Porosity analysis and oxidation behavior of plasma sprayed YSZ and YSZ/LaPO4 abradable thermal barrier coatings

In this research, the high temperature oxidation behavior, porosity, and microstructure of four abradable thermal barrier coatings (ATBCs) consisting of micro- and nanostructured YSZ, YSZ-10%LaPO₄, and YSZ-20%LaPO₄ coatings produced by atmospheric (APS) method were evaluated. Results show that the volume percentage of porosity in the coatings containing LaPO₄ was higher than the monolithic YSZ sample. It was probably due to less thermal conductivity of LaPO₄ phases. Furthermore, the results showed that the amount of the remaining porosity in the composite coatings was higher than the monolithic YSZ at 1000 °C for 120 h. After 120 h isothermal oxidation, the thickness of thermally growth oxide (TGO) layer in composite coatings was higher than that of YSZ coating due to higher porosity and sintering resistance of composite coatings. Finally, the isothermal oxidation resistance of conventional YSZ and nanostructured YSZ coating was investigated.     

Formation of vertical cracks in air plasma sprayed YSZ coatings using unpyrolyzed powder

Thick thermal barrier coatings (TTBCs) with vertical cracks deposited by air plasma spray (APS) and solution precursor plasma spray (SPPS) techniques have been widely investigated to achieve good thermal insulation along with reasonable service life. In this study, synthesized unpyrolyzed YSZ powder was air plasma sprayed in order to produce segmentation crack TTBCs. The microstructure and hardness of the deposits were then compared with those of the conventional TTBCs and dense vertically cracked (DVC)TTBCs. In this regard, spraying parameters were optimized to achieve deposits with the appropriate amount of unpyrolyzed particles in them to assist inducing vertical cracks in the deposited layers. The effect of the unpyrolyzed particles on microstructure, porosity, and microhardness of plasma sprayed coatings were also evaluated and compared. The new fabricated coating showed a bimodal structure combining non-molten sub-micron size particles and conventional splats along with segmentation cracks with higher amount of porosity and lower hardness compared to those of the DVC coatings. The results implied that, depositing unpyrolyzed powder by APS, as a new approach for achieving segmentation crack TTBCs, is very promising.     

Melting index characterization and thermal conductivity model of plasma sprayed YSZ coatings

The melting index of particle was measured to quantitatively characterize the spraying parameters of as-sprayed YSZ coatings. Moreover, new and reliable representation of melting index was achieved, using in-flight particle temperature and velocity. The prediction of microstructure features, such as total porosity and spheroidal porosity of as-sprayed coatings, could be available by the quantitative relationship between melting index and porosity. Based on the real microstructure characteristics, finite element models were generated to simulate heat transfer and calculate thermal conductivity of coatings. The large deviation between the experimental thermal conductivity and simulation results was attributed to the influence of microcracks, which was not shown in as-analyzed images due to resolution limit. Taking all the effects of microcracks and porosity into account comprehensively, the calculation model of thermal conductivity was established with the calculated error lower than 10%.     

Review of suspension and solution precursor plasma sprayed thermal barrier coatings

As one of the promising methods that can be employed to fabricate high-performance thermal barrier coatings (TBCs), suspension plasma spraying (SPS) or solution precursor plasma spraying (SPPS) has received significant attention in academic research. Enhanced performances have been shown in the SPS-/SPPS-coatings due to their special microstructures, such as uniformly distributed micro-pores, vertical cracks or columnar structures. Since there are more complexities than conventional plasma spraying methods, many works have been devoted to study the mechanism and properties of SPS-/SPPS-coatings during the past decades. In this work, the latest development of SPS or SPPS is reviewed in order to discuss some key issues in terms of preparation of suspension or solution precursor, injection mode of liquid phase, interaction between liquid and plasma jet, microstructure of as-sprayed coatings and corresponding deposition mechanism. Meanwhile, the potential application of SPS or SPPS in some new-type TBCs is introduced at the end of this paper.     

