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.

Oxide compounds basically composed of calcium, magnesium, aluminum and silicon cations also known as CMAS, can be deposited on the surface of thermal barrier coatings (TBC) of gas turbine blades. Under certain operation conditions these compounds have been found to aggressively degrade the TBC, hence affecting the thermo-mechanical properties of the underlying component. Detailed investigation on the interaction of CMAS and the atmospheric plasma sprayed (APS) yttria-stabilized zirconia (YSZ) TBC was performed in a burner rig test facility under thermal gradient cycling conditions and at the same time CMAS deposition. This novel and unique test approach promises a coating screening and characterization test under service conditions. Variable exposure times at approximately 1250°C/1050°C surface/substrate temperatures were applied. The lifetime of the TBC was indicated by the number of thermal cycles until significant spallation occurred. X-ray spectroscopy and microstructural analyses were conducted on the cycled samples to determine the effect of thermo-chemical interactions. It was found that with extended heating period of 10 times the standard cycle, the number of sustainable load alternations heating/cooling was reduced. Interaction of CMAS and YSZ induces formation of glassy soda-silicate phase. Thermal cycling of thermo-physically mismatched TBC and glass melt causes crack formation and coating failure.

Plasma-sprayed ceramic coatings are often used as thermal barrier or abradable coatings in high-pressure stages of gas turbines. They are exposed to high thermo-mechanical loadings, due to the harsh operating conditions. Today, a material typically used in engines as thermal barrier coating material is yttria-stabilised zirconia (YSZ). This material has a low conductivity and a high thermal expansion coefficient, but a limited temperature capability of about 1200°C in long-term applications. For the use as abradable coatings, thicker coatings with a thickness above one millimetre are necessary. However with increasing coating thickness and limited cooling efficiency there is a risk of premature failure. As a result new ceramic materials have been developed. For the lifetime analysis they were tested by thermal gradient cycling tests. In the present work an APS ceramic double-layer topcoat composed of 7YSZ and a top layer of non-stoichiometric magnesia alumina spinel (Mg-Al-Spinel) was used. The layer was sprayed on disc-shaped IN738 superalloy substrates which were coated with a VPS bondcoat. Under specific thermal cycling conditions with temperatures above 1400°C, these samples showed a typical failure mechanism with exfoliation of thin coating lamellae, starting from the coating surface. This failure mechanism was analysed in detail, e.g. by scanning electron microscopy (SEM), X-ray diffraction, and chemical analysis. From these findings, a description of the failure mechanism was developed.

Fracture toughness and phase stability are crucial properties of thermal barrier coatings (TBC) during highly loaded thermomechanical operations in gas turbines. While several alternative TBC materials have exhibited excellent thermal resistance, their potential applicability has been limited due to poor endurance to cyclic stresses. The addition of TiO 2 to the non-transformable tetragonal t´-YSZ has been found to effectively enhance the fracture toughness and phase stability of YSZ at high temperature exposures. Thermal cycling tests in a burner rig were conducted on TBCs prepared from atmospheric plasma sprayed titania-doped YSZ to verify this phenomena. Exposure temperature was 1400°C at the surface and thermal gradient across the sample was provided by simultaneous back-cooling treatment. Cycling tests reveal that the slight increase in the tetragonality of the deposited coatings with increasing amount of dopant did not cause a significant effect to the lifetime of the TBCs. Moreover, increasing amount of Ti-substitution did not influence the fracture toughness of the bulk YSZ.

The manufacture of submicrometer-structured coatings by thermal spraying is subjected nowadays to increasing research efforts in order to obtain unique and often enhanced properties compared to conventional coatings. Injecting suspensions of submicron ceramic particles into the plasma jet or the flame enables to deposit finely-structured coatings. Such fine microstructures can be advantageous for applications in the field of thermal barrier coatings (TBCs) for gas turbines. Often, suspension plasma sprayed (SPS) TBCs show unique mechanical, thermal and optical properties compared to conventional atmospheric plasma sprayed (APS) TBCs. They have thus the potential of providing increased TBC performances under severe thermo-mechanical loading. Experimental results show the capability of SPS to obtain yttria-stabilized zirconia (YSZ) coatings with high density of vertical segmentation cracks, yielding high strain tolerance and low Young’s modulus, while the porosity is still large compared to APS segmented coatings. Besides, sintering behavior of complete TBC systems under a thermal gradient exposure is of high importance. The evolution of the coating microstructure during thermal cycling test at very high temperature (1400°C) in our burner rigs as well as under isothermal annealing and its effects on the coating properties such as Young’s modulus were investigated.

