A new laser thermal spraying method has been developed and experimentally realized. The new method makes possible independent energy input to the powder stream and workpiece using conical laser beams and thus is more efficient than other methods. The new method offers environmental benefits in comparison to other techniques.

In many empirical studies on the structure and properties of thermally sprayed coatings, a set of two predefined parameters (e.g. porosity and elastic modulus) is correlated over a narrow range of structural variation assuming a continuous correlation function. Such a data evaluation assumes the existence of physical correlation’s between material behavior and microstructure. The experimental approach, undertaken in this study, comprises a maximum range of morphologies for starting materials with nearly identical chemical compositions to reveal the influence of microstructural changes of diverse defect species on different coating properties. The large matrix of structural and physical data is statistically correlated without any preconceived assumptions concerning the mathematical functions or the physicochemical nature of the property-microstructure-correlation’s. The divergent morphologies are realized by using different coating processes such as vacuum (VPS) and atmospheric (APS) plasma spraying, water stabilized plasma spraying (WSP), wire arc (WAS)- and flame spraying (FS), including variation of process specific parameters. The microstructure is systematically analyzed along length scales starting from defects in the micrometer down to the nanometer range. The microstructure and its anisotropy is quantified by small angle neutron scattering (SANS). The phenomenological coating behavior is successively investigated starting from basic properties such as electrical and thermal conductivity, elastic constants, residual stresses up to application oriented properties such as wear resistance. Property combinations presuming high sensitivity to microstructural changes are preferentially characterized and statistically correlated.

This article gives an overview of thermal spraying of polymers with respect to the different spraying processes, the polymer materials in use for thermal spraying and new trends of using polymers as separate spraying material and in combination with plastic and non-plastic materials. Flame spraying is by far the most common process used for thermal spraying of plastic materials. In addition in the past years two other processes have been used to produce thermal sprayed plastic coatings: plasma spraying and high-velocity oxy fuel spraying (HVOF). The areas where the different processes are used as well as the modifications to conventional plasma and HVOF devices and the advantages and disadvantages using these two processes to produce plastic coatings will be described. In addition to the common materials used for flame spraying (e.g., PA 11, PA 12 or EVAL), other materials giving new opportunities of application of thermal sprayed coatings have been used like PEEK and LCPs. The areas where these materials are used are described as well as the special features of these materials. Furthermore there are new trends in using plastic materials for thermal spraying. Thermal sprayed polymer materials are for example combined with plastic as well as non-plastic materials or pigments giving special effects to the coatings, e.g, reflective or anti-skidding coatings. It is described how coatings with the mentioned effects can be produced.

Nanocrystalline Inconel 718 and Ni powders were prepared using two approaches: methanol and cryogenic attritor milling. High velocity oxy-fuel (HVOF) spraying of milled Inconel 718 powders was then utilized to produce Inconel 718 coatings with a nanocrystalline grain size. Isothermal heat treatments were carried out to study the thermal stability of the methanol milled and cryomilled Inconel 718 powders, as well as the HVOF Inconel 718 coatings. All nanocrystalline Inconel 718 powders and coatings studied herein exhibited significant thermal stability against grain growth as evidenced by a grain size around 100 nm following annealing at 1273 K for 60 min. In the case of the cryomilled nanocrystalline Ni powders, isothermal grain growth behavior was studied, from which the parameters required for the prediction of the microstructural evolution during a non-isothermal annealing were acquired. The theoretical simulation of grain growth behavior of nanocrystalline Ni during non-isothermal annealing conditions yields results that are in good correspondence with the experimental results.

A high speed thermoanalytical method has been developed to determine the thermophysical properties of the powders used in thermal spraying. This method is based on heating the powder by means of an electron- or photon-beam in vessels made of materials with excellent heat conductivity. By comparing heating and melting behavior of powders with similar composition but different particle sizes and shapes, their properties can be determined. The suggested high speed thermoanalytical method makes it possible to investigate the heating and melting behavior of spray powders under high speed heating conditions. The results of the experiments, elaborated by this method can be used for further modeling work. Paper text in German.