Design of high lifetime suspension plasma sprayed thermal barrier coatings

Thermal barrier coatings (TBCs) fabricated by suspension plasma spraying (SPS) have shown improved performance due to their low thermal conductivity and high durability along with relatively low production cost. Improvements in SPS TBCs that could further enhance their lifetime would lead to their widespread industrialisation. The objective of this study was to design a SPS TBC system with optimised topcoat microstructure and topcoat–bondcoat interface, combined with appropriate bondcoat microstructure and chemistry, which could exhibit high cyclic lifetime. Bondcoat deposition processes investigated in this study were high velocity air fuel (HVAF) spraying, high velocity oxy fuel spraying, vacuum plasma spraying, and diffusion process. Topcoat microstructure with high column density along with smooth topcoat–bondcoat interface and oxidation resistant bondcoat was shown as a favourable design for significant improvements in the lifetime of SPS TBCs. HVAF sprayed bondcoat treated by shot peening and grit blasting was shown to create this favourable design.     

Investigation of the crystallinity of suspension plasma sprayed hydroxyapatite coatings

Hydroxyapatite coatings were deposited on stainless steel substrates. The arc current was varied to study its effect on the coating crystallinity. The crystallinity was calculated according to the XRD patterns via Jade 6.0 software and the full width at half maximum (FWHM) of Raman peak at 962 cm⁻¹. The FE-SEM images showed that HA coatings had rod-like nanostructures and agglomerated into microspheres. The XRD patterns indicated that the as-sprayed coatings were composed of HA and some decomposition phases. Micro-Raman spectroscopies demonstrated that the main phase in the coatings was HA. The results showed that the crystallinity was increased from 68.68% to 76.84% while the FWHM varied from 9.74 to 6.38 cm⁻¹, when the arc current increased from 400 A to 600 A. The selected area electron diffraction (SEAD) patterns were used to analyze the crystallinity qualitatively, and the results agreed with the conclusions of XRD and FWHM of Raman peak.     

Sintering resistance of suspension plasma sprayed 7YSZ TBC under isothermal and cyclic oxidation

This study examines sintering resistance of a thermal barrier coating (TBC), composed of a 7YSZ suspension plasma sprayed (SPS) top coat (TC), an air plasma sprayed (APS) NiCoCrAl bond coat (BC), and an INCONEL 625 substrate, under isothermal and cyclic conditions with a peak temperature of 1080 °C for 400, 800, and 1300 h/cycles. Microstructure, phase composition and microstrain were examined using SEM and XRD. Mechanical properties of fracture toughness, hardness and elastic modulus were obtained using nano-indentation. Samples under cyclic conditions presented faster sintering rate than under isothermal condition due to larger compressive strain and frequent heating and cooling cycles. Faster degradation of mechanical properties due to sintering leads to shorter lifetime of SPS coating under cyclic conditions. Moreover, vertical cracks within SPS coatings reduces compressive stress leading to a greater lifetime as compared to APS coatings exposed to similar conditions.     

Microstructural,mechanical and tribological properties of suspension plasma sprayed YSZ/h-BN composite coating

Brittleness, relative high friction coefficient and wear rate limit the applications of ceramic coatings as wear-resistant layers. However, because embedding additives with ceramic matrix has demonstrated to be an effective way to improve coating performances, different contents and size of h-BN were added into an YSZ suspension. Afterwards, the YSZ/h-BN composite coatings were manufactured by suspension plasma spray and their tribological analysis indicated that: i) the reduction of the friction coefficient and wear rate can be achieved by incorporating h-BN into YSZ coating. ii) finer h-BN particle is more helpful to enhance the tribological properties of the coating. iii) the optimum content is dependent on h-BN particle sizes. iv) when the contents and the size of the h-BN inclusion increase, the probability distribution of the micro-hardness can become bi-modal. Three worn surface conditions were summarized and their wear mechanisms were discussed as well.     

