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.

Technological properties of thermally sprayed deposits are to a great extent related to the underlying microstructure. The present project aims to relate macroscopic properties of metallic coatings to their microstructure. For this purpose, thermally sprayed deposits of nickel based alloys (NiCr, NiCrAlY) were manufactured by various spraying techniques - atmospheric and vacuum plasma spraying, flame spraying, high velocity oxygen fuel and water-stabilized plasma spraying. One of the key microstructural features is the void system. This system is usually characterized by the total volume of voids, the so called porosity. An additional characteristic parameter of the void system is the specific surface area. The method of anisotropic Small Angle Neutron Scattering (SANS) in the "Porod Regime" allows the determination of the anisotropic specific surface area of the complex void system that consists of intralamellar cracks and interlamellar pores. In contrast to optical microscopy, the SANS technique is capable of resolving the pore structure down to the nanometer scale, and the measured specific surface area represents a statistically relevant average value for the whole illuminated sample volume which is usually a few mm 3 . Besides the presence of voids and cracks the performance of thermally sprayed coatings is also significantly influenced by residual stresses. In the present work residual strains were determined by the technique of neutron diffraction as well as by bending tests, i.e. laser profilometry of the substrate before and after the spraying process. The specific surface area and the residual stresses are discussed with respect to total porosity, the presence of secondary phases like oxides and wear behavior. Special attention is drawn to the anisotropy of the apparent surface area, which is discussed with respect to the anisotropy of macroscopic properties like electrical resistance.

This paper presents novel results of a series of experiments intended to study the role of the size of the feedstock powder on the microstructure of the deposits. For this purpose, Metco and the feedstock powder, yttria-stabilized (8% wt) zirconia, with number-weighted mean particle sizes of 32, 47, 56, and, 88 micrometer, are used. Small-angle neutron scattering and multiple small-angle neutron scattering (MSANS) methods are applied to determine the microstructure of the four deposits. Companion indentation measurements are performed to determine the elastic moduli of the deposits. The paper also discusses the MSANS 3-void model in relation to the anisotropic elastic properties. Paper includes a German-language abstract.

This paper describes the technique of anisotropic multiple small-angle neutron scattering (MSANS). Anisotropic MSANS, when combined with anisotropic Porod scattering, electron microscopy, and measurements of elastic modulus and density, has made possible the determination of the porosities, surface areas, mean opening dimensions, mean diameters, and approximate orientation distributions, of the intra-splat cracks and interlamellar pores, as well as the porosity, surface area, and mean diameter, of the globular pores. The changes in these parameters, as a function of annealing, are studied. Paper includes a German-language abstract.

The microstructure of plasma-sprayed deposits (PSD) is dominated by two void systems - interlamellar pores and intralamellar cracks - each with a different anisotropy. Varying anisotropics and crack-to-pore ratios within PSDs are responsible for the anisotropic properties observed in the deposits. While it is difficult to apply standard porosity measurement techniques to the assessment of anisotropic microstructures, novel techniques utilizing different approaches have recently emerged. Image analysis (IA) of impregnated PSD samples is the most direct technique. The structure is stabilized by impregnation and then polished and imaged. The limitations of IA lie in the impregnation process and in the subsequent polishing. Also, the images produced from anisotropic materials can be difficult to interpret quantitatively. The technique of small-angle neutron scattering (SANS) has recently been successfully applied to the study of PSDs. The major advantages of SANS are that it does not require sample preparation and that quantitative information can be gotten about the separate crack and pore systems, including their distinctive anisotropics. However, the relationship between the SANS results and the underlying structure is more complex and less intuitive than for IA, and the availability of the SANS technique is limited by the need to have access to a powerful neutron source, such as a reactor. Also, the two techniques present different views of the microstructure because of the different sensitivities in different parts of the size range. This paper compares results from IA and SANS from a set of thick plasma-sprayed ceramic deposits possessing a range of crack/pore microstructures, and discusses how the two techniques might complement one another.

The evolution of the void microstructure of yttria-stabilized zirconia (YSZ) plasma-sprayed deposits (PSD) was studied as a function of heating in air from room temperature to 1400°C , and during a constant temperature hold at 1100°C for 19 hours. The samples were studied using the terminal slope (Porod scattering) of small-angle neutron scattering (SANS), modified for the analysis of anisotropic structures. The experiment was done in-situ using a special furnace built for use on the small-angle scattering instrument. SANS Porod scattering can distinguish between the two major void systems - interlamellar pores and intralamellar cracks - that are present in the PSD microstructure. Thus, changes in the void surfaces of the cracks and the pores could be followed separately as a function of temperature. The surface area attributable to the interlamellar cracks significantly decreased at temperatures below 1000°C, whereas the surface area of the interlamellar pores only began to decrease at temperatures above 1000°C. This suggests that there are significant differences in the sintering of these two void systems, probably associated with differences in their sizes and shapes. The first noticeable changes in the void surfaces were observed at temperatures just above 600°C, which is a very low temperature for YSZ. During annealing at 1100°C for 19 hours, there was a decrease in the interlamellar surfaces of about 10%.

The microstructures of as-sprayed and thermally-cycled freestanding and on-substrate deposits of yttria-stabilized zirconia were studied using small-angle neutron scattering (SANS). The SANS analysis allows the interlamellar pores and the intralamellar cracks, which are the two dominant void systems in the microstructure, to be characterized separately. Whereas up to 20% of the void surface area in the as-sprayed deposits was found to be in the cracks, the thermally-cycled deposits contained only a negligible quantity of cracks. At the same time, changes in the pore surface areas between the lamellae (i.e., the interlamellar pores) were much smaller. As a result, the microstructure of the thermally-cycled deposits was much more anisotropic than the microstructure of the as-sprayed deposits. Varying the cooling and the heating rates did not significantly change the microstructure but varying the total time that the deposits were at high temperature did affect the evolution of the surface area. The presence or absence of a bond coat and substrate also did not measurably influence the results.

A technique has been developed to characterize the elastic modulus of zirconium oxide - 8 % yttrium oxide plasma sprayed deposits. A commercial hardness indenter has been modified to record load - displacement as a spherical ball is elastically loaded onto the surface of the material to be measured. The resulting data are used to calculate the elastic modulus. Since the loads used are in the elastic region, the technique is, in theory, nondestructive. Relatively small areas of the material, approximately 50 μm in diameter, are sampled by the indenter, allowing local mapping of elastic modulus variations throughout the deposit. Using this technique, elastic modulus variations have been measured through the thickness of the deposit. Also, different moduli were measured in the cross-section and through the thickness and these differences are correlated with the microstructure. Finally, significant increases in elastic modulus have been found in samples annealed for 2.5 h at 1100°C. These changes have been correlated with small angle neutron scattering measurements of void surface area.