of alumina, zirconia and silica. The powder feedstock materials have been plasma sprayed using water stabilized plasma torch (WSP) and subsequently heat-treated to prepare nanocomposite materials with varying nanocrystallite size. The as-sprayed materials have very low open porosity and are mostly amorphous. The as-sprayed amorphous materials crystallize at temperatures around 950°C with an associated volume shrinkage of 1-2%. The resulting structure is best described as nanocomposite with very small crystallites (12 nm on average) embedded in inter-crystallite network. Role of the silica compound on phase composition, microstructure, and mechanical properties of the as-sprayed and annealed materials is discussed. Elastic properties were measured for the nanocrystalline materials. The as-sprayed amorphous materials exhibit high hardness and high abrasion resistance. Both properties are significantly improved in the heat treated nanocrystalline samples.

In result of the spray process normally a phase change from α-alumina (corundum) in the feedstock powder to predominantly α-alumina in the coating takes place. This is a well known but often neglected fact in the preparation and use of alumina coatings. This is of special interest since the high usage properties of thermally sprayed alumina coatings are generally derived from sintered alumina ceramics which consist of corundum. It is expected that the prevention of this phase transformation will significantly change the mechanical, electrical and other properties of thermally sprayed alumina coatings. There is controversial information about the possibility of stabilization of α-alumina by additions of chromia in the literature. In this work the stabilization using different spray processes (water stabilized plasma WSP, gas stabilized plasma APS and HVOF) was studied. Mechanical mixtures of alumina and chromia were used, as well as pre-alloyed powders consisting of solid solutions. The coatings were studied by X-ray diffraction and metallographic cross-sections. It was shown that in the case of the mechanically mixed powders the stabilization predominantly depends on the applied spray process. The stabilization by use of the WSP process was confirmed.

Agglomerated titania nanopowder and a “classical” titania were sprayed by the high throughput WSP and thoroughly compared. Optical microscopy with image analysis as well as mercury intrusion porosimetry were utilized for quantification of porosity. Results indicate that the “nano” coatings in general exhibit finer pores than coatings of the “conventional” micron-sized powders. Mechanical properties like Vickers microhardness and slurry abrasion response were measured and linked to the structural investigation. Impact of the variation in the slurry composition on wear resistance of tested coatings and on character of the wear damage is discussed. The over-all results however suggest that the “nano” coatings properties are better only for carefully selected sets of spraying parameters, which seem to have a very important impact.

TiO 2 nanopowder was used as a feedstock for spraying with the water stabilized plasma (WSP®) in search for superior mechanical properties and wear resistance of titania coatings. It has been proved that good quality coatings can be made even with the high throughput WSP®. Single splats evaluation and the free flight particles were used for the spray optimization. Phase compositions, stoichiometry and selected properties, such as density and elastic modulus, were then studied at the as-sprayed coatings. As for the phase composition of coatings, mainly rutile with possible traces of Magneli phases have been found. A comparison between tension and compression loading shows that values of the Elastic modulus for compression are slightly higher than these for tension, as it is usual in plasma sprayed coatings.

Individual particles of various ceramic materials sprayed by water stabilized plasma torch (WSP) were characterized in flight by an optical sensing device DPV-2000. Temperature, velocity, and diameter of individual particles were measured at the center of particle plume and maps of the particle plume cross-section were acquired as well. Plasma jet and consecutively particle plume of the WSP torch is much larger compared to gas stabilized torches and even larger than the maximum span of the DPV-2000 sensing head. In summary, temperatures of particles varied from 2000 to 2600°C and their velocities from 60 to 140 m/s depending on the powder feedstock cut size, particle density, feeding distance, spraying distance, and feed rate. The last three parameters were varied to study their effect on the particle states and their distribution in the plasma jet and to correlate these results with selected properties of the corresponding coating. Some of the spraying parameter effects are difficult to interpret, nevertheless, general trends have been established.

