The goal of this study is to find applicable spray conditions for producing tungsten (W), zirconium carbide (ZrC), and W-ZrC cermet layers. In the experiments, W and ZrC powder mixtures were fed into the plasma of a water-stabilized plasma gun and coatings approximately 1 mm thick were sprayed on graphite substrates. Pure W and pure ZrC were deposited under similar conditions. Microhardness, surface roughness, XRD, XRF, dilatometry, and spectroscopic techniques were used to characterize the coatings. The resulting coatings were found to be hard with a high elastic modulus.

A short survey is given of various techniques of 3D visualization of voids and other structural defects that are inherently present in thermally spray structures. It is proven that the only condition for visualization is possibility to set up a distinguishable threshold based on the gray scale of the microscopical image of the structure. Segmented images are then further processed by commercial software for image analysis, animations and anaglyph files creation. Several softwares were applied and combined, such as Lucia, Voxblast, Amira and Voxler. The visualization technique was demonstrated on a ceramic plasma sprayed coating, where two kinds of voids – semi-globular pores and large interlamellar pores could be separated. Similarly, this visualization technique can be used to distinguish between pores and oxide particles in case of metallic coatings. The visualization is done in a real Cartesian space without any transformation. The results can be useful mainly for: a) teaching to get a better insight into the microstructure of thermally sprayed coatings, b) research, where in combination with mathematical quantification the visualized structure can show important distinctions between coatings sprayed by different techniques and with variety of process parameters.

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.

Thermal spray is a flexible technique enabling deposition of wide choice of feedstock materials including ceramics, metals or the mixture of both. Various spray technologies are available, such as different types of thermal plasma methods, electric arc based methods, HVOF and other combustion methods. Obviously, the fatigue properties of coated bodies will differ based on the choice of feedstock material and on the spray technology used. Comparison was made of fatigue properties of bodies with Alumina, Ni-5wt%Al and composite coatings produced by gas and water stabilized plasma spray. It has been found, for instance, that Alumina coatings sprayed by water stabilized plasma torch (WSP) had substantially increased fatigue life times of specimens compared to specimens with coatings of the same feedstock deposited by the gas stabilized plasma torch. Measured fatigue data were related to a detailed structural characterization of the tested coatings. Obtained results are discussed with regard to our previous results obtained during fatigue tests of specimens with one-component coatings.

Chromia admixture to alumina feedstock is used to block the formation of γ-Al 2 O 3 in plasma sprayed coatings. In this work, a mechanical blend of alumina-chromia powders was used with the water stabilized plasma to make thick coatings. When additional post-treatment by a quasi-continuous laser was applied to the surface, the amount of the corundum phase substantially increased. Careful examination of the treated surface revealed that the individual splats at and near the surface were fully remelted and the structure is formed by a homogeneous phase with no visible splat boundaries. Segregation of Chromium has been detected in the remelted zones, which strongly affects the final properties of coatings. Fast melting and cooling of the ceramic material under certain laser parameters may result in the formation of undesirable cracks between traces of individual passes of the laser beam.

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.

Alumina and stabilized Zirconia were plasma sprayed in air using the water-stabilized plasma torch. In the case of Alumina two different stand-off distances were applied at spraying. Nd-YAG laser was then used for additional treatment of plasma sprayed coatings. The laser was maintained in a quasi-continual regime and defocused from the surface to increase the treated coating's area. Energy density was varied together with the laser scanning velocity to ensure variance in thermal history of the treated surfaces. Microhardness, surface roughness and slurry abrasion resistance (SAR) were measured before and after the laser treatment. Results vary in dependence on the laser treatment's parameters. When the treatment results in substantial changes of the structure (up to a complete re-melting of the surface), enhancement of all measured properties was proven. It is demonstrated that the extent of change of mechanical properties can be correlated with optical properties of coating materials at the laser wavelength. Microstructural aspects of the laser treatment are discussed as well, especially at the boundary between the laser-annealed layer and the basic coating's microstructure. It is pointed out that laser overheating due to use of an extremely high energy density can cause delaminating of the coatings.

A Ni-Al pseudo-alloy powder was studied from the point of view of spheroidization during spraying by a water-stabilized plasma gun. The powder particles of irregular shape were conglomerates of elemental Ni and Al, the average Al content being 9.7 %. To conserve the shape and composition of particles flying in the plasma stream, these were trapped in liquid nitrogen. Scanning electron microscopy and X-ray microanalysis were used to obtain information about particle shape and element distribution. Most plasma sprayed particles trapped in liquid nitrogen were composed of a Ni-Al alloy, where the Al content varied in a wide range. Spherical "caps" composed of Al-oxide covered partially their surfaces. It follows that on the interface between molten Ni and Al, the interaction of both components gave rise to a Ni-Al alloy. On the contrary, if Al was exposed to air, it oxidized rapidly during the flight of the particles. The X-ray diffraction lines of the metallic phase in the particles trapped in liquid nitrogen were shifted from the positions corresponding to pure Ni as observed in the feedstock powder. This, together with the line asymmetry, showed the presence of Ni-Al alloy containing varying amounts of Al. The X-ray diffraction did not find any elemental Al in the liquid nitrogen trapped powder, i.e. neither in the metallic phase nor in the "caps". This means that all Al accessible to the ambient oxygen was converted into oxide. The "caps" contained metastable γ- and δ- Al 2 O 3 . The mechanism of the "cap" formation appears to be based on the fact that after an acceleration and melting period, significant slowing down of a molten particle occurs. Due to the drag forces, the lighter Al 2 O 3 melt concentrates on the rear part of the droplet surface. The main condition, under which this mechanism holds, is the presence of two immiscible melts in the droplets and the significantly differing densities of both melts.

