Thermal stability and mechanical properties of HVOF/PVD duplex ceramic coatings produced by HVOF and cathodic vacuum arc

Duplex ceramic coatings, consisting of an inner NiCr-Cr₃C₂-based coating and an outmost AlCrN film, were produced on the steel substrate in succession by velocity oxygen-fuel spraying (HVOF) and cathodic vacuum arc methods, and then isochronally annealed at annealing temperatures below 900 °C for 2 h. The thermal stability and mechanical properties of the annealed samples were systematically studied by means of X-ray diffraction, Optical microscope and transmission electron microscope, in association with mechanical property measurements. The results show that the microstructure, phase evolution and mechanical properties of duplex ceramic coatings are significantly dependent on the annealing temperature. Metastable fcc-AlCrN solid solution in AlCrN film first decomposes to rich-Al and rich-Cr domains by spinodal decomposition at 700 °C, leading to a notable increase in hardness due to its smaller grain size and high elastic strain field, and then to equiaxed hcp-AlN and Cr₂N by the nucleation and growth at 900 °C, leading to a notable decrease in hardness due to the recrystallization and the formation of hcp-AlN. Meanwhile, the both decarburization of Cr₃C₂ to Cr₇C₃ occurs at 800 °C, but becomes more intensive at 900 °C, leading to a notable loss in hardness. In addition, the dissolution of Cr₃C₂ produces high density of porosity, which also reduces the hardness. The hardness tests show the following ordering of load-bearing capacity for the duplex ceramic coatings: 700 °C>As-deposited >800 °C>900 °C. Tribological property measurements demonstrate that the wear resistance of the tested duplex ceramic coatings obeys the following ordering: 700 °C>As-deposited >800 °C>900 °C. The improved wear resistance is due to high surface hardness, load-bearing capacity and thermal stability. In addition, the wear mechanisms are shown.     

Comparative study of the corrosion resistance of thermally sprayed ceramic coatings and their bulk ceramic counterparts

A comparative study of the corrosion properties of thermally sprayed ceramic coatings (Al₂O₃, Al₂O₃–TiO₂ with different ratios, mullite, and ZrSiO₄) and their sintered bulk ceramic counterparts was performed. The coatings were deposited on corrosion-resistant steel substrates using atmospheric plasma spraying (APS) and high velocity oxy-fuel (HVOF) spraying processes. The corrosion properties were investigated in 1 N solutions of NaOH and H₂SO₄ at 85 °C, respectively. The coating microstructures and phase compositions, as well as the corrosive environment were shown to have a strong effect on the corrosion resistance of the coatings. Al₂O₃–coatings were more sensitive to these factors than Al₂O₃–TiO₂ coatings were.The corrosion resistance of the bulk ceramics was superior to that of the thermally sprayed coatings. This is mainly because the coatings exhibited specific microstructure and contained amorphous and/or metastable phases not appearing in the bulk ceramics.     

Effects of the chemistry of coating and substrate on the steam oxidation kinetics of environmental barrier coatings for ceramic matrix composites

Environmental barrier coatings (EBCs) are an enabler for SiC/SiC ceramic matrix composites (CMCs) in gas turbines by protecting CMCs from environmental degradation. A critical EBC failure mode is the EBC spallation due to a build-up of elastic strains caused by the formation of SiO₂ scale, known as TGO (thermally grown oxide). H₂O, a byproduct of combustion reactions, accelerates the TGO-induced EBC failure by increasing TGO growth rates by orders of magnitude. NASA’s approach to improve the EBC life, therefore, is to reduce TGO growth rates. NASA discovered that modifying the TGO chemistry by modifying the EBC chemistry of Gen 2 EBC (Si / Yb₂Si₂O₇) reduces the TGO thickness by up to ～80 %. A study was undertaken to understand the oxidation mechanism of modified Gen 2 EBCs as well as to investigate the effect of EBC and CMC chemistry on TGO growth rates. This study confirmed the previously proposed TGO-controlled oxidation mechanism of modified Gen 2 EBCs and determined the correlations between the EBC and CMC chemistry, TGO chemistry, and TGO growth rates.     

Thermal stability and oxidation resistance of C/Al2O3 composites fabricated from a sol with high solid content

To improve fracture toughness of monolithic Al₂O₃ ceramics, three-dimensional carbon fiber preform was used as reinforcement, and the C/Al₂O₃ composites without interfacial coating were fabricated through vacuum impregnation-drying-heat treatment route with an Al₂O₃ sol as starting material. Characteristics of the Al₂O₃ sol with high solid content were firstly analyzed. Then thermal stability and oxidation resistance of the C/Al₂O₃ composites were investigated. It is found that the Al₂O₃ sol is an appropriate raw material for the fabrication of C/Al₂O₃ composites. The C/Al₂O₃ composites with a total porosity of 15.5% show a flexural strength of 208.5 MPa and a fracture toughness of 8.1 MPa m^1/2. Strength loss is observed after the composites were annealed at 1400 °C and 1600 °C under inert atmosphere. Oxidation resistance of the C/Al₂O₃ composites is unsatisfactory because of the existence of open pores and microcracks. When Al₂O₃ matrix was modified with SiO₂, the oxidation resistance is remarkably improved due to the viscous flow effect of SiO₂.     