Calcium zirconate and magnesium zirconate prepared by synthesis and agglomeration were sprayed using a water stabilized plasma gun under varied spraying conditions. The same set of conditions was maintained during spraying of fused lime stabilized zirconia and magnesia stabilized zirconia. The intent of the study was to compare spraying behaviour and deposit properties of pairs of feedstock material that have just about the same chemical composition but differ considerably in the way of preparation. Free-flight particles as well as deposits were characterised by standard techniques, such as light microscopy, scanning electron microscopy with energy-dispersive spectroscopy, X-ray diffraction, differential thermal analysis, and pycnometry. The differences between relevant coatings were evaluated namely in terms of morphology, chemical and phase composition, density and porosity. Sources of observed differences are discussed.

Plasma sprayed tungsten and tungsten-copper coatings are being developed for potential application as plasma facing materials for fusion reactors. Initial spray tests indicated difficulties in tungsten melting and in-flight oxidation. Numerical modeling was performed to help explain these issues. A complex study of the process and its products was performed, including: in-flight diagnostics, characterization of isolated splats, and structure, composition, thermal and mechanical properties of the coatings. Based on these results, the process was optimized, with respect to powder size and various spraying parameters, to improve melting of the particles, reduce oxidation and increase the deposition efficiency.

A novel material has been used for plasma spraying by WSP. The material is composed of three main phases, namely corundum (aluminum oxide), baddeleyite (zirconium oxide), and glassy phase (silicon oxide). The material is a refractory and exhibits very high hardness, extremely high abrasion resistance, and chemical resistance. Conventionally, the material is fabricated by melt casting and machining. Cast tiles of the material were ground and sieved to obtain the right powder cut size for plasma spraying by water stabilized plasma torch (WSP). Both dense coatings and free standing parts were achieved with the new material, which sprays very well with WSP. Spraying parameters were varied and molten particles were monitored in flight by DPV 2000. The coatings exhibit very low porosity and high hardness. The as-sprayed material is mostly amorphous with some nanocrystalline grains of aluminum and zirconium oxide present. The phase composition of the as-sprayed material is thus different from that of the feedstock material, which is mostly crystalline with a small fraction of amorphous silica glass. The microstructure of the newly sprayed material was studied by electron microscopy (SEM, TEM) and is very complex. Upon annealing, the as-sprayed material crystallizes around 950ºC. This result and other thermal properties were measured by TMA and DTA. The ease of plasma spraying and the coating properties make this material a suitable candidate for many industrial applications.

By modification of parameters in plasma spraying it is possible to alter porosity of the deposits only in a relatively small range. Industrial applications may require to adjust the porosity in wider range, to double or triple the original value in some cases. Such changes can be achieved only by special procedures. One of them is plasma spraying of ceramic/metal deposit followed by removal of the metal within the coating. The material removal is performed by dissolving, by leaching or by its extraction with an appropriate process. The paper describes preparation of very porous Cr 2 O 3 coatings by this method from a composite Cr 2 O 3 /Al deposit. The initial porosity of approximately 13% (total porosity) was increased to 37% or 51% respectively by changing the initial volume of aluminum in the ceramic/metal plasma-sprayed composite. The discussion is complemented by observation of the resulting coating structure and detailed characterizations of the pore structure and porosity.

CaZrO 3 is a material for thermally sprayed ceramic coatings to which so far only a little attention was paid. This material has a high melting point, good thermal stability and a coefficient of thermal expansion close to that of steel. In this paper water stabilized plasma spraying (WSPR) and atmospheric plasma spraying (APS) were used to prepare CaZrO 3 coatings. The spraying feedstock was prepared from fine CaZrO 3 powder by agglomeration (spray drying) and sintering. Powders with three different particle sizes (- 45 + 20 µm, - 63 + 45 µm and -90+63 µm) were used in the experiments. The coarse fractions were used for WSP spraying, while the fine one was sprayed with the APS process. Plasma sprayed materials were studied from the point of view of phase changes and influence of the powder size on structure of coatings. The changes of phase composition were studied by X-ray diffraction on coatings as well as on free flight particles. Formation of a cubic phase with a reduced content of CaO in comparison to CaZrO 3 was observed. Its formation is probably connected with evaporation of CaO during spraying. This cubic phase is similar to the phase obtained by spraying of ZrO 2 +5%CaO. Plasma sprayed coatings were characterized by light and scanning electron microscopy (SEM) and by density and porosity. Coefficients of thermal expansion of plasma sprayed layers from CaZrO 3 were measured.