It is generally known that plasma sprayed coatings exhibit rather a low strength thanks to their characteristic microstructure with porosity and microcracks. To determine the role of varying types of deformation in different parts of the coatings profile, 1.8 mm thick chromia coatings on a steel substrate were made using WSP plasma spray. Stress gradients were then measured "in-situ" on a four-point bending device during bend deformation of the coated beam using neutron diffraction. Only compressive loading in coatings increased the resulting stresses. From the plot of stresses vs. applied strain (linear dependence) the Young’s moduli of the substrate and the coating were determined. Both values agree well with those obtained by mechanical testing. In general it is believed that, in a simplified way, interlamellar voids (cohesion defects) roughly parallel to the substrate decrease the tensile strength in the direction perpendicular to the substrate, while intralamellar cracks, roughly perpendicular to the substrate, significantly affect the Young’s modulus of coating. It is supposed that the tensile deformation of coatings opens the cracks and no stress increase is observed. On the other hand the applied compressive deformation in the coating closes the intralamellar microcracks and the internal stresses increase, as suggested by obtained results.

Basalt, an abundant and inexpensive natural raw material, is a glass-ceramic with good abrasion-wear resistance and chemical stability. Traditionally cast-shaped into flag stones, pipe linings and even fibrous composites, basalt can be processed by thermal spraying, potentially yielding highly dense coatings with few defects. Such overlays can seal base materials for wear applications in corrosive environments. Basalt coatings are produced by a number of common thermal spray techniques, including water-stabilized plasma spraying (WSP), high-velocity oxy-fuel (HVOF) and conventional air plasma spraying (APS). In-flight particle temperature and velocities are monitored with a particle diagnostic system (DPV 2000). Using different feedstock size cuts, the attainable ranges of particle states are delineated. Spray parameters are selected for each of the processes, based on deposition efficiency and porosity criteria. For typical conditions, particle velocities vary from 100 m/sec for WSP to 800 m/sec with HVOF. The microstructure and composition of the coatings are evaluated by scanning electron microscopy (SEM) and EDS-SEM. Crystal phase analysis is performed by X-ray diffraction (XRD). Abrasion resistance (ASTM G-65) and hardness (Vickers) of the as-sprayed coatings are compared. The microstructures and tribological properties are related to the particle size, temperature and velocity distributions, which are distinctly different for each process.

Atmospheric plasma spraying of alloys often results in their composition changes. The main source of the changes is usually preferential oxidation of some elements composing the alloy. As a rule, these are the alloying elements whose affinity to oxygen is high. Changes due to this effect are well known from metallurgy; however, they were scarcely studied from the point of view of plasma spraying. Preferential evaporation of some elements may also contribute to the alloy composition changes. The aim of the present paper is to give quantitative data on composition changes of selected alloys sprayed by a water-stabilized plasma gun. Two Ni-base alloys and one high-alloy Cr-Ni-steel were studied. The main tool for determining the sample composition was electron probe X-ray microanalysis. To quantify the results and to eliminate the systematic errors, the data obtained by this method were calibrated by repeated chemical analysis of feedstock powders. The alloy composition was determined after both stages of plasma spraying, i.e. after the inflight stage of molten particles and after the stage comprising particle impact, solidification, coating formation and cooling. To study the situation after the former stage, the flying particles were trapped and quenched in liquid nitrogen. In the Ni-Cr alloy containing 20%Cr, strong Cr depletion was observed. The Fe depletion in the Ni-Fe alloy (47%Fe), though unambiguous, was less significant. The high-alloy steel (Czech equivalent of AISI 316) was also Cr depleted, whereas the concentrations of other alloying elements (Mo, Ni) remained effectively unchanged. In all cases, the depletion occurred at the first spraying stage and became more pronounced during the second stage. Strong air entrainment occurs not only in a plasma jet produced by a water-stabilized plasma gun, but also if gas-stabilized plasma guns are used in atmospheric plasma spraying. It follows that the dominant mechanisms of composition changes during plasma spraying by both techniques are similar.