The thin film low pressure plasma spray process (LPPS-TF) has been developed with the aim of efficient depositing uniform and thin coatings with large area coverage by plasma spraying. At high power input (~150 kW) and very low pressure (~100 Pa) the plasma jet properties change considerably and it is even possible to evaporate the powder feedstock material providing advanced microstructures of the deposits. This relatively new technique bridges the gap between conventional plasma spraying and physical vapor deposition. In addition, the resulting microstructures are unique and can hardly be obtained by other processes. In this paper, microstructures made by LPPS-TF are shown and the columnar layer growth by vapor deposition is demonstrated. In addition to the ceramic materials TiO 2 , Al 2 O 3 or MgAl 2 O 4 , the focus of the research was laid on partially yttria-stabilized zirconia. Variations of the microstructures are shown and discussed concerning potential coating applications.

The very low pressure plasma Spray (VLPPS) process has been developed with the aim of depositing uniform and thin coatings with large area coverage by plasma spraying. At typical pressures of 100-200 Pa, the characteristics of the plasma jet change compared to conventional low pressure plasma spraying processes (LPPS) operating at 5 – 20 kPa. The combination of plasma spraying at low pressures with enhanced electrical input power has led to the development of the LPPS-TF process (TF = thin film). At appropriate parameters it is possible to evaporate the powder feedstock material providing advanced microstructures of the deposits. This technique offers new possibilities for the manufacturing of thermal barrier coatings (TBCs). Besides the material composition, the microstructure is an important key to reduce thermal conductivity and to increase strain tolerance. In this regard, columnar microstructures deposited from the vapor phase show considerable advantages. Therefore, physical vapor deposition by electron beam evaporation (EB-PVD) is applied to achieve such columnar structured TBCs. However, the deposition rate is low and the line of sight nature of the process involves specific restrictions. In this paper, the deposition of thermal barrier coatings by the LPPS-TF process is shown. It is investigated how the evaporation of the feedstock powder could be improved and to what extend the deposition rates could be increased.

Processing of powder feedstock materials often influences the deposition behavior and ultimately, the properties of the atmospheric plasma spray (APS) deposited coatings. The necessity of materials design and the control of deposition parameters are therefore, of high importance. Feedstock from promising ceramic thermal barrier coating materials with Ba(Mg 1/3 Ta 2/3 )O 3 and La(Al 1/4 Mg 1/2 T 1/4 )O 3 perovskite structures (λ~ 2 W/m-K and α~11x10-6 /K at 1473 K) were prepared through solid state and conventional spray drying techniques. The powders were then deposited on metallic substrates by APS process. Monitoring of in-flight particle characteristics and splat formation as well as characterization of deposited coatings, were conducted. It was found that these types of perovskite materials tend to lose constituents during deposition by atmospheric plasma spraying. This paper reports on the challenges of powder feedstock design and the control of critical deposition parameters to prevent or minimize the non-stoichiometric deposition of decomposition-prone perovskite coatings by APS process.

Powder injection parameters like gas flow, injection angle and injector position strongly influence the particle beam and thus coating properties. The interaction of the injection conditions on particle properties based on DPV-2000 measurements using the single-cathode F4 torch is presented. Furthermore, the investigation of the plasma plume by emission computer tomography is described when operating the three-cathode TriplexPro torch. By this imaging technology, the three-dimensional shape of the radiating plasma jet is reproduced based on images achieved from three CCD cameras rotating around the plume axis It is shown how the formation of the plasma jet changes with plasma parameters and how this knowledge can be used to optimize particle injection.

