Ultra-fine hydroxyapatite powders were successfully synthesized using radio frequency (RF) suspension plasma spraying (SPS). This novel technique utilises the inherent characteristics of the RF plasma to axially feed and spheroidise a liquid suspension to produce spherical ultra-fine HA powders. This offers an alternative approach over conventional D.C. and flame spheroidising techniques which are better suited for solid feed stocks. Rietveld analysis was subsequently applied using Rietquan Quantitative Analysis software package to determine the amount of decomposed phases and amorphous content of the as-sprayed powder. This was also compared against quantitative XRD analysis employing internal and external standards. However, pure phases needed for calibration is scarce and amorphous calcium phosphate (ACP) is virtually impossible to isolate. In addition, the long and laborious task of obtaining calibration curves makes this technique unpopular. Nevertheless, conventional quantitative phase analysis (QPA) was carried out, using relative peak height ratios of HA and the phase involved, but the calculated decomposition only shows relative trends for a particular parameter variation. Determining the actual phase content is critical because of possible variations in biological responses when used as coatings and inserts in restorative orthopaedic implants. Varying tissue responses can arise from decomposed phases such as α and β-tricalcium phosphate (TCP) and tetra-calcium phosphate (TTCP) as well as ACP which generally have higher solubility as compared to crystalline. QPA via the Rietveld method provides a powerful tool that offers the user simultaneous quantitative phase determination of multiphase systems containing amorphous content. Unlike XRD QPA, the amorphous content could be indirectly calculated using crystalline alumina standard. XRD QPA results showed that decomposition generally rose with plate power without considering the amorphous content. With Rietveld QPA, the results showed an initial rise in decomposition before decreasing at higher plate powers. The amorphous phase content was calculated at different plate powers and concentration of suspension with the aid of alumina as an external standard. Results showed that the amorphous content increased substantially at higher powers. This study demonstrates the ability of Rietveld analysis to completely quantify all associated amorphous and crystalline phases within a multiphase system for any thermally treated material.

Ultra-fine hydroxyapatite (HA) powders were produced with radio frequency (RF) suspension plasma spraying (SPS). This novel technique utilizes the inherent properties of the RF plasma enabling axial feeding of the suspension into the plasma producing spherical ultra-fine HA powders. These powders were examined by XRD and Rietveld analysis using the Rietquan 2.3 Quantitative Analysis software package. The aim of the analysis was to determine the various amounts of decomposed phases and amorphous content after SPS of HA. Results showed that the amount of decomposed phases rose up to a plate power of 15 kW there after decreasing at higher plate powers. The amorphous phase however kept increasing with plate power reaching about 35 wt.% in the powders sprayed at 21 kW. These trends have led to the belief that the phase content and hence, the characteristics of the powders are controlled mainly by the competitive processes of decomposition and melting and evaporation within the plasma. The morphology of the powders was also observed through TEM and changes in molecular structure were investigated by FTIR. DSC was carried out to observe the crystallisation of amorphous calcium phosphate into HA.

For most HVOF sprayed tungsten carbide coatings powders with identical particle-size distributions and compositions are interchangeable, within the meaning that as long as the manufacturing process is identical other properties are nearly irrelevant. In plastic foil industry often complex strains occur on the surfaces of the used tools. These strains comprises from a chemical attack by means of released process gases due to the thermal conditions and from an abrasive component caused by additives of the plastic. Shaping calender rolls with a high gloss mirror finished surface may show only a minimal wear in such complex strains because otherwise the quality of the foil is affected in a negative way. In this range of applications the practical experience shows that with commercial characterization values such as microhardness and porosity HVOF sprayed tungsten carbide coatings are not sufficiently described. The article describes the effects of different microstructures on the application behaviour of a coating. For that purpose analytical methods such as quantitative phase analysis due to X-ray diffraction by means of Topas-Rietveld-Method were used. Preliminary results of the use of a novel high frequency eddy current test method suggest the potential to allow a local correlation of specific properties of the coatings with their microstructure.

