Microstructural evolution and micromechanical properties of thermally sprayed hydroxyapatite coating

ABSTRACT

The effects of preheating and annealing processes on the micromechanical features of thermally sprayed hydroxyapatite (HA) coatings were investigated. The results indicated that subsequent heat treatment at 700°C for 60?min promotes the development of a crystalline HA coating. The EDS line scan showed that the oxygen content was homogeneous along the thickness direction from the coating surface to the titanium–HA interface, whereas the calcium and phosphorus concentration gradually decreased at 7?μm from the interface. From the roughness profiles, the coatings on preheated substrates gave lower roughness compared to the coatings at room temperature. According to the nanoindentation results, the sample preheated at 300°C after annealing at 700°C exhibited an elastic modulus of 108.1?±?6?GPa and hardness of 5.97?±?0.3?GPa, which were almost 3% lower and 171% higher than the bare substrate, respectively.     

Present status and future prospects of plasma sprayed multilayered thermal barrier coating systems

Thermal barrier coatings (TBCs) play a pivotal role in protecting the hot structures of modern turbine engines in aerospace as well as utility applications. To meet the increasing efficiency of gas turbine technology, worldwide research is focused on designing new architecture of TBCs. These TBCs are mainly fabricated by atmospheric plasma spraying (APS) as it is more economical over the electron beam physical vapor deposition (EB-PVD) technology. Notably, bi-layered, multi-layered and functionally graded TBC structures are recognized as favorable designs to obtain adequate coating performance and durability. In this regard, an attempt has been made in this article to highlight the structure, characteristics, limitations and future prospects of bi-layered, multi-layered and functionally graded TBC systems fabricated using plasma spraying and its allied techniques like suspension plasma spray (SPS), solution precursor plasma spray (SPPS) and plasma spray –physical vapor deposition (PS-PVD).     

Microstructural evolution and mechanical properties of atmospheric plasma sprayed Y2O3 coating with state of in-flight particle

Y₂O₃ coating on Al₂O₃ substrate was prepared by atmospheric plasma spray (APS). Computational fluid dynamics (CFD) was carried out to predict the state of in-flight Y₂O₃ particles at different powder feeding rates. Microstructure and mechanical properties were found to be affected by the spray distance and powder feeding rate. In this study, the hardness was calculated using a field emission-scanning electron microscope (FE-SEM) because the indentation in the coating is too small to measure using a hardness test machine. The formation of pores causes a decrease in the mechanical property, and the pore length of over 10 μm substantially decreases the hardness. Meanwhile, the solidification behavior is affected by the maximum temperature of the in-flight particles. Based on computational fluid dynamics (CFD) analysis, the maximum temperature of the in-flight particles was found to decrease with increase of the powder feeding rate at the same spray distance. At the powder feeding rate of 60 g/min, a lower adhesion strength was confirmed than that at feeding rate of 30 g/min because splats were insufficiently spread due to the lower maximum temperature of the in-flight particles. The roughness and height of the coating surface were evaluated by confocal microscopy and atomic force microscopy(AFM) analyses. The roughness is the resultant of accumulated splats and the accumulation mechanism of splats is affected by the state of the in-flight particles. Furthermore, there were nano-scale differences of height on the splat surface, on which the nucleation looks like ‘rugged bark’ during solidification of splats when the in-flight particles impact the substrate.     

Role of Lamellae Morphology on the Microstructural Development and Mechanical Properties of Small-Particle Plasma-Sprayed Alumina

The influence of spray parameters on the microstructure and flexural strength of plasma-sprayed alumina was investigated. Coatings were applied using a small-particle plasma spray (SPPS) method, which is a recently patented process that allows submicrometer-sized powders to be sprayed. Using identical starting powders, coatings that were produced using two distinctly different spray conditions exhibited significant differences in both microstructure and strength. Scanning electron microscopy investigations of single lamellae (or splats) revealed that, for one spray condition, melted alumina particles will splash when they contact the substrate. The morphology of the splats that comprised the subsequent layers of the coating also were highly fragmented and thinner than lamellae formed under "nonsplashing" spray conditions. The surface roughness was strongly dependent on the morphology of the lamellae; increased roughness was noted for fragmented splats. Thick coatings that were comprised of splashed splats developed a unique microstructural feature that was responsible for the observed increase in roughness. These microstructural differences greatly influenced the flexure strength, which varied from 75 ± 21 MPa for the nonsplashing spray condition to 17 ± 2.4 MPa for the "splashing" condition.     