Evolution of porosity in suspension thermal sprayed YSZ thermal barrier coatings through neutron scattering and image analysis techniques

Porosity is a key parameter on thermal barrier coatings, directly influencing thermal conductivity and strain tolerance. Suspension high velocity oxy-fuel (SHVOF) thermal spraying enables the use of sub-micron particles, increasing control over porosity and introducing nano-sized pores. Neutron scattering is capable of studying porosity with radii between 1 nm and 10 μm, thanks to the combination of small-angle and ultra-small-angle neutron scattering. Image analysis allows for the study of porosity with radii above ～100 nm. For the first time in SHVOF 8YSZ, pore size distribution, total porosity and pore morphology were studied to determine the effects of heat treatment. X-ray diffraction and micro-hardness measurements were performed to study the phase transformation, and its effects on the mechanical properties. The results show an abundant presence of nano-pores in the as-sprayed coatings, which are eliminated after heat treatment at 1100 °C; a transition from inter-splat lamellar to globular pores and the appearance of micro-cracks along with the accumulation of micro-strains associated with the phase transformation at 1200 °C.     

Taguchi optimization of YSZ/alumina/silica colloids for suspension plasma sprayed coating process

The stability of suspensions plays a key role in the water-based suspension plasma sprayed coating process. The effects of suspension parameters, such as the solid content and the type/content of dispersants on the suspension stability were studied in this work. In this regard, a Taguchi L9 array design of experiments was used to optimize submicron-sized YSZ/nano-sized alumina/silica additive suspensions with low viscosity, high steady-state turbidity, and inter-particle electrostatic charges. The optimal stable suspension with the viscosity of 4.2 cp, the zeta potential of 65 mV, and the Nephelometric Turbidity Units (NTU) of 3503 was used as the feedstock for suspension plasma spraying. Accordingly, a typical columnar coating morphology was obtained with the porosity of almost 19.3 vol%, which is a desirable feature for high-temperature applications. In conclusion, this study reflects the merit of the Taguchi design of experiments to optimize multicomponent thermal barrier coatings.     

Thermal stability and sintering behavior of plasma sprayed nanostructured 7YSZ, 15YSZ and 5.5SYSZ coatings at elevated temperatures

Nanostructured scandia, yttria doped zirconia (5.5SYSZ), 7 wt% yttria stabilized zirconia (7YSZ) and 15YSZ thermal barrier coatings (TBCs) were produced by plasma spraying on nickel-based superalloy substrates with NiCrAlY as the bond coat. The thermal stability and sintering behavior of the three as-sprayed TBCs at 1480 °C were investigated. The results indicated that the thermal stability of SYSZ and TBCs was longer than the 7YSZ TBCs due to higher amount of tetragonal phase. Furthermore, the results demonstrated that the nanostructured 7YSZ coating exhibits higher sintering resistance than 5.5SYSZ TBC.     

Unmelted particles in plasma sprayed coatings

A technique is described for investigation of unmelted particles in plasma spraying and for porosity investigation in coatings. A study of unmelted particles is made. The technique is based on large area section (LAS) images, superimposed to obtain a densely packed “column” of images as a 3-D map of a certain volume of the plasma sprayed coating. Optical micrographs of a polished cross section of the coating were used. The LAS technique combines two parameters—magnification and field size. Such a combination is normally beyond the range of optical microscopy. The method makes it necessary to polish the sample again and again and after each polishing step align precisely the new LAS with the previous one. The unmelted particles are considered to have been spheroidized in the plasma plume during plasma spraying, but to have cooled below the melting point before reaching the substrate. Such particles are embedded in the coating as previously solidified, i.e. with globular shape. The 3-D map makes it possible to observe their distribution inside the coating. These globular particles represent defects in the deposited coating. Moreover they have a tendency to behave isotropically under the influence of stress or other physical factors and in this way serve in the anisotropic structure of the coating as centers of secondary defects deteriorating the functional properties of the coatings.     