Alumina-zirconia ceramic material has been plasma sprayed using a water stabilized plasma torch (WSP) 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 GPa has been applied to the their surface. After such post-treatment, the ceramic samples are crystalline and exhibit very low open porosity. The as-sprayed amorphous materials also exhibit high hardness and high abrasion resistance. Both properties are significantly improved in the heat-treated samples whose microstructure is best described as nanocomposite with the very small crystallites embedded in an amorphous matrix.

Biomaterial coatings must have high degrees of crystallinity and phase purity, good adhesive and cohesive integrity and adequate porosity to promote bone ingrowth. The most used coating method is atmospheric plasma spraying. However, the main drawback of this technique is the generation of an amorphous phase and other calcium phosphate phases after the spraying process, which are not present in the feedstock and are not desirable. The use of HVOF as a process for obtaining hydroxyapatite coatings on Ti-6Al-4V was used successfully. With optimised HVOF process parameters, coatings with similar bond strength to plasma sprayed HAp coatings, good microstructure and higher crystallinity degree than atmospheric plasma sprayed ones where hydroxyapatite was the only crystalline phase present were obtained. Coating characteristics were analysed with XRD, EDS, SEM, FTIR which indicated that the coatings had a high degree of crystallinity and good bond strength. Moreover, in vitro response were also evaluated and the strength of the coating to the substrate.

Thermally sprayed ceramic coatings are used in environments requiring good wear- and corrosion resistance among others. However, a typical issue with ceramic coatings is their low impact resistance and tendency to fail catastrophically by cracking. In bulk ceramics, the Al 2 O 3 -ZrO 2 –composition has been of interest for long since already small additions of ZrO 2 into Al 2 O 3 have shown improvements in fracture toughness compared to pure Al 2 O 3 . Efforts are being made to induce this increased resistance to fracturing in thermally sprayed coatings as well, resulting in higher wear resistance due to a more predictable behavior and damage-tolerance. In this work, Al 2 O 3 -ZrO 2 -coatings have been deposited by atmospheric plasma spray (APS) and high-velocity oxy-fuel spray (HVOF) processes. The wear characteristics of the coatings were evaluated with cavitation erosion, delving into the mechanics of the erosion and the resulting microstructural changes in the coatings. Evidence of phase transformation of t-ZrO 2 to m-ZrO 2 was found during the erosion. The HVOF-sprayed coating exhibited greater wear resistance against the cavitating bubbles due to its finer microstructure.

Nanostructured and conventional Al 2 O 3 powders have been plasma sprayed, under the same parameters, to produce coatings on 304 stainless steel. The nanopowder was fabricated by mechanical attrition techniques and composed of agglomerates of nanoparticles, whereas the conventional powder consisted of solid granules. In order to maintain the beneficial effect of the nanostructure in the final coating, a fraction of the powder’s nanostructure should be retained in the coating after spraying. Dissimilarities were observed between the two types of coating, regarding porosity, roughness, deposition efficiency and α-Al 2 O 3 to γ-Al 2 O 3 proportions, which are related with the different percentages of semimolten particles in the coatings. The nanocoatings retained a higher percentage of semimolten particles than the conventional coatings, owing to the higher porosity of the nanoparticle agglomerates, as compared to the conventional solid granules. The molten part of both conventional and nanostructured coatings consisted of γ-Al 2 O 3 of columnar morphology. In order to investigate the mechanism of the melting front advance into the particle interior during their presence in the plasma stream, the particles were sprayed directly into distilled water. The nanoparticles mainly formed hollow spheres, whereas the conventional particles mainly formed compact spheres. The internal porosity of the solidified nanoparticle agglomerates, which affected the overall coating porosity, was linked to the hollow sphere phenomenon.