Fabrication and properties of CNT/Ni/Y/ZrB2 nanocomposites reinforced in situ

Carbon nanotubes (CNTs) were synthesized in situ by chemical vapor deposition of methane over nano‐ZrB₂ matrix using Ni/Y catalysts. Well‐grown CNTs with tangled and long bodies and mainly composed of well‐crystallized graphite were obtained when the Ni content reaches 10 wt%. The CNT/ZrB₂ nanocomposites obtained by spark plasma sintering at 1400°C exhibited full density and optimal mechanical properties. The flexural strength and fracture toughness of the nanocomposites were 1184 ± 52 MPa and 10.8 ± 0.3 MPa·m^1/2, respectively. Results indicated that the dispersion of CNTs in situ can improve composite performance, rendering the mechanical properties of the CNT/ZrB₂ nanocomposites synthesized in situ considerably superior to those of monolithic ZrB₂ nanoceramics and CNT/ZrB₂ nanocomposites synthesized using the traditional method. The toughening mechanisms included crack deflection, crack bridging, CNT debonding, pull‐out, and fracture.     

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.     

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.     

高温球阀喷涂Al2O3-TiO2和WC-Co涂层的耐磨粒磨损性能

采用激光等离子喷涂技术在已失效的高温球阀基体材料上制备Al2O3-TiO2与WC-Co金属陶瓷涂层,在摩擦磨损试验机上对涂层的耐磨粒磨损性能进行研究,利用扫描电镜、光学显微镜对涂层的显微组织结构、磨损表面及其相组进行分析,并采用维氏显微硬度计、WE-50型液压拉伸验机和箱式电热炉对涂层的显微硬度、结合强度及抗热震性进行测试.结果表明,Al2O3-TiO2金属陶瓷涂层的综合性能最好,可以用于失效高温球阀的再制造.     

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.     

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.     

Temperature-dependent fracture strength of whisker-reinforced ceramic composites: Modeling and factor analysis

In this study, a temperature-dependent fracture strength model for whisker-reinforced ceramic composites was developed. This model considers the strength degradation of both whisker and ceramic matrix at elevated temperatures, as well as the evolution of residual thermal stress with temperature. It was verified by comparison with the available flexural strengths of five types of whisker-reinforced ceramic composites at different temperatures, and good agreement between the model predictions and the experimental data is obtained. Moreover, based on the established model, we systematically analyzed the effects of six influencing factors, including the volume fraction and the aspect ratio of whisker, the Young's modulus of matrix and whisker, the thermal expansion coefficient difference and the stress-free temperature, on the temperature-dependent flexural strengths of whisker-reinforced ceramic composites. Some new insights which could help optimize and improve the temperature-dependent fracture strength of whisker-reinforced ceramic composites are obtained.     

Laser thermal gradient testing of air plasma sprayed multilayered,multi-material thermal barrier coatings

Air plasma sprayed (APS) thermal barrier coatings (TBCs) are a widely used technology in the gas turbine industry to thermally insulate and protect underlying metallic superalloy components. These TBCs are designed to have intrinsically low thermal conductivity while also being structurally compliant to withstand cyclic thermal excursions in a turbine environment. This study examines yttria-stabilized zirconia (YSZ) TBCs of varying architecture: porous and dense vertically cracked (DVC), which were deposited onto bond-coated superalloys and tested in a novel CO₂ laser rig. Additionally, multilayered TBCs: a two-layered YSZ (dense + porous) and a multi-material YSZ/GZO TBC were evaluated using the same laser rig. Cyclic exposure under simulative thermal gradients was carried out using the laser rig to evaluate the microstructural change of these different TBCs over time. During the test, real-time calculations of the normalized thermal conductivity of the TBCs were also evaluated to elucidate information about the nature of the microstructural change in relation to the starting microstructure and composition. It was determined that porous TBCs undergo steady increases in conductivity, whereas DVC and YSZ/GZO systems experience an initial increase followed by a monotonic decrease in conductivity. Microstructural studies confirmed the difference in coating evolution due to the cycling.     