Ultra-high temperature oxidation resistance of a novel (Mo,Hf, W,Ti)Si2 ceramic coating with Nb interlayer on Ta substrate

In order to solve the challenge of recyclability of tantalum substrates in high temperature oxidation environments, a novel MoSi₂-WSi₂-HfSi₂-TiSi₂ composite ceramic coating containing an Nb interlayer was prepared on the surface of tantalum substrate by a three-step method. The mix ceramic silicide coating exhibited superior performance and effective protection for 10.2 h at 1800 °C, possibly due to the formation of an outer SiO₂-HfO₂-HfSiO₄ composite oxide film with low oxygen permeability, moderate viscosity and thermal expansion coefficient, as well as good self-healing ability. Furthermore, the coating successfully passed 537 thermal cycles from room temperature to 1800 °C. The presence of Nb interlayer significantly mitigated the thermal mismatch between the ceramic coating and the tantalum substrate, and the bidirectional diffusion of Nb element during the high temperature oxidation and thermal shock process further reduced the tendency of the coating to crack.     

Preparation and high temperature oxidation of SiC compositionally graded graphite coated with HfO2

SiC compositionally graded (SCG) graphite was coated with sol-gel-derived HfO₂ films and oxidized at 1500 °C in air. SCGed graphite was produced by reaction of graphite with molten Si at 1450 °C for 10 h. The sol-gel HfO₂ precursor solution was prepared by dissolving HfCl₄ in ethanol and refluxing with diethanol-amine and HNO₃, and was coated on SCGed graphite by dipping. The HfO₂-coated SCGed graphite was produced by decomposition of the precursor under conditions determined from the results of TG, DTA, and MS analysis. Oxidation of HfO₂-coated SCGed graphite was performed at 1500 °C in air, revealing a small weight loss (0.6 mg cm⁻²) after 15 h. It was found that HfO₂-coated SCGed graphite exhibits extremely high oxidation resistance, which may be due to the formation of HfSiO₄ acting to heal pores or cracks.     

高温熔烧法制备金属基陶瓷涂层的研究

以玻璃熔块、氧化铬粉、粘土粉和硅酸锆微粉为原料制成的涂料,用滚涂法将其均匀涂覆在不锈钢管上,经高温(1000~1050℃保温20min)熔烧制备出了耐磨、抗高温氧化的陶瓷涂层。对陶瓷涂层的耐磨性、抗高温氧化性、抗热震性等性能进行了测试,并对影响涂层性能的因素进行了研究。结果表明:引入具有较大热膨胀系数的玻璃熔块料有利于提高涂层结合性;加涂层的试样均能明显改善基体的耐磨性和抗高温氧化性。涂层的耐磨性随硅酸锆微粉加入量的增加而提高,加入量为15%时耐磨性和抗热震性最好,其热震循环(1000℃空冷)可达22次。     

Microstructural,mechanical and thermal shock properties of triple-layer TBCs with different thicknesses of bond coat and ceramic top coat deposited onto polyimide matrix composite

In this study, a triple-layer thermal barrier coating (TBC) of Cu-6Sn/NiCrAlY/YSZ was deposited onto a carbon-fiber reinforced polyimide matrix composite. Effects of different thicknesses of YSZ ceramic top coat and NiCrAlY intermediate layer on microstructural, mechanical and thermal shock properties of the coated samples were examined. The results revealed that the TBC systems with up to 300 µm top coat thicknesses have clean and adhesive coating/substrate interfaces whereas cracks exist along coating/substrate interface of the TBC system with 400 µm thick YSZ. Tensile adhesion test (TAT) indicated that adhesion strength values of the coated samples are inversely proportional to the ceramic top coat thickness. Contrarily, thermal shock resistance of the coated samples enhanced with increase in thickness of the ceramic coating. Investigation of the TBCs with different thicknesses of NiCrAlY and 300 µm thick YSZ layers revealed that the TBC system with 100 µm thick NiCrAlY layer exhibited the best adhesion strength and thermal shock resistance. It was inferred that thermal mismatch stresses and oxidation of the bond coats were the main factors causing failure in the thermal shock test.     