Environmental barrier coatings (EBCs) are required to protect SiC based composites in high temperature, steam containing combustion environments found in the latest generation of high efficiency gas turbine aeroengines. Ytterbium disilicate has shown promise as an environmental barrier coating, showing excellent phase stability at high temperature and a coefficient of thermal expansion close to that of SiC; however, its performance is dependent on the conditions under which the coating was deposited. In this work, a parametric study was undertaken to demonstrate how processing parameters using a widely used Praxair SG-100 atmospheric plasma spraying torch affect the phase composition, microstructure and mechanical properties of ytterbium disilicate environmental barrier coatings. Ytterbium disilicate coatings were deposited using 5 sets of spray parameters, varying arc current and secondary gas flow. The phases present in these coatings were quantified using X-ray diffraction with Rietveld refinement, and the level of porosity was measured. Using this data, the relationship between processing parameters and phase composition and microstructure was examined. Abradable coatings are used throughout gas turbine engines to increase efficiency in the compression and combustion phases of the turbine. Abradable coatings are soft enough to be worn away by turbine blade tips (without damaging the tip itself), allowing for tighter clearances to be used, limiting leakages and increasing efficiency. Using the optimum process parameter window determined in this work, a low density abradable Yb 2 Si 2 O 7 layer will be deposited in future research.

Lanthanum zirconate (La 2 Zr 2 O 7 ) was proposed as a promising material for thermal barrier coatings. At atmospheric plasma spraying (APS) of La 2 Zr 2 O 7 a considerable amount of La 2 O 3 can evaporate in the plasma flame, resulting in a non-stoichiometric coating. As indicated in the phase diagram of the La 2 O 3 -ZrO 2 system, in the composition range of pyrochlore structure, the stoichiometric La 2 Zr 2 O 7 has the highest melting point and other compositions are eutectic. APS experiments were performed with a TriplexPro-200 plasma torch at different power levels to achieve different degrees of evaporation and thus stoichiometry. For comparison, some investigations on Gd 2 Zr 2 O 7 were included which is less prone to evaporation and formation of non-stoichiometry. Particle temperature distributions were measured by the DPV-2000 diagnostic system. In these distributions, characteristic peaks were detected at specific torch input powers indicating evaporation and solidification processes. Based on this, process parameters can be defined to provide stoichiometric coatings intended to show good thermal cycling performance.

Low-pressure cold spray has been used as an innovative method to deposit metal matrix composite (MMC) coatings: boron carbide-nickel (B4C-Ni) and tungsten carbide-cobalt-nickel (WC-Co-Ni) composites. The coatings were studied using scanning electron microscopy, X-ray diffraction with Rietveld refinement, and acoustic emission-coupled four-point flexural test. Indentation fracture toughness tests were performed on the WC-Co-Ni coatings, only. The results showed that the composites had reinforcing particle volume fractions of 45.8 ± 0.3 vol.% and 22.7 ± 0.1 vol.% for the WC-Co-Ni and B4C-Ni MMC coatings, respectively. Flexural tests were used to evaluate the fracture strain of the composites. In these tests, the WC-Co-Ni composite failed by brittle facture at approximately 0.5% nominal strain. The B4C-Ni composite showed flexural behaviour similar to that of an unreinforced Ni matrix. These results suggest that there was insufficient B4C within the coating to affect significantly the ductile failure mode of Ni matrix. Post bending fracture analysis showed the presence of straight, continuous cracks on the WC-Co-Ni surface and the indentation fracture toughness of WC-Co-Ni was found to be 1.2 ± 0.2 MPa·m0.5. Discontinuous, random cracks were observed on the B4C-Ni surface. The quantification of these properties is essential in evaluating the performance of the low-pressure cold sprayings to determine their potential applications.

Corrosion resistance of coatings deposited by thermal spraying technology HVOF (High Velocity Oxygen Fuel) requires high density in coating and good adhesion to substrate material. The majority of thermally sprayed materials meet the requirements of high corrosion resistance in terms of their composition. However, porous structure raises doubts about the performance of thermally sprayed coatings regarding sufficient protection to the base material. In fact, corrosion protection is a basic coating function. However, , no sufficient attention has been dedicated to the issue of component protection against corrosion attack using HVOF sprayed coatings. In this study, NiCoCrAlY, NiCoCrAlTaReY, NiCoCrAlYHfSi, and CoCrAlYTaCSi coatings were deposited on the substrate material 1.4923. The coatings were deposited using HP/HVOF (High Pressure / High Velocity Oxygen Fuel) thermal spraying technology. The coatings were exposed to the corrosive-aggressive environment in the form of molten salts mixture with composition of 60 % V 2 O 5 and 40 % Na 2 SO 4 at the selected temperature of 750 °C. Further, all coatings were exposed to cyclic conditions. Weight changes of individual specimens were measured after every cycle and results were recorded in diagrams. After the corrosion test, all evaluated coatings were analyzed using scanning electron microscope (SEM), analysis of elemental composition (EDS) and X-Ray diffraction. The NiCoCrAlY and NiCoCrAlTaReY coatings showed the best corrosion protection in selected corrosive aggressive environment, forming the protective oxide layer that prevented further corrosion attack. On the contrary, NiCoCrAlYHfSi and CoCrAlYTaCSi coatings were found not to be suitable for corrosion protection of components working in selected corrosive environment.