Effect of BN nanoparticle content in SiC matrix on microstructure and mechanical properties of SiC/SiC composites

BN-nanoparticle-containing SiC-matrix-based composites comprising SiC fibers and lacking a fiber/matrix interface (SiC/BN + SiC composites) were fabricated by spark plasma sintering (SPS) at 1800°C for 10 min under 50 MPa in Ar. The content of added BN nanoparticles was varied from 0 to 50 vol.%. The mechanical properties of the SiC/BN + SiC composites were investigated thoroughly. The SiC/BN + SiC composites with a BN nanoparticle content of 50 vol.%, which had a bulk density of 2.73 g/cm³ and an open porosity of 5.8%, exhibited quasiductile fracture behavior, as indicated by a short nonlinear region and significantly shorter fiber pullouts owing to the relatively high modulus. The composites also exhibited high strength as well as bending, proportional limit stress, and ultimate tensile strength values of 496 ± 13, 251 ± 30, and 301 MPa ± 56 MPa, respectively, under ambient conditions. The SiC fibers with contents of BN nanoparticles above 30 vol.% were not severely damaged during SPS and adhered to the matrix to form a relatively weak fiber/matrix interface.     

Preparation and properties of an oxide fiber‐reinforced silica matrix composite

Oxide (Nextel? 440) fiber‐reinforced silica composites, with the density and porosity of 1.97 g/cm³ and 21.8%, were prepared through sol‐gel. Their average flexure strength, elastic modulus, shear strength, and fracture toughness at room temperature were 119.7 MPa, 25.6 GPa, 10.8 MPa, and 4.0 MPa·m^1/2, respectively. The composites showed typical toughened fracture behavior, and distinct pullout fibers were observed at the fracture surface. Their mechanical properties were performant up to 1000°C, with the maximum flexural strength of 132.2 MPa at 900°C. Moreover, the composites showed good thermal stability, even after thermal aging and thermal shock at elevated temperatures.     

Laser surface modification of plasma sprayed CYSZ thermal barrier coatings

In this study, Inconel 738 LC superalloy coupons were first sprayed with a NiCoCrAlY bond coat and then with a ceria and yttria stabilized zirconia (CYSZ) top coat by air plasma spraying (APS). After that, the plasma sprayed CYSZ thermal barrier coatings (TBCs) were treated using a Nd:YAG pulsed laser. The effect of laser glazing on the microstructure of the coatings was investigated. The microstructures and surface topographies of both as-sprayed and laser glazed samples were investigated using field emission scanning electron microscope (FESEM) and atomic force microscope (AFM). The phases of the coatings were analyzed with X-ray diffractometry (XRD). The microstructural analysis results revealed that laser surface glazing of ceramic top coat reduced the surface roughness considerably, eliminated the surface porosities and produced a network of continuous cracks perpendicular to the surface. XRD patterns also showed that both as-sprayed and laser glazed top coats consisted of nonequibrium tetragonal (T′) phase.     

Temperature‐dependent tensile strength model for 2D woven fiber reinforced ceramic matrix composites

This paper presents a temperature‐dependent model for predicting the tensile strength of 2D woven fiber reinforced ceramic matrix composites. The model takes into account the combined effects of temperature, temperature‐dependent residual thermal stress, temperature‐dependent matrix strength, and fibers strength on the tensile strength of composites. To verify the model, the tensile strengths of 2D woven fiber reinforced ceramic matrix composites available are predicted at different temperatures. The model predictions agree well with the experimental data. This work could provide a practical technical means for predicting the temperature‐dependent tensile strength of 2D woven fiber reinforced ceramic matrix composites and uncovering the dominated mechanisms leading to the change of tensile strength and their evolution with temperature.     

