Within a Brite Euram project thick thermal barrier coatings for combustor applications were produced by plasma spraying of yttria partially stabilised zirconia (ZrO2 + 8 wt.% Y2O3). The material properties of such coatings strongly depend on their microstructure which can be altered by manipulating the parameters controlling the plasma spraying process. Covering a variation of possible microstructures, the coatings considered had a thickness of about 2 mm and were six to eight times thicker than the coatings currently in service. This investigation was concerned with an evaluation of the thermophysical and mechanical properties of these coatings and their correlation with the microstructure and the plasma spray parameters. Particular attention was paid to the influence of coating segmentation, microcracking and porosity. The experimental work included the measurement of the thermal diffusivity using the laser flash technique, thermal expansion measurements, and the determination of flexural strength and Young's modulus by means of a specially constructed four-point bend rig. Since some of the samples considered were sprayed according to a partially factorial test plan a statistical evaluation of the material data was possible yielding the correlation between process parameters and material properties.

During Thermal Spraying material is partially or totally melted in between milliseconds, accelerated to high velocities and propelled onto the surface to be coated. Different temperatures, velocities and cooling times of the particles arise from different spraying techniques and conditions. The microstructure can be widely varied by tuning the spraying parameters. To optimize the coating properties with respect to a specific function one has to know i) the influence of the spraying conditions on the microstructure and ii) the correlation between microstructure and coating properties. Therefore analyzing methods are needed to determine the microstructure and to characterize mechanical, physical and chemical properties of the coatings. The proposed paper summarizes methods to characterize the microstructure including metallographic techniques, electron microscopy and X-ray analysis. Methods to determine the properties of the coatings including various adhesion tests, residual stress measurement, tribological and corrosion tests will be described in more detail. The increasing importance of Quality Management in all industrial sectors call heavily for reliable, destructive and especially non-destructive characterization techniques of coatings. An overview of common characterization techniques as well as new trends will be given. Recent development of International standardized tests will also be reported.

Rotating bending fatigue tests have been conducted at room temperature in laboratory air using specimens of medium carbon steel (S45C), low alloy steel (SCM435) and titanium alloy (Ti-6AI-4V) with HVOF sprayed coating of a cermet (WC-12%Co) and S45C with WFS sprayed coating of a 13Cr steel (SUS420J2). Plane bending fatigue tests were also conducted at stress ratios, R, of -1, -0.5 and 0 for S45C with WC-12%Co coating. The fatigue strength and fracture mechanisms were studied. The fatigue strength evaluated by nominal stress was strongly influenced by substrate materials, R and the thickness of sprayed coatings. Detailed observation of crack initiation on the coating surface and fracture surface revealed that a crack was initiated in the coating and then cracks were initiated in the substrate due to the stress concentration of the crack in the coating. The fatigue strength of the sprayed materials was dominated by that of the sprayed coating. Therefore, the fatigue strength could be evaluated uniquely in terms of the true stress on the coating surface. The influence of compressive residual stress of the sprayed coatings on fatigue strength was discussed based on the fatigue mechanisms at different stress ratios.

Impact performance of plasma spray coatings is usually evaluated by means of surface observation after impact action. As a matter of fact, the dynamic response characteristics of coatings in the course of impact action are also very important. In this paper, a method of response frequency spectrum analysis is developed for the impact evaluation of plasma spray coatings. An impact test machine, in which the impact load is generated by a pivot-rod-lever system, is specially designed, allowing both single impact test and repeated impact test. The frequency spectra of Cr2O3 ceramic coating and WC-Co17% alloy coating under single and repeated impact action are analyzed. The results show that there is an obvious relationship between the impact performance and the impact response frequency spectrum. Abrupt changes in the coating, such as appearance of surface cracks and surface damage, correspond the sudden changes of the response frequency spectrum.

Pure copper thick deposits were vacuum plasma sprayed in such a way that several porosity levels were obtained. Mechanical compressive tests permitted to assess the mechanical behavior of these materials and to study the associated pore microstructural changes. A linear porosity level decrease was observed during the first stages of the compressive squeezing, until the stress reached a specific value corresponding to a transition between pore contraction and copper splats deformation. Stereological measurements showed that the pore squeezing was isotropic.

Polyphenylene-sulphide (PPS) and polyphenyletheretherketone (PEEK) have high heat and corrosion-resistant performance. Thermal sprayed coatings of PPS and PEEK have been produced by the HVAF spray system. The molecular structures of these coatings have been analyzed by Fourier Transform Infrared Spectrophotometer (FT-IR) and Differential Scanning Calorimeter (DSC). The microstructures of cross-section and surfaces of these coatings have been observed. The formation mechanism of these coatings has been estimated as follows; (1) PPS and PEEK powders are melted and oxidized during thermal spraying. However, the amount of coating oxidation is very small, so that high anti-corrosion performance of sprayed coatings is obtained. (2) These coatings have some pores including the incomplete melting particles. However, it is estimated that these pores are closed-pores.