Plasma sprayed ceramic coatings have much lower stiffness in comparison to sintered ceramics. The reason for that is their characteristic microstructure with porosity and microcracks. Microcracks decrease the interlamellar cohesion in vertical direction, but also affect the individual splat properties in the horizontal direction. For that reason sealing treatments are often applied with plasma sprayed ceramic coatings in order to improve their corrosion resistance and mechanical properties. In this paper the effect of aluminum phosphate sealing treatment on the elastic properties of plasma sprayed Al 2 O 3 and Cr 2 O 3 coatings were studied. Residual stresses in the plane of coating surfaces were compared using the X-ray diffraction analysis (XRD). A special four point bending device, designed for the X-ray diffractometer, was used in determining the effect of additional load on coating elastic behavior. In as-sprayed alumina coatings tensile stresses of about 400 MPa were detected while only about 40 MPa of compressive stresses were measured in the as-sprayed chromia coatings. Microstructural characterization revealed that sealing treatment had apparently affected the coating microstructure and filled some microcracks and interlamellar spacings. As a result, in both sealed coatings, compressive stresses of about 100 up to 150 MPa were observed. Also a better stiffness of both materials was detected during the bending of specimens. In addition, the sealing treatment increased nearly ten times the Young’s modulus, determined by XRD analysis under various tensile loads.

During air plasma spraying, molten metal particles flying in the plasma jet are oxidized. As a result, a part of the metal melt is converted into oxide melt. After the particle impact and solidification, oxidation continues as a gas – solid reaction. The present paper deals with oxidation of two binary Ni-based alloys. One of them, Ni-20%Cr, is frequently used in thermal spray applications. Another one was a Ni-Fe alloy with an approximate proportion of both components 1:1. The feedstock powders were plasma sprayed by a water-stabilized gun WSP. PAL 160. To analyze the reaction products of the in-flight oxidation stage, the flying particles were trapped and quenched in liquid nitrogen. Oxides resulting from both oxidation stages were studied in the as-sprayed deposits after their cooling down to room temperature. The oxide amounts in the samples were determined indirectly by oxygen level measurement using "extractive fusion" (LECO-method). Structure of the oxides, separated by dissolution of the metallic phase, was investigated by X-ray diffraction. Iron-containing oxides were also characterized by Mössbauer spectroscopy. From the point of view of reaction kinetics, both alloys behaved in a similar way. The particles quenched in liquid nitrogen contained less than 2% of oxygen, whereas in the deposits these values were higher, up to 4.5 %. Two oxide phases were found in all plasma sprayed Ni-Cr samples: a rhombohedral phase similar to (Ni,Cr) 2 O 3 and a tetragonally distorted spinel phase (Ni,Cr) 3 O 4 , both of them very rich in chromium. Another oxide, NiO, was present mainly in the deposits. In the oxidation products of Ni-Fe alloy, the dominant phase was similar to nonstoichiometric wüstite FeO. The results of thermodynamic calculations are in sound agreement with the experiments except for the presence of the tetragonal phase, the composition of which is near to Cr 3 O 4 , in oxidation products of Ni-Cr alloy.

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.

Fatigue behavior and Young’s modulus of plasma sprayed gray alumina on low-carbon steel substrates were investigated. The investigation of the properties of composite material “coating-substrate” included the measurements of microhardness profile, residual stress on the top of the coating and residual stress profile in substrate. Fatigue samples were periodically loaded as a cantilever beam on a special testing machine. Failed samples were observed in SEM to determine failure processes in the coating. The Young’s modulus of the coating was measured by the four-point bending method. Samples were tested both in tension and compression at low (300 N) and high (800 N) loads. Our experiments revealed that the average fatigue lives of coated specimens were nearly 2 times longer than those of the uncoated specimens. The Young’s modulus of the coating varied between 27 and 53 GPa with an average value of 43 GPa. Loading in tension caused decrease in Young’s modulus of the coating while loading in compression lead to increase in Young’s modulus. Increase in the lifetime of coated samples was likely due to compressive residual stresses in the substrate, originating from the spray process. Failure of the coating consisted of several processes, among which the most important are splat cracking, splat debonding and coalescence of cracks through the voids in the coating.

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.

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.

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.

Spraying distance (SD) is one of the main parameters that can affect the spraying process - its efficiency as well as deposit's character. The reason lies in a different thermal history of particles corresponding to different spraying distances. Variation in the structure, preferred orientation, variation of the phase contents and/or in the chemical composition of deposits can be then found for different SDs. Consequently, properties of coatings can greatly vary, not only in the resistance state but also on deposit's annealing. Some materials are, however, more and some less sensitive to that effect. The goal of this work is to compare CaTiO 3 samples produced by plasma spraying with WSP at SD = 350 and 450mm with sintered samples. The following properties were compared: microhardness, thermal expansion coefficient, permittivity and reflectivity. Porosity and the differential thermal analysis of resistance and annealed deposits were also compared. Perovskite CaTiO 3 belongs among materials very stable during spraying - neither chemical nor phase differences were found between the feedstock powder, free-flight particles, as-sprayed deposit and annealed deposit. Despite that there are significant differences in behavior of deposits and freestanding parts sprayed from different SDs. All the recorded differences for CaTiO 3 plasma sprayed deposits with varying SDs must be therefore accounted to the deposit's structural differences, such as pore and splat sizes and shapes and preferred orientation. Additional differences on annealing can be probably attributed to the different amount of "stored" thermal energy in deposits due to the varying SD. However, there is a lower limit for SD assuring a quality deposit on spraying.

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.