Damage evolution in SiC/SiC unidirectional composites by X-ray tomography

Melt infiltrated SiC/SiC ceramic matrix composite unidirectional (UD) composite specimens were imaged under load using X-ray microtomography techniques in order to visualize the evolution of damage accumulation and to quantify damage mechanisms within the composite such as matrix cracking and fiber breaking. The data obtained from these in situ tensile tests were used in comparison with current models and literature results. Three-dimensional (3D) tomography images were used to measure the location and spacing of matrix cracking that occurred at increasing stress increments during testing within two UD composite specimens. The number of broken fibers and the location of each fiber break gap that occurred within the volume of both specimens were also quantified. The 3D locations of fiber breaks were correlated with the location of each matrix crack within the volume of the specimen and it was found that at the stress scanned directly before failure, most of the fiber breaks occur within 100 microns of a matrix crack.     

Preparation of plasma sprayed nanostructured GdPO4 thermal barrier coating and its hot corrosion behavior in molten salts

Nanostructured GdPO₄ coatings, designed as the outer layer of double-ceramic-layer thermal barrier coatings (DCL-TBCs), were produced by air plasma spraying (APS). The coatings have close chemical composition to that of the agglomerated particles used for thermal spray. Nanozones with porous structure are embedded in the coating microstructure, having a percentage of ~30%. Hot corrosion tests of the coatings were carried out in V₂O₅ and Na₂SO₄+V₂O₅ salts at 900 °C for 4 h. Results indicate that dense reaction layers, consisting of GdVO₄ and Gd₄(P₂O₇)₃, form on the coating surfaces, which could suppress further penetration of the molten salts. In the V₂O₅ molten salt, the reaction layer is thicker and less molten salt trace could be found beneath the layer.     

Thermoset IM-LSI-based C/C-SiC: Influence of flow direction and weld lines on microstructure and mechanical properties

The production of ceramic matrix composites (CMC) based on C/C-SiC is still very cost-intensive and therefore only economical for a few applications. The fabrication of the preforms involves many costs that need to be reduced. In this work, the shaping of the CFRP-preforms is realized by thermoset injection molding, which enables large-scale production. The polymeric matrix used is a multi-component matrix consisting of novolak resin, curing agent and lubricant. Six millimeter chopped carbon fiber with a proportion of 50 wt.% were used as a reinforcement. These ingredients are processed by an industrial equipment for compounding and injection molding in order to manufacture a CFRP demonstrator representing a brake disc. Test specimens are cut out of the demonstrator in different directions in order to investigate influences of flow direction and weld lines on microstructural and mechanical properties. Afterward, the CFRP samples were converted to C/C-SiC composites by the liquid silicon infiltration process. The article addresses the flow behavior of the compound during the injection molding and the building of the weld lines in the demonstrator. In addition, results of the directional dependence of the microstructural and mechanical properties within the fabricated disc in the different production steps are presented.     

Formation of Ti3SiC2 interphase coating on SiCf/SiC composite by electrophoretic deposition

To improve the oxidation resistance of SiC composites at high temperature, the feasibility of using Ti₃SiC₂ coated via electrophoretic deposition (EPD) as a SiC fiber reinforced SiC composite interphase material was studied. Through fiber pullout, Ti₃SiC₂, due to its lamellar structure, has the possibility of improving the fracture toughness of SiC_f/SiC composites. In this study, Ti₃SiC₂ coating was produced by EPD on SiC fiber; using Ti₃SiC₂‐coated SiC fabric, SiC_f/SiC composite was fabricated by hot pressing. Platelet Ti₃SiC₂ powder pulverized into nanoparticles through high‐energy wet ball milling was uniformly coated on the SiC fiber in a direction in which the basal plane of the particles was parallel to the fiber. In a 3‐point bending test of the SiC_f/SiC composite using Ti₃SiC₂‐coated SiC fabric, the SiC_f/SiC composite exhibited brittle fracture behavior, but an abrupt slope change in the strength‐displacement curve was observed during loading due to the Ti₃SiC₂ interphase. On the fracture surface, delamination between each layer of SiC fabric was observed.