Architecture designs for extending thermal cycling lifetime of suspension plasma sprayed thermal barrier coatings

Suspension plasma spraying (SPS) as a relatively new spraying technology has great potential on depositing high performance thermal barrier coatings (TBCs). In some cases, however, columnar SPS TBCs show premature failure in thermal cycling test. To explain the reasons of such failure, a failure mechanism for columnar SPS TBCs was proposed in this work. The premature failure of TBCs might be related to the radial stresses in the vicinity of top coat/bond coat interface. These radial stresses were introduced by the thermal misfit and the roughness of bond coat. According to this mechanism, two architecture designs of SPS TBCs were applied to improve the thermal cycling lifetime. One was a double layered top coat design with a lamellar atmospheric plasma sprayed (APS) sub-layer and a columnar SPS top-layer. The other one was a low roughness bond coat design with a columnar SPS top coat deposited on a low roughness bond coat which was grinded before the spraying. With both designs, lifetimes of SPS TBCs were significantly extended. Especially, a lifetime even better than conventional APS TBCs was achieved with the double layered design.     

A comparative study on the synthesis and properties of suspension and solution precursor plasma sprayed hydroxyapatite coatings

In the present study, hydroxyapatite (HAp) coatings were deposited on Ti-6Al-4V alloy by solution precursor plasma spray (SPPS) and suspension plasma spray (SPS) processes and the properties of the coatings were compared. The feedstock powder for SPS method was prepared by coprecipitation technique and characterized for phase and morphology. The obtained HAp coatings were characterized by X-ray diffractometry, Raman spectroscopy and FT-IR spectroscopy. The biocompatibility of the coatings was evaluated using osteoblast like cells. Both the SPS and SPPS hydroxyapatite coatings exhibited similar crystallinity. Interestingly, the HAp-SPS coating showed marginally higher biocompatibility compared to HAp-SPPS and control samples. The wear and corrosion behavior of these coatings was also studied in Hanks' medium. The hydroxyapatite coating fabricated from SPS technique exhibited better corrosion and wear resistance compared to SPPS coating.     

Structure and properties of plasma sprayed BaTiO3 coatings

Plasma spraying enables to create layers with thickness in a millimeter range adhering on various substrates. This paper provides a study of electric and mechanical properties of BaTiO₃ coatings prepared by atmospheric plasma spraying. The spraying was carried out by a direct current gas-stabilized plasma gun. BaTiO₃ was fed into the plasma jet as a feedstock powder prepared by a reactive sintering of micrometer-sized powders of BaCO₃ and TiO₂. Microstructure and phase composition are reported and discussed in connection with electric and mechanical properties. The ability of the used techniques to detect precisely the phase transformation temperatures of BaTiO₃ plasma sprayed coatings is discussed as well. A depth-sensing indentation measurement was done between 290 and 520 K to provide local mechanical characterization. The elastic modulus has shown slightly higher values than that reported typically in papers focused on BaTiO₃ ferroelectric thin films. The average Vickers microhardness is tested to characterize the samples in larger scale. A wear resistance in a slurry environment is reported as well. Dielectric properties are reported for the temperature window of existence of the tetragonal ferroelectric phase. Relative permittivity and loss factor are studied at frequency from 50 Hz to 1 MHz and temperature from 260 to 400 K.     

Microstructural and thermal properties of plasma sprayed mullite coatings

Thick mullite (3Al₂O₃–2SiO₂) coatings were fabricated by atmospheric plasma spraying (APS) in a mixture of crystalline and amorphous phases, as confirmed by X-ray diffraction (XRD) analysis. The coatings were isothermally heat treated in order to study recrystallization mechanism of the glassy phase. The morphology and the microstructure of both mullite feedstock and coatings were investigated by using scansion electron microscopy (SEM). The porosity of as-sprayed coating was in the range between 2 and 3% and substantially remained unchanged after thermal treatment. The thermal expansion of as-sprayed and annealed coatings was measured during heating up to the temperature of crystallization and the corresponding high-temperature extent of shrinkage was calculated. The differential scanning calorimetry (DSC) curves at different heating rates showed a sharp exothermic peak between 1243 and 1253 K, suggesting a rapid recrystallization of the amorphous phase. Finally, the heat capacity of recrystallized mullite coating was measured by DSC experiments. It was approximately 1.02 × 10³ J/kg K at 373 K and increased with increasing test temperature.     