La0.58Sr0.4Co0.2Fe0.8O3-δ (LSCF), deposited on a metallic porous support by means of plasma spray-physical vapor deposition (PS-PVD) is a promising candidate for oxygen-permeation membranes. However, after O2 permeation tests, membranes show vertical cracks leading to leakage during these tests. In this work, a feature leading to crack formation has been identified. More specifically; Membrane residual stress changes during thermal loading have been found to be related to a phase transformation in the support. In order to improve the performance of the membranes, the metallic support has been optimized by applying an appropriate heat treatment. Additionally, it has been found that coatings deposited at lower oxygen partial pressures consist of 70% cubic and 26% rhombohedral perovskite phases. This increases the non-stoichiometry, which drives the formation of non-perovskite phases during annealing, affecting the membrane stability and the ionic conductivity. The amount of oxygen added during spraying can be used to suppress the cubic to tetragonal phase transformation.

Hydroxyapatite (HAp) is known to be bioactive, i.e. able to bond to bone. This makes HAp very suitable to be applied as coatings on bone-metallic implants. In this work high velocity oxy-fuel spraying (HVOF) was used successfully for obtaining hydroxyapatite coatings on Ti-6Al-4V substrates. With optimized HVOF process parameters, coatings with similar bond strength to plasma sprayed HAp coatings, good microstructure and higher crystallinity degree than atmospheric plasma sprayed ones were obtained. As-deposited HAp coatings contains amorphous calcium phosphate (ACP) that can be crystallized by a heat-treatment of 60 minutes at 700 °C, resulting in a more stable coating when they are immersed in simulated body fluid (SBF).Coating structural characteristics of as-sprayed and post heat treated coatings were analysed with X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy analyser (EDS), Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). Furthermore, in vitro tests were done in order to evaluate the coating response. Surface changes were observed for as-sprayed coating but not after a post heat treatment. Moreover, the strength of the coatings were evaluated after in vitro leaching. The high degree crystallinity of the post heat treated coating improves the adhesion between the coating and the substrate after an in vitro test in a free-protein simulated body fluids (SBF). Consequently a relation between the amorphicity, the in vitro response and mechanical degradation of the coating was found.

For the engines used in small turboprop aircrafts, the introduction of abradable coatings represents a feasible way to reach higher levels of overall engine efficiency, specifically by improving the fuel consumption and increasing the inter turbine temperature margin. Abradable coatings on seals also contribute to improved hot restarts capability of an engine and lead to substantial extension of service life of the rotating counter bodies. In our contribution, we concentrate on flame sprayed nickel graphite abradable coating that can be used in turboprop engines both for seals and clearance control. The focus is the impact of spraying parameters on the physical and function properties of the abradable coating.

The phase transformation and reaction of ZrO 2 -CaO- ZrSiO 4 and ZrO 2 -Y 2 O 3 -ZrSiO 4 coatings with manganese oxide at 1273 K were investigated using X-ray diffraction (XRD) and scanning electron microscopy (SEM). SiO 2 phase formed in the coatings, which was from the ZrSiO 4 decomposed and easy react with manganese oxide or CaO. SiO 2 has precedence over react with CaO than manganese oxides for ZrO 2 -CaO-ZrSiO 4 coatings, and which result in to promote t-m phase transformation. On the contrary, the reaction between SiO 2 and MnO is primary for the ZrO 2 -Y 2 O 3 -ZrSiO 4 coatings and result in the damage or exfoliation on the surface of the coatings.