This study investigates the influence of segmentation crack density on the strain tolerance of thermal barrier coatings produced by atmospheric plasma spraying. A Triplex II plasma gun is used to spray fused and crushed yttria-stabilized zirconia, forming thick deposits with high segmentation crack densities, low porosity, and low branching crack density, which is necessary for good interlamellar bonding. Thermal cycling and burner rig tests yield promising results in terms of lifetime and strain tolerance behavior and microstructural analysis shows that the segmentation crack network was stable during thermal shock testing. The main failure mechanism was delamination and horizontal cracking in the vicinity of the TBC-TGO (thermally grown oxide) interface.

In this investigation, two complex perovskite powders, Ba(MgTa)O and Ta(AlMgT)O, are deposited by atmospheric plasma spraying and evaluated for use as thermal barrier layers. Process parameters are optimized to provide sufficient melting without causing the formation of secondary phases. Deposited coatings are assessed based on composition, morphology, porosity, and thermal cycling lifetime. It is shown that the nature of the starting powders has a significant effect on the lifetime and performance of perovskite-based thermal barrier coatings.

Suspension plasma spraying (SPS) offers the manufacture of unique microstructures which are not possible with conventional powder feedstocks. Due to the considerably smaller size of the droplets and also the further fragmentation of these in the plasma jet, the attainable microstructural features like splat and pore sizes can be downsized to the nanometer range. Our present understanding of the SPS deposition process including injection, suspension plasma plume interaction, and deposition is outlined in this report. The conclusions drawn are based on microstructure analysis in combination with enthalpy probe and particle temperature and velocity and measurements. Measurements with a water-cooled stagnation probe provide valuable information on the interaction of the carrier fluid with the plasma plume. The examples presented include segmented thermal barrier coatings for turbine components, LSM cathode deposits for SOFCs, and TiO 2 layers for photovoltaic Gratzel cells.

Very low pressure plasma spraying (VLPPS) processes operate at a pressure of approximately 100 Pa, where the interaction of the plasma jet with the surrounding atmosphere is very weak and, as a result, plasma velocity is almost constant over a long distance from the nozzle exit. At these low pressures, the collision frequency is distinctly reduced and the mean free path is strongly increased. As a consequence, the specific enthalpy of the plasma is substantially higher, but at lower density. These particular plasma characteristics offer enhanced possibilities to spray thin and dense ceramics compared to conventional processes which operate in the pressure range between 5 and 20 kPa. This paper presents examples of gas-tight and electrically insulating layers with thicknesses less than 50 μm for solid oxide fuel cell applications. Plasma spraying of oxygen conducting membrane materials like perovskite is also discussed.

The potential of atmospheric plasma spraying (APS) technology has been investigated for the manufacture of anode, electrolyte and cathode of a solid oxide fuel cell. As substrates tape-casted or commercial available porous plates both made of a FeCr-alloy were used. The functional layers were applied by atmospheric plasma spraying, however, it turned out that screen printed LSCF cathodes performed better than thermally sprayed versions. Anode layers with high electrochemical activity could be produced by APS using separate injections of NiO and YSZ powders. The manufacturing of gas-tight electrolyte layers was a key-issue of the present development. With adequate processing conditions and advanced gun technology it was possible to produce highly dense ceramic coatings with a very low amount of micro-cracks and pores. These electrolytes gave high open cell voltages above 1 V corresponding to the low measured leakage rates (<10-3 mbar*l/s) of the rather thin (<50 µm) coatings. Additional layers have been applied to reduce the interdiffusion especially of species from the metallic substrates into the anode. These layers could significantly reduce degradation of the cells. SOFCs with a power density at 800°C well above 0.7 W/cm² could be produced by the developed technology.

Normally the conventional thermal spray processes as the atmospheric plasma spraying (APS) have to use easily flowable powders in a size range between 10 and 100 µm. In contrast the suspension plasma spraying (SPS) makes it possible to process nano sized particles directly. Due to the use of nano materials new microstructures and properties could be generated. One point is the possibility to influence the porosity level, its size range and micro crack densities in a wide band. Microstructure features like the porosity and cracks serve as scattering centres and lead to changes of optical properties. Furthermore the thermal conductivity is affected by the porosity level. In this work yttria partially stabilized zirconia coatings were generated by the SPS and APS process. The influence of the different microstructures on the thermal conductivity, the hemispherical reflectance and transmittance for wavelengths between 0.3 to 2.5 µm has been investigated. Due to the higher porosity and crack level of the SPS coatings the thermal conductivity and hemispherical transmittance was significant reduced.