Fe-Cr(-Mo) alloy coatings were thermal sprayed by different processes of LPPS, HVOF and HPS. The as-sprayed coating by LPPS is perfectly amorphous and coatings by other processes contain partly crystalline phases. The amorphous phases crystallize at 773 K or more and shows a high hardness of about 1000 to 1400 DPN just after crystallization. The anodic polarization curves of the coatings shift from active to passive state in 1N H2SO4 and 1N HCl solutions. The coatings obtained by LPPS indicate the lowest active and passive current densities and possess the best corrosion resistance. The corrosion resistance of the coatings obtained by other processes are better than a SUS316L stainless steel coating. The LPPS coating of Fe-Cr-C-P alloy is not attacked on immersion test in 6% FeCl3·6H2O solution containing 0.05N HCl at the corrosion potential, while large pit corrosion is developed in a SUS316L stainless steel sheet.

The corrosion characteristics of two bespoke Ni-Cr-Mo-B alloy powders sprayed by the high velocity oxy-fuel (HVOF) process have been studied using potentiodynamic and potentiostatic corrosion analysis in 0.5M H2SO4. The deposits have also been microstructurally characterised using X-ray diffraction (XRD), scanning electron microscopy (utilising both secondary electron (SE) and backscattered electron (BE) modes), and transmission electron microscopy (TEM). Results from the microstructural examination of the two alloys have revealed a predominantly amorphous/nanocrystalline (fcc) matrix containing submicron boride precipitates as well as regions of martensitically transformed laths. Apparent recrystallisation of the amorphous matrix has also been observed in the form of cellular crystals with an fcc structure. The oxide stringers observed at splat boundaries were found to be columnar grained α-Cr 2 O 3 , though regions of the spinel oxide NiCr 2 O 4 with a globular morphology were also observed. The coatings of the two alloys exhibited comparable resistance to corrosion in 0.5M H 2 SO 4 , as revealed by potentiodynamic tests. They both had rest potentials approximately equal to -300mV(SCE) and passive region current densities of around 1mAcm-2. Microstructural examination of samples tested potentiostatically revealed the prevalence of degradation at splat boundaries, especially those where significant oxidation of the deposit had occurred.

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.

Thermally-sprayed coatings are applied to various materials to provide protection for beat-loaded parts as well as corrosion and wear. They also serve as a thermal barrier to reduce metal substrate temperatures. Microstructural analysis is used to characterize the substrate, the coating, and the adherence of the coating to the substrate. Accurate evaluation or these coatings depends heavily upon the quality of the polished surface produced by metallographic preparation. A well-prepared surface must first be free of plucked material and have minimal relief between the hard and soft constituents. The entire surface must be flat to allow a clear view of the interface and any reaction products that might be present in the coating or the substrate. Furthermore, the finished polished specimen must be scratch-free and have no resolution destroying films or stains. Various metal and oxide coatings on ferrous substrate material are used to demonstrate the excellent microstructural detail that is revealed when correct polishing procedures are used. These special techniques successfully address the problems normally encountered when preparing hard, brittle coatings or softer metallic coatings and substrates. As a result, clear microstructures are revealed across the specimen surface and valuable information is obtained.

HVOF and plasma spray processes were used to apply Cr3C2-NiCr coatings, which were then characterized by X-ray diffraction and various other tests. The results revealed that the HVOF coatings were more stable than their plasma-sprayed counterparts as well as harder, tougher, less porous, and more erosion resistant. The HVOF coatings have been successfully used in industry and have proven to be an acceptable alternative to electroplated chromium.

Physical properties of coatings based on Fe-B, Fe-Ni-B, Fe-Cr-P-C, Fe-Ni-Si-B, Ni-P, Ni-Nb and Co-Fe-B-Si, deposited by the methods of flame, plasma-arc, and detonation spraying were investigated. The coatings have mostly the amorphous structure with the volume content of the amorphous phase equal to 75-95 %. Values of the distribution and temperature coefficients of electric resistance of the coatings, depending upon a method and conditions of spraying, as well as upon their treatment parameters, were determined. Comparative studies of these coatings and thin amorphous strips produced by the melt spinning method were conducted. The amorphous coatings of ferromagnetic iron and cobalt alloys are shown to be magnetically soft materials and are characterized by a high magnetic induction combined with a high magnetic permeability. As compared with the amorphous strips, Curie temperature of the amorphous ferromagnetic coatings is by 50-140 K higher and their anisotropy of magnetic properties is lower.

This paper examines the stress state of plasma-sprayed amorphous coatings of Fe-B with additions of Ni, Cr, and Mo. Internal stresses depend on the type of plasma gas used, the thickness and composition of the coating, and the material and temperature of the substrate. In this study, additional cooling of the substrate was found to be the most efficient way to reduce internal stresses. Amorphous coatings were also found to improve fatigue strength by as much as 25-30%, which is attributed to the formation of compressive stresses in the coating layers adjoining the substrate.