Despite their light weight, 2.3 times lighter than Al, polymers are limited to application with low thermal, wear, and abrasion demands. The enhancement of the functional surfaces of the polymers using thermal spraying techniques is a challenging task due to the thermal degradation of polymers, the low wettability, and the disparate atomic properties. The twin-wire arc spraying (TWAS) process comprises two contradictory features. Almost all spraying particles are in a molten state on the one hand, and on the other hand, the spray plume has the lowest heat output among the different thermal spraying techniques. Therefore, it is a promising spraying technique for the required surface improvement. The surface of the 3D-printed parts was metalized using two successive layers. The first layer is a TWAS coating made of low-melting ZnAl 4 to avoid thermal degradation and provide a bond coat. The topcoat is also applied using a TWAS process and was made out of Ni-WC-Co as cored wires. The top hard coating has improved the wear resistance of the polymers by 14.6 times. The erosion of the coated and uncoated specimens was determined using a low-pressure cold gas spray gun. Ni-WC-Co coating led to more than five times higher erosion resistance.

Thermal spraying of silicon nitride has been considered impossible because the high temperatures involved lead inevitably to decomposition/oxidation of the material. To address these issues, improved silicon nitride-based powders were developed, two of which have been tested as reported in this paper. The powders were applied using low pressure plasma spraying (LPPS) and the resulting coatings characterized based on microhardness, adhesion, and cohesion strength. Phase transformations of the powders during spraying were also investigated and preliminary optimization strategies by statistical variation of plasma spray parameters were tested.

This paper presents a mathematical model of the plasma-spray coating formation process that allows one to estimate bond strength energy, a parameter related to coating quality. Bond strength energy is defined on the basis of particle-substrate or system balance. Unknown quantities in the energy equation are obtained from nonstationary Navier-Stokes equations for velocity field and pressure and from thermoelasticity equations for temperature and stress. Complexities associated with particle spreading and nonlinear hydrodynamics have made it necessary to develop a stable numerical technique.

Tungsten carbide cobalt thermal spray coatings are used in the aircraft industry to reduce wear damage of lightweight metals such as titanium The performance and life of tungsten carbide (WC-Co) coated titanium materials depend on many factors. An important factor that has received increased attention in thermal spray research is the residual stresses in the coating and substrate. Residual stresses depend on the parameters of the application process. Parameters affecting residual stresses include the prespray treatment of the substrate material (grit blasting, shot peening) and the type of spray application process (HVOF, plasma arc) During the in-service life of a WC-Co coated material, residual stresses can change significantly. The goal of this work is to quantitatively evaluate the changes in residual stresses of the substrate and the WC-Co coating during various stages of processing. A destructive laboratory method, called the "Modified Layer Removal Method," was used to evaluate the through-thickness residual stresses of the WC-Co coating and the titanium substrate material. Residual stresses are determined for three conditions: (1) shot peened, (2) shot peened and grit blasted, and (3) shot-peened, grit blasted and thermal spray coated. The changes in the residual stresses are shown at selected stages during the processing history of the coated materials. Differences between residual stress levels at selected stages are identified and discussed. The effect of coating thickness and HVOF application process on the residual stress in the coating is also examined.

The direct conversion of heat into electric current is still less developed form of energy conversion. Thermoelectric material working in a temperature gradient is able to induce a voltage that can drive a serial resistor. New research activities try to broaden the employment of thermoelectric generators from spacecraft technologies to terrestrial applications. The main problem at the moment is rather the lack of economic production methods, than the low efficiency of conversion. After an overview about the basics of thermoelectrics and possible applications the paper presents the thermal spraying as an alternative processing method with first attempts to realize graded structures. Al-doped and Co-doped FeSi 2 has been consolidated by APS, SPS, VPS and HVOF spraying. The microstructure, phase composition and oxygen input have been investigated and set into relation to thermoelectric properties.