In-flight particle temperature measurements during atmospheric plasma spraying (APS) of Tungsten, Molybdenum, and Yttria stabilized Zirconia by two-color pyrometry are analyzed statistically. The particle temperature distributions allow assessing the melting status of the particles. Particularly the melting temperature and the particle fractions being still molten or already solidifying can be identified. Furthermore, the relevant systematic and material dependant sources for measurement errors using two-color pyrometry are investigated. Their influence is estimated and corrected best possible. As far as there is reliable data available on the emissivity of the powder material there is good agreement between the corrected measured melting temperatures and reference data.

Advanced ceramic materials of perovskite structure have been developed for potential application in thermal barrier coating systems, in an effort to improve the properties of the pre-existing ones like yttria stabilized zirconia. Yb 2 O 3 and Gd 2 O 3 doped strontium zirconate (SrZrO 3 ) and barium magnesium tantalate (Ba(Mg 1/3 Ta 2/3 )O 3 ) of the ABO 3 and complex A(B’ 1/3 B” 2/3 )O 3 systems respectively, have been synthesized using ball milling prior to solid state sintering. Thermal and mechanical investigations show desirable properties for high temperature coating applications. On atmospheric plasma spraying, the newly developed TBCs reveal promising thermal cycle lifetime above 1300°C.

One major shortcoming of thermal barrier coatings applied to gas turbine components is the spallation of the ceramic coating under mechanical stress developing during thermal cycling environments. In order to study the evolution of failure and the expectancy of lifetime under realistic conditions cycling burner rig tests are a well established matter of choice. In the same way the techniques of acoustic emission (AE) testing and infrared (IR) thermography have been widely proofed to provide insight to microscopic crack formation and localization of hidden delaminations, respectively. Both techniques can be utilized to record the evolution of microscopic and macroscopic defects in advance to the apparent failure. Indirectly, this knowledge allows to verify and to improve lifetime models. The aim of this study is to expand the use of AE and IR testing as a rugged in-situ monitoring tools for combustion driven cycling rigs and to provide spatial resolved information on thermal load and failure evolution of the TBC in those tests. For a successful application to an experiment using a gas fired and air cooled burner rig some it is necessary to overcome some limitations which are mainly due to the high level of interfering signals under those experimental conditions.

Segmentation cracked coatings are promising candidates for thermal barrier coatings (TBC) because of their high strain tolerances. By atmospheric plasma spraying (APS), cylindrical stand-alone YSZ coatings with and without segmentation cracks were fabricated. The diameter of the tubes was 10 mm, and the thickness of the coatings approximately 1 mm. The segmentation crack densities were in the range up to 3.5 cracks/mm, while the porosity amounted for all coatings between 5% and 7%. Further details of the spraying process and the obtained microstructures will be given and discussed. The samples were tested in an uniaxial high temperature compression rig to measure the stress relaxation. The comparison of the stress relaxation measurements yielded a different performance of segmented and non-segmented coatings with advantages for the cracked ones. It was observed that the cracks increase the resistance to stress relaxation.

Thermal barrier coatings (TBCs) with different types of microstructures were produced with the atmospheric plasma-spraying (APS) process. The investigation includes a variation of the micro-crack density and of the porosity level. In addition, also segmented TBCs were produced. Finally, also PVD-TBC systems have added to the investigation. The different TBC systems were cycled in a natural gas/oxygen burner rig with a surface temperature of about 1250°C and a bond coat temperature of about 1100°C or below. The use of relatively low surface temperature guarantees a failure mode close to the bond coat promoted by the growth of the thermally grown oxide (TGO). After failure, metallographic inspection was made to determine the thickness of the TGO layer and the β-phase depleted zone. In addition, the crack path was analyzed and compared for the different microstructures.