An integrated approach was developed for investigation of thermal spray coatings with the amorphous-crystalline structure. The new approach combines methods of metallography, differential thermal and X-ray phase analysis, scanning electron microscopy and X-ray microanalysis. This makes it possible to reveal structural, phase and chemical heterogeneity, determine the degree of amorphization of coatings, temperature and heat of crystallization of the amorphous phase during heating. The new integrated approach was used to study amorphous-crystalline coatings of the Ni-P, Fe-Ni-B and Fe-B systems produced by thermal spraying.

Al-Cu-Fe quasicrystalline coatings, due to their high hardness and low friction coefficients, are potential candidates for improving the wear resistance of ductile materials. However, technological applications may be limited on account of their brittle nature. This study examines the effects of starting powder composition and thermal spray process parameters on the phase assemblage, microstructure, and tribological response of Al-Cu-Fe thermally sprayed coatings. It was found that the coatings fail by a delamination mechanism in unlubricated unidirectional sliding wear. Furthermore, the coatings produced by the high velocity oxy-fuel technique showed a very low coefficient of friction and wear rate.

Alumina coatings plasma-sprayed on alumina substrate with metallic bond coating (50Ni-50Cr) and on metal (Ni) substrate have been investigated in terms of adhesion strength and a veined structure formed in alumina coating. The veined structure is formed to heal up cracks and pores in sprayed alumina and substrate alumina after heat-treatment in air. The veined structure consists of oxides of NiAl 2 O 4 (spinel-type) and NiO (NaCl-type). This indicates that the metallic elements in the bond coating or the metallic substrate diffuse along the cracks and pores in alumina and react with alumina. The alumina coating with veined structure shows high strength due to the mechanical anchoring of veined oxide and chemical bonding.

The structure of a thermally sprayed coating is generally of lamellar structure. There is generally porosity in the coating. The examination shows that the relationship between properties and porosity for conventionally processed porous materials is difficult to be applied to thermally sprayed coating because of complex pore networks. The lamellar structure of the coating and the bonding at the interfaces between lamellae often determine the properties of coating. It is generally difficult to evaluate quantitatively the structure of a thermally sprayed coating because of complicated pore networks in the coating. With the filling of the material different from the composition of the coating into the pores the structure of the coating including nonbonded interface area and also generally referred pores can be visualized. According to the distribution of filler in the coating the structure of a coating can be quantitatively evaluated using structural parameters such as lamellar thickness, lamellar bonding ratio, the width of interface gap and so on. The structural parameters necessary to describe the lamellar structure of thermal sprayed coatings and a method based on the pore filling and analysis of the distribution of filled materials are proposed.

Self-fluxing nickel based materials are widely used as hard coating materials. HVOF process is promising to produce dense coating with high adhesion. In present study the effects of HVOF spray conditions, and WC-Co addition into self-fluxing nickel based material (NiCrBSi) and the introduction of HVOF WC-Co bond coat on the adhesion of HVOF NiCrBSi coatings are investigated. With regarding to NiCrBSi material, the spray conditions are optimized by orthogonal regression experimental design method with adhesive strength. The adhesive strength is estimated by tensile test. The results show that the adhesive strength of the NiCrBSi coating sprayed at the optimized conditions reaches to about 40MPa. It is found that the addition of WC-Co material through mechanical blending can improve the adhesion of HVOF NiCrBSi coating. The adhesive strength is increased with the increase in WC-Co content in the composite powder. The introduction of HVOF WC-Co bond coat between NiCrBSi coating and substrate can improve the adhesive strength. The multiply enhancing effect on the adhesive strength of HVOF nickel based coating is recognized by applying HVOF WC-Co bond coat to NiCrBSi-WC-Co composite coating.

Within the framework of a scientific collaboration between the University of Limoges, France and the State University of New York, Stony Brook, USA, a joint work has been conducted on microstructure development and properties of plasma-sprayed molybdenum coatings. This first part of the work is devoted to the study of the effect of substrate nature and temperature on splat cooling, solidification and crystalline structure. They were investigated by means of a heat transfer model in the splat and the substrate, and the observation of splats by a scanning electron microscope and an atomic force microscope. The model takes into account melt undercooling, nucleation and crystal growth, as also a possible melting and re-solidification of the substrate. It has the capability to predict the grain size distribution under assumptions that the quality of contact between the splat and the underlying layer is uniform, nucleation takes place only on the substrate surface, crystal grains grow perpendicular to the substrate surface and no grain coalescence occurs during crystal growth.

This is part II of the two part paper based on international collaboration between the University of Limoges, France and the State University of New York, Stony Brook, USA, aimed at fundamental understanding the relationship between processing condition and microstructure development and properties of thermally sprayed materials. In this study, the effects of deposition temperature on the microstructure and properties development of molybdenum coating was investigated. It is found that with the increase of steel substrate temperature, the molybdenum splat morphology changes from fragmented to more contiguous disk-like shape. The splats on molybdenum substrate show predominantly disk shape. With the increase in deposition temperature, the coating exhibits better lamellar structure with less interlayer pores and debris. The fracture characteristics changes gradually from interlamellar to trans-lamellar and, thermal conductivity is enhanced. Higher deposition temperature improves dramatically the adhesion and bonding of the splats, therefore the physical and mechanical properties of coatings.