A novel plasma spray process for producing nanostructured coatings, hypersonic plasma particle deposition (HPPD), has been experimentally investigated. In HPPD, vapor phase precursors are injected into a plasma stream generated by a DC arc. The plasma is quenched by supersonic expansion through a nozzle into a vacuum (~ 2 torr) deposition chamber. Ultrafine particles nucleated in the nozzle are accelerated in the hypersonic free jet downstream of the nozzle and inertially deposited onto a substrate. The short transit times between the nozzle and the substrate (< 50 μs) prevent inflight agglomeration, while the high particle deposition velocities result in the formation of a consolidated coating. We have investigated the production of silicon and silicon carbide coatings using SiCl 4 and CH 4 precursors. Silicon deposits analyzed by transmission electron microscopy were found to have nanostructured regions with grain sizes varying from 5-20 nm. Corresponding particle size distributions measured before deposition using an extractive aerosol probe peaked around 15 nm, suggesting negligible grain growth occurred in the samples studied. Silicon carbide particle size distributions measured at various deposition chamber pressures verify that the low residence time characteristic of the HPPD process minimizes in-flight agglomeration.

At the present, components which require both nitriding and locally a thermal sprayed coating or nitrided components which should l)e reworked are usually nitrided before spraying and the area to be coated is masked during nitriding or is prepared before spraying by locally removing the nitrided layer by grinding. Seen technically, advantages are to be expected if the nitriding process can be carried out after spraying. Moreover a post-nitriding of thermal sprayed coatings is of interest for improving coating characteristics, mainly wear resistance. Understanding the behaviour of sprayed coatings during nitriding in comparison to bulk materials will help to understand generally the behaviour of such coatings in gas atmospheres at increased temperatures. The objectives of the project are the investigation of the interaction between thermal spraying and nitriding, and the optimisation of both processes to achieve improved bonding, wear and corrosion characteristics respectively to get nitriding of the substrate through the coating without spalling or cracking. Furthermore the behaviour and structural changes of different coatings at increased temperatures are determined. The metallographic, X-ray, wear and corrosion results of the resulting compound coatings and parts are presented. Possible new applications are discussed. The project is funded by the German Research Ministry.

Engineering analytical formulas describing variations of the final values of the splat thickness and radius during flattening of composite particles in thermal spraying are obtained. The effective values of the droplet parameters (impact velocity and viscosity) and the Reynolds number are introduced taking into account a composition of the composite particles. Analytical results obtained agree well with the experimental data available.

It is widely recognized that substrate surface roughness, or topography, plays an important role in droplet-substrate interaction and the adhesion of sprayed coatings. A key difficulty in understanding the role that topography plays during droplet impact, wetting and solidification has been the availability of methods for appropriate characterization of the topography. The complex nature of the substrate topographies cannot be adequately characterized by conventional methods such as Ra. In this work, scale-sensitive fractal analyses are considered for advancing the understanding of roughness of grit blasted surfaces in thermal spray applications. Area-scale analysis is performed on 3D data sets acquired from different grit-blasted substrates. From fractal analysis it is known that the apparent area of a rough surface increases as the scale of observation decreases. The area-scale relations are used to guide experimental design for topographical data acquisition and analysis and to better understand the influence of grit blasting on substrates for thermal spray. The potential of these scale-sensitive analysis techniques to fulfill the above bases for supporting statistical correlations and clear physical interpretations is discussed.

Different mechanisms of development of the substrate-coating adhesion during thermal spraying are considered. One of the most important is mechanical interlocking formed chiefly due to roughness of the substrate surface, high pressures developed upon the droplet impact and solidification of the lower part of the splat. Possible deformation of the substrate surface and rebounding of the impinging droplets are considered. Thermal mechanisms involving partial or complete melting and subsequent solidification in the substrate interfacial region is shown to be effective in creation of the adhesive bonds. The role of the diffusion processes and the influence of the splat morphology on adhesion is discussed. Mechanisms of splashing of droplets impinging onto the substrate surface during thermal spraying and their influence on the coating-substrate adhesion are considered. Roughness of the substrate surface is shown to be critically important to obtain good adhesion. Transition temperature is shown to exist which determines the splat morphology on the smooth surface of the substrate. With a "cold" substrate when its initial temperature is less than the transition temperature the splashing occurs. When the substrate initial temperature exceeds the transition one a regular splat is formed. The theoretical results agree well with the observed behaviour of the thermal spray coatings and in the case of the thermal mechanisms of adhesion these results are in a good agreement with the experimental data.