An investigation was conducted to assess the potential of water-stabilized plasma (WSP) spraying for applying protective boron carbide coatings to fusion reactor components. This paper describes how test samples were produced and how coating quality was determined. The authors sprayed boron carbide powder onto steel and stainless steel substrates using different powder feeding and spraying distances, substrate preheat temperatures, and carrier gases. They also investigated methods for optimizing the plasma jet and improving coating adhesion. The boron carbide coatings were characterized based on phase composition, porosity, oxygen content, and flexural strength. Paper includes a German-language abstract.

This paper examines the dielectric properties of silicate coatings including mullite (3Al 2 O 3 -2SiO 2 ), steatite (MgSiO3), spodumene (Li 2 O-Al 2 O 3 -4SiO 2 ), and olivine with near-forsterite (Mg 2 SiO 4 ) composition. The materials were sprayed using a water-stabilized plasma gun and the deposits were removed from the substrate, polished, and sputtered with aluminum on both sides. Electrical tests consisting of voltage, resistance, and capacitance measurements showed that the relative conductivity of plasma-sprayed silicates is stable between 200 Hz and 1 MHz, which is suitable for many insulation applications. Paper includes a German-language abstract.

Among candidate materials for plasma spraying titanates ATiO3, where A is an element from the alkaline earth group (11), were not systematically tested until today. This paper reports on plasma spraying of synthetic perovskite CaTiO3 and geikielite-perovskite system MgTiO3-CaTiO3. Perovskite CaTiO3 is well known as dielectric material and a basic component of complex dielectric ceramics. Since it is relatively chemically simple and inexpensive material it has been selected for the basic preliminary studies. Mixture of geikielite-perovskite MgTiO3-CaTiO3, with Mg:Ca ratio equal to 94:6, was chosen because its permittivity is independent of temperature. Plasma spraying was done with the water stabilized plasma gun WSP. Plasma spraying conditions were optimized using single splat observation for various substrates and varying substrate temperature. Standard experimental techniques were used for studying of microstructures, chemical and phase compositions and porosity of as-sprayed and annealed deposits. Mechanical properties such as Young’s modulus and microhardness were measured.

For utilization of free-standing ceramic parts produced by plasma spraying it is very important to know the temperature dependence of the linear thermal expansion coefficient and its relation to the porosity of the structure. Zircon ZrSiO4 and gray alumina (96 wt % AI2O3) were plasma sprayed by the water stabilized plasma gun WSP PAL 160. Samples of both materials were cut from thick coatings with respect to their orientation to the gun axis during the gun's horizontal spraying cycling with a constant speed. Thermal expansion coefficients and the differential thermal analysis were performed using SETARAM complex measuring system (up to 1750 °C), the density/porosity was measured by several techniques, such as Archimedean weighing, helium pycnometry, etc. It was found that both, the porosity and the thermal expansion coefficient, change for different locations in the thick deposit due to the varying trajectories of individual particles/droplets in the plasma stream. Measured data for deposits are then compared with data for bulk ceramics. The dependence of the thermal expansion coefficient on porosity in a given location was determined and its general applicability for free-standing plasma spraying is then discussed in the paper.