This study deals with the deposition of coating materials that can be difficult to process by plasma spraying, including lanthanum and gadolinium zirconate, two pyrochlores of interest for thermal barrier applications, and lanthanum strontium cobalt ferrite (LSCF), a perovskite of interest for gas separation membranes. In addition to conventional atmospheric plasma spraying (APS), the feedstock powders were applied by suspension plasma spraying (SPS) and plasma spray-physical vapor deposition (PS-PVD). The spraying processes are described in detail along with the characteristics of the powders and coatings and the effects of various spray parameters on splat behavior and coating composition and structure.

Plasma sprayed zirconium (Zr) metal coatings onto uranium-molybdenum (U-Mo) alloy nuclear reactor fuel foils act as a diffusion barrier between the fuel and the aluminum fuel cladding. Neutron diffraction was performed to investigate the crystallographic phase composition, crystal orientations and lattice parameters of the plasma sprayed Zr and the U-Mo substrate. The neutron diffraction results show that the plasma sprayed Zr coating is crystalline, phase pure (alpha-Zr) and has preferred crystalline orientation likely due to directional solidification. Also, there is a slight (~0.01 Å for a direction and ~0.016 Å for c direction) increase in the plasma sprayed Zr lattice parameter indicating oxygen in the lattice and some residual thermo-mechanical strain. There is little or no modification of the underlying U-Mo following plasma spraying. In particular, there is no detectable allotropic transformation of the starting gamma-U (body-centered cubic) to alpha-U (orthorhombic). The unique neutron diffraction capabilities at LANL are well suited for nuclear fuel characterization offering distinct advantages over conventional X-ray diffraction and destructive metallography.

Up to now no coating systems are marketable in the field of direct hot extrusion, which provide both surface protection of the parts being in contact to the billet (i.e. container and die), and a significant reduction of the frictional losses being induced by the billet passing along the container walls. To dispense the use of lubricants and to enhance the usable forming capacity of the process, different oxide ceramics were given in one suspension and plasma sprayed. The aim is to reach a mixing of the feedstock to obtain deterministic solid solutions of the oxide phases which show a reduction of their coefficient of friction under dry sliding conditions. To reach this goal the high surface-to-volume ratio of feedstock with primary particle sizes below 100 nm was used. By means of X-ray diffraction it could be proven, that the desired phases could be synthesized. The coatings showed a considerable lowering of their frictional coefficient in tribological testings against 100Cr6 in the region of the operation temperatures for the hot extrusion of aluminium alloys. Besides the experimental work the fundamentals of the mixing process of different oxides regarding crystallographic aspects are discussed.

In this work, computational fluid dynamics (CFD) results confirm earlier calculations indicating that significant evaporation occurs in plasma torch nozzles. In addition, experimental work is performed, investigating the nature of ceramic deposits produced by plasma spray-physical vapor deposition (PS-PVD), particularly coatings composed of nanosized clusters. It was found that as the hot plasma jet comes close to the relatively cool substrate, a boundary layer is formed due to the rapid drop in temperature and velocity. In summary, coatings produced by PS-PVD are a mixture of nanocluster and vapor deposition.

Suspension plasma sprayed (SPS) coatings can be produced with fine powder particles and tailor-made porosity. This allows to achieve low thermal conductivity which makes the coatings attractive as e.g. topcoats in thermal barrier coatings (TBCs). Used in gas turbine applications, the TBCs are exposed to high temperatures which leads to alterations of the microstructure. To obtain coatings with optimized properties, possible microstructure alterations like closing of pores and opening of cracks have to be taken into account. Hence, in this study, TBC topcoats consisting of 8 wt.% yttria-stabilized zirconia (YSZ) were heat treated in air at 1150°C and thereafter investigated using scanning electron microscopy, X-ray diffraction, and nuclear magnetic resonance (NMR) cryoporometry. For all investigated samples, the porosity decreased as a result of the heat treatment. The finer pores and cracks disappeared and the larger pores grew slightly and achieved a more distinct shape as the material seemed to become more compact.