Thermally sprayed coatings of high performance thermoplastics are of interest especially for the chemical industry for anti-corrosion applications at elevated temperatures. In this paper coatings of polyetherether-keton (PEEK) and polyphenylen-sulphide (PPS) have been produced by simple flamespraying. They have been investigated by optical metallography, FT-IR analysis and DSC-analysis. Among the coating properties also the "in-flight" particles have been studied by wipe-tests and FT-IR analysis in order to assess possible decomposition effects during spraying.

A reaction-formed NiAl intermetallic compound (IMC) powder has been deposited as a coating onto low carbon steel test coupons by the High Velocity Oxy-Fuel (HVOF) process using both gaseous and liquid fuels. The microstructure of this coating has been examined using scanning electron microscopy and x-ray diffraction and was found to depend on spraying conditions. Oxidation tests on the coating in air, between the temperatures of 800°C-1200°C, revealed that an α-alumina (Al 2 O 3 ) scale formed on the coating's surface. At 1200°C, a nickel spinel (NiO/NiAl 2 O 4 ) and haematite (Fe 2 O 3 ) phases were observed. Diffusion studies were performed to calculate an activation energy for iron ion diffusion in NiAl.

The cavitation erosion of various hardfacing coatings was investigated by using a vibratory cavitation apparatus according to ASTM G 32. Coatings of austenitic stainless steel containing 10 % cobalt were applied by arc welding. High velocity oxy-fuel spraying (HVOF) was employed to produce coatings of various kinds of cermets and metallic alloys. For each coating, the steady state erosion rate was determined and the effect of process parameters and alloy composition on the microstructure and erosion rate was investigated. The morphology and microstructure of the coatings before and after cavitation testing were analysed by metallographic methods in order to study the erosion mechanism. It is demonstrated that the high resistance to cavitation erosion of the cobalt-alloyed steel can even further increase when the fluxed core arc welding process and an improved pulsed power source are used to produce the coatings. The erosion resistance of the HVOF coatings, however, was limited by pores, microcracks and oxides and did not significantly exceed the level typical for bulk stainless steel 316 L.

Effect of nozzle geometry (such as throat diameter of a barrel nozzle, exit diameter and exit divergence angle of a divergent nozzle) on HVOF thermal spraying process (thermodynamical behavior of combustion gas and spray particles) was investigated by numerical simulation and experiments with Jet Kote II system. The process changes inside the nozzle as obtained by numerical simulation studies were related to the coating properties. A NiCrAlY alloy powder was used for the experimental studies. While the throat diameter of the barrel nozzle was found to have only a slight effect on the microstructure, hardness, oxygen content and deposition efficiency of the coatings, the change in divergent section length (rather than exit diameter and exit divergence angle) had a significant effect. With increase in divergent section length of the nozzle, the amount of oxide content of the NiCrAlY coatings decreased and the deposition efficiency increased significantly. Also, with increase in the exit diameter of the divergent nozzle, the gas temperature and the degree of melting of the particle decreased. On the other hand the calculated particle velocity showed a slight increase while the gas velocity increased significantly.

Analytical correlations between the flattening characteristics and the Reynolds number and the spraying angle are obtained. The final splat thickness is shown to decrease and the final splat radius is found to vary nonuniformly with a decrease in the spraying angle. Analytical formulae are obtained describing the pressure distribution in a flattening droplet along the droplet-substrate interface during thermal spraying at off-normal angles. The magnitudes of droplet-substrate microadhesion, deformation of the substrate surface and the coating porosity depend upon the spraying angle. The spraying angle 45° can be recommended as a reasonable limit for off-normal thermal spraying for achieving the quality coatings. The theoretical results obtained on flattening characteristics agree with those of the experimentally observed tendencies of thermal spraying at off-normal angles. The theoretical results for % relative porosity are in a reasonable agreement with experimental observations at off-normal angles between 30° and 90°.