Visualisation of the local electrochemical activity of thermal sprayed anti-corrosion coatings using scanning electrochemical microscopy

Scanning electrochemical microscopy was used to study the electrochemical activity of anti-corrosion coatings formed from Inconel 625, a Ni-Cr-Mo alloy commonly used in engineering applications. The coatings were formed using a high velocity oxygen fuel thermal spraying technique. Upon spraying the alloy onto mild steel substrates, clear splat boundaries were formed at the interface between adjacent droplets as they cooled on the substrate surface. Scanning electrochemical microscopy in the feedback mode, employing ferrocenemethanol as redox mediator, was used to study the local electrochemical activity of samples of the wrought alloy, the sintered alloy and the thermal sprayed coating. The wrought and sintered materials showed responses typical of that expected for a purely insulating material. However, SECM approach curve data showed that the electrochemical activity of the thermal sprayed material was higher than that of the bulk alloy. Local variations in the coating's electrochemical activity were then visualised using SECM imaging, which appear to be related to the splat boundaries formed during the thermal spray process.     

Phase evolution in plasma sprayed Nb2O5 coatings

Nb₂O₅ polymorphism and defect chemistry depend on the temperature, pressure, atmosphere composition and the initial crystallography. Plasma spray of Nb₂O₅ is a pathway to form coatings with in-situ metastable and nonstoichiometric phases, however so far unexplored. This study aimed to understand the phase evolution of plasma sprayed Nb₂O₅ coatings, and its effect on their morphology and properties. Phase evolution from H-Nb₂O₅ in the feedstock, to T-Nb₂O₅, TT-Nb₂O₅, N-Nb₂O₅, H-Nb₂O₅, Nb₁₂O₂₉ and NbO₂ in the coatings depends on the plasma Ar/H₂ ratio and its related enthalpy. The microstructure shows a layered distribution of nonstoichiometric phases at the splat boundaries and splat cores composed of T-Nb₂O₅ or TT-Nb₂O₅. The presence and distribution of these phases are related to the thermomechanical and electrical properties. The mechanisms driving the formation of these coatings are based on the Nb₂O₅ incongruent vaporization which promote retention of nonstoichiometric phases and the rapid solidification of metastable phases.     

Processing and properties of plasma sprayed silicon nitride-glass composite coatings

Abstract

Abstract

Silicon nitride decomposes before it can melt, and so thermal spraying of pure silicon nitride powder is impracticable. To address this difficulty, feedstock powder for plasma spray deposition has been developed in which each particle is a composite of silicon nitride in a low temperature borosilicate glass matrix. The research showed that the silicon nitride did not decompose in the plasma because the low thermal conductivity of the glass matrix ensured a low heat transfer rate and the particle temperature remaining below the decomposition temperature. The coating density initially increased with plasma arc power because of increasing splat flow but then declined at high power levels owing to decomposition of the glass matrix. The silicon nitride dispersion substantially reduced the splat flow, particularly near the maximum packing fraction, but also had the beneficial effect of restricting crack propagation, resulting in an optimum content for wear resistance of 30?vol.-% silicon nitride.     

Preparation of crystalline ytterbium disilicate environmental barrier coatings using suspension plasma spray

In high-speed modern industries, high-temperature stability of materials is essential. A promising high-temperature material currently attracting attention is silicon carbide (SiC)-based ceramic matrix composites (CMC). However, a disadvantage of these materials is their reduced lifetime in an oxidizing atmosphere. To overcome this, environmental barrier coating can be employed. In this study, we aimed to fabricate an environmental barrier coating using suspension plasma spray with Yb₂Si₂O₇, which exhibits excellent oxidation resistance and a similar thermal expansion coefficient to SiC. To prepare the crystalline Yb₂Si₂O₇ coating layer, the gas concentration of the plasma spray was adjusted, and then the suspension manufacturing solvent was adjusted and sprayed. The prepared coating samples were analyzed by X-ray diffraction, scanning electron microscope, transmission electron microscopes, and energy dispersive X-ray spectroscopy to determine phase and microstructure changes. Highly crystalline ytterbium disilicate was observed at low plasma enthalpy with no hydrogen and 20% addition of water.