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.

Thermally sprayed coatings have residual stresses due to the processing techniques where the particles go through thermal softening / melting, high velocity impact and rapid solidification. The nature and magnitude of residual stresses in these coatings determine the bond strength and failure mechanisms. This investigation thus involves a non-destructive neutron diffraction residual stress evaluation of suspension high-velocity oxy-fuel (S-HVOF) thermal sprayed alumina and YSZ coatings onto 304 stainless steel substrates. SHVOF spray is a high deposition efficiency process to deposit coatings from sub-micron or nanometric feedstock particles. Neutron diffraction measurements were performed at the UK ISIS facility, using ENGIN-X pulsed neutron diffractometer to obtain through thickness residual stress profiles. The Z-scanning method was used to avoid pseudo-strains in the neutron diffraction measurements near the coating surface whereby the incident neutron beam/gauge volume was partially submerged and traversed vertically out of the horizontal coating surface. The residual stress in the alumina coating was compressive across the whole thickness while the stress changed from tensile to compressive in the YSZ coatings. The residual stress measurements were complemented by lab based X-ray diffraction residual stress measurement techniques. Depth sensing indention of the coatings were also performed to gain a comprehensive understanding of the stresses in SHVOF sprayed ceramic coatings.

The mechanical integrity of WC-Co coatings is critical for their performance in wear, corrosion, and impact resistance applications. Residual stress, with its role in development of cracking, micro-cracking, and delamination, is another integral part of the mechanical characterization of the coated systems. In the given study, the residual stress of the WC-Co coatings on steel and stainless steel substrates was examined in two conditions, after deposition and after subsequent surface grinding. Several experimental techniques, including bi-layer curvature, X-ray diffraction, and neutron diffraction, were used to assess residual stress in the coatings and to enable comparison between the methods. Residual stresses induced by deposition are mostly due to rapid particle quenching and solidification upon impact, as well as any cold working induced by high velocity particle impact, but for the WC ceramic particles both effects are insignificant and result in small deposition stress. Thermal mismatch between materials of coating and substrate is the major source of stress and scale accordingly to the CTE of the substrate and coating materials and deposition temperature. It was demonstrated that the grinding applied to surface does not modify the as-sprayed residual stresses in the coatings significantly therefore assuming absence of microcracking that could have potentially affect the residual stresses.

Residual stress build up in thick thermal spray coatings is a property of concern. The adhesion of these coatings to the substrate is strongly influenced by the residual stress generation during the coating deposition process. In the HVOF spray process, due to lower processing temperature and higher particle velocity as compared to plasma spraying, significant peening stresses are generated during the impact of semi molten particles on the substrate. The combination of these peening stresses together with quenching and cooling stresses that arise after deposition can be of significant importance. In this paper both a numerical finite element analysis (FEA) method, to calculate peening, quenching and cooling residual stresses, and experimental methods, as Modified Layer Removal Method (MLRM) and Neutron Diffraction analysis, are applied. The investigation is performed for thick Inconel 718 coatings on Inconel 718 substrates. Combined, these numerical and experimental techniques yield a deeper understanding of residual stress formation and a tool for process optimisation. The relationship between the stress state and deposit/substrate thickness ratio is given particular interest.

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.

Phase stability of the thermal barrier deposits made from yttria-partially-stabilized zirconia (Y-PSZ) is a requirement for extended service lifetime. The response of Y-PSZ plasma-sprayed deposits to annealing at 1000 °C, 1200 °C, and 1400 °C with times from 1 to 1000 hours has been evaluated using Rietveld analysis of neutron diffraction data. Results show that yttria concentration of the as-sprayed tetragonal zirconia component generally decreased with increasing annealing temperature and time. As the yttria content in the tetragonal phase approached a limiting concentration, the tetragonal phase transformed into monoclinic phase on cooling. An increase in monoclinic phase content was clearly observable after annealing 24 hours at 1400 °C and was nearly 35 % after 100 hours at 1400 °C. A similar trend was observed at 1200 °C for longer annealing times, with monoclinic phase formation beginning after 400 hours. At 1000 °C experimental times were not sufficient for monoclinic phase to form although a decrease in the yttria concentration in the tetragonal phase was observed. Keywords: neutron scattering, yttria-stabilized zirconia, phase composition, Rietveld analysis

Properties of thermally sprayed coatings, including residual stress, are controlled by various parameters of the spraying process. This study is focused on three thermal spraying techniques with significantly different particle temperatures and velocities. These are plasma spraying, twin wire arc spraying and high velocity oxy-fuel spraying. For each method, in-flight particle diagnostics was performed. Through-thickness residual stress profiles in Ni+5%A1 coatings on steel substrates were determined nondestructively by neutron diffraction. The stresses range from high tensile in the plasma sprayed coating to compressive in the HVOF one. Various stress generation mechanisms, including splat quenching, peening, and thermal mismatch, are discussed with respect to process parameters and material properties.

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.

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.

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.

Thermal spraying induces stresses, which strongly influence thermomechanical properties of the deposits. To study both generation and influence of these stresses, various techniques could be used separately and/or concurrently. "In-situ" curvature, neutron diffraction and incremental hole drilling methods are often presented as complementary techniques. In this study, partially stabilized zirconia coatings, performed onto steel substrates at various spraying temperatures, have allowed to compare these three different methods.

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 phase composition of plasma sprayed (8wt%) YSZ was studied using neutron and X-ray scattering. Comparison shows that neutron scattering is superior for analysis of the phase composition as well as for the analysis of the yttria content of the tetragonal phase. The presence of large amounts of the cubic phase are probably often neglected in standard XRD analysis due to scattering-related limitations and the inherent difficulty of the analysis. The importance of this fact needs to be addressed in future studies. The amount of monoclinic, tetragonal, and cubic phases was determined for as-sprayed deposits and for samples annealed at various temperatures. The as-sprayed deposit was composed of metastable phases, and the phase composition on annealing did not change significantly until 1400 °C for one hour. This indicates the relative stability of the phase composition. The influence of the spray distance is not clear, but the resultant phase composition may be related to the deposition temperature.

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.

Neutron diffraction is a promising tool for the investigation of residual stresses in thermally sprayed coatings. In principle, the neutron diffraction method has several distinct advantages over other methods. 1) It is possible to perform triaxial stress analysis throughout the thickness of both the coating and the substrate without material removal. 2) The stress can be determined in all phases of a multi-phase coating. 3) Repeated measurements can be performed on mechanically or thermally fatigued specimens. 4) Stress concentrations and shape/edge effects in actual parts can be located. In this paper, these unique capabilities will be reviewed first. In the second part of the paper it will be shown how the analysis of these coatings differs from experimental analysis of bulk materials. Finally, the analysis of the stress distribution in plasma sprayed NiCrAlY and ZrO 2 +Y 2 O 3 thermal barrier coatings in as-sprayed and annealed states will be presented and discussed.