This paper describes a novel application of OF-boride layers on steel surfaces. The plasma-sprayed boron carbide powder on steel was diffusion annealed to form a suitable iron-hemiboride intermediate layer with a coefficient of thermal expansion between the coefficients for the steels used and ceramic coatings to create. In the next step, this system was completed with a second plasma-sprayed layer on aluminum oxide o zirconium oxide. The adhesion of these samples was checked after dynamic loading as a result of alternating thermal loads at 600, 800, 1000 or 1200 deg C. The resulting values were compared both with the adhesion values of the same ceramic coatings on steel without a boride intermediate layer and with the adhesion values of these ceramic coatings on steel that were borated according to the classic method in a boron carbide pack with activators. Paper includes a German-language abstract.

Silicates represent a broad group of industrially important ceramic materials. The only silicate that is widely used for plasma spraying is zirconium silicate. Other silicates are generally not used, although they can offer interesting application properties. This paper presents results with other silicates: synthetic wollastonite, stoichiometric mullite, cordierite, and steatite. The input materials were produced in selected sizes from ceramic in industrial quality and applied with the water-stabilized plasma spray system PAL160 to form free-standing panels. The morphology of the microstructure, the thermal expansion, the bulk and filling densities, the open and closed porosity, the phase, and the chemical changes were evaluated. Paper includes a German-language abstract.

The formation of the microstructure is influenced by a number of parameters. The spray angle is considered to be one of the most important and difficult to control parameters, especially for substrates with complex shapes. In this paper, the influence of the spray angle on the microstructure of gray aluminum oxide and yttrium oxide stabilized (8% by weight) zirconium oxide applications is investigated. Plots are made from each material at four spray angles (90 degree, 70 degree, 55 degree, and 45 degree). Their microstructure is characterized by means of intrusion porosimetry and SEM. The results show clear differences between the two materials. The aluminum oxide microstructure is significantly influenced by the spray angle, while the YSZ microstructure is almost independent of the spray angle. Paper includes a German-language abstract.

The mechanical properties of plasma sprayed metals and alloys are important in most applications. It a posttreatment by forming of plasma deposited coatings is required, their response to compressive loading is decisive. This paper is concerned with the compressive behaviour of two high-alloy steels sprayed by a water stabilized plasma gun. Martensitic (13.2 % Cr) and austenitic (19.6 % Cr, 11.6 % Ni) steels were plasma sprayed onto plain steel substrates. Small cube-shaped test samples were cut out of thick coatings by an electrospark technique. Compressive load was applied along axes parallel and perpendicular to the substrate and coating surfaces. In addition, comparative samples of bulk steels produced by conventional metallurgy were tested. The compressive behaviour of the as-sprayed martensitic steel was anisotropic at room temperature, i.e. dependent on the orientation of the compression axis. As a result of compression, the splat shapes changed in a manner depending on the orientation of the compression axis. The room temperature compression tests showed that the yield stress of this steel was decreased and the anisotropy was reduced by annealing after plasma spraying. At room temperature, the anisotropy of the as-sprayed austenitic steel and the effect of annealing were less pronounced in comparison with the martensitic steel. Very low values of the yield stress were observed in both steels compressed at the annealing temperature. In spite of the presence of oxide films enveloping each splat, the coatings were prone to considerable plastic deformation, in particular if compressed along the axis perpendicular to the surface.

This paper examines ways to control the porosity of thermally sprayed deposits. All spraying was done with a water-stabilized plasma system using different combinations of alumina, zircon, Ni, and Al powders. Sandwiched structures with alternating ceramic and metal layers were sprayed as were thick deposits consisting of metal and ceramic mixtures. Porosity was characterized by methods such as gas permeability, water immersion, MIP, SEM, and SANS. In addition, several post-processing methods were tested to determine their effect on porosity volume. For example, removing metallic phases by leaching or by annealing at temperatures above the melting point was found to effectively increase porosity, while the use of sealing materials proved effective at reducing porosity. Another method tested was calcination, which resulted in an increase or decrease of porosity depending on the deposit's chemistry and annealing conditions.