TiO2涂层耐蚀性能和抗高温氧化性能

用溶胶－凝胶法在碳钢表面制备TiO2涂层。用正交设计法对水解反应温度、涂覆次数、热处理温度和时间4因素进行了优化，并考察了上述4因素对涂层在10％（体积分数）H2SO4介质中的耐蚀性能和650℃空气气氛中的抗高温氧化性能的影响。     

Steam oxidation of ytterbium disilicate environmental barrier coatings with and without a silicon bond coat

The current generation of multilayer Si/Yb₂Si₂O₇ environmental barrier coatings (EBCs) are temperature limited by the melting point of Si, 1414°C. To investigate higher temperature EBCs, the cyclic steam oxidation of EBCs comprised of a single layer of ytterbium disilicate (YbDS) was compared to multilayered Si/YbDS EBCs, both deposited on SiC substrates using atmospheric plasma spray. After 500 1-h cycles at 1300°C in 90 vol%H₂O-10 vol%air with a gas velocity of 1.5 cm/s, both multilayer Si/YbDS and single layer YbDS grew thinner silica scales than bare SiC, with the single layer YbDS forming the thinnest scale. Both coatings remained fully adherent and showed no signs of delamination. Silica scales formed on the single layer coating were significantly more homogeneous and possessed a markedly lower degree of cracking compared to the multilayered EBC. The single layer EBC also was exposed at 1425°C in steam with a gas velocity of 14 cm/s in an alumina reaction tube. The EBC reduced specimen mass loss compared to bare SiC but formed an extensive 2nd phase aluminosilicate reaction product. A similar reaction product was observed to form on some regions of the bare SiC specimen and appeared to partially inhibit silica volatilization. The 1425°C steam exposures were repeated with a SiC reaction tube and no 2nd phase reaction product was observed to form on the single layer EBC or bare SiC.     

Analysis of crack initiation and propagation in Thermal Barrier Coatings using SEM-Based geometrical model with extended finite element method

Thermal Barrier Coatings (TBC) are widely used to protect the metallic components that operate at harsh conditions of elevated temperatures and oxidizing environments. Thermally grown oxide (TGO) causes cracks formation in the top coat (TC) that may lead to spallation failure of TBC. This work investigates effect of pores and TGO thickness on crack initiation and propagation due to thermal mismatch between TBC layers. Image processing is used to convert an SEM image, including pores, into a finite element (FE) model. An FE model using XFEM implemented in ABAQUS was developed to investigate crack initiation and propagation for various TGO thicknesses considering the effect of plastic deformation of BC, TGO and substrate. Results show that presence of pores changes the critical sites for crack initiation from the TC/TGO interface to be around the pores within the TC. Crack initiation temperatures and crack lengths were found to be affected with both TGO thickness and pores.     

Mechanical and high temperature oxidation behavior of HfB2-ZrB2-SiC-B4C-CNT composites joined with and without Ni interlayer

Difficulties associated with the manufacturing of diboride based large and complex shapes mandate them to be joined for extreme applications. In the present work, spark plasma sintering is utilized to join HfB₂-ZrB₂-SiC-B₄C-CNT (HZSBC) based composites with Ni-interlayer at 1100 °C and without interlayer at 1800 °C. Microstructural analysis has elicited the formation of Ni diffused reaction zone (150–200 μm), and unaffected HZSBC composite for HZSBC-Ni-HZSBC joined composite (at 1100 °C), which gets merged into a homogeneous microstructure (without any distinguishable interface) in the HZSBC-HZSBC joint (without Ni-interlayer). An overall reduction of 18% and 14% is elicited in hardness and elastic modulus, respectively, in the HZSBC-Ni-HZSBC joint, whereas in HZSBC-HZSBC joined composite, uniform hardness and elastic modulus of ～22 GPa and ~398 GPa, respectively, is observed. Further, the bending and shear strength of the joined composites was obtained to be ～209 MPa and ～41 MPa, respectively, for HZSBC-Ni-HZSBC, which increased to ~342 MPa and ～81 MPa, respectively, for HZSBC-HZSBC. In conjunction, though superior high-temperature (1500 °C) oxidation protection is witnessed in HZSBC-HZSBC joint, with a thinner oxide layer, both display SiO₂-rich protective glassy layer, making these composites potential candidates for use in atmospheric re-entry conditions.     

A study of the oxidation behavior of CrN and CrZrN ceramic thin films prepared in a magnetron sputtering system

CrN and CrZrN ceramic thin films were produced by a planar type reactive sputtering system on glass and stainless steel substrates. We investigated oxidation resistance of CrN and CrZrN ceramic thin films with different Zr contents. The structure of the films at different thermal-annealing temperatures was investigated by X-ray diffraction (XRD), atomic force microscopy (AFM) and scanning electron microscopy (SEM). The mechanical properties of the films at different thermal-annealing temperatures were measured by nano-indentation. The results of this study showed that the addition of few amount of Zr (0.4 at%), can improve thermal stability of CrZrN ceramic thin film and increase the oxidation temperature of the film from 600 °C to 800 °C. The relatively good oxidation resistance (800 °C) and high hardness of the film with the lowest Zr content, indicates that this film is a good candidate for high temperature applications.     

Preparation of high performance MgO ceramic filter and its interaction with molten steel: Effect of porous MgO powder

In this study, two kinds of MgO ceramic filters were prepared by using porous magnesia powder and fused magnesia powder as raw material, respectively. The microstructures, mechanical properties and purification efficiency on the molten steel of two MgO ceramic filters were investigated by mercury porosimetry measurement, SEM, EDS and immersion test with molten steel, etc. The results demonstrate that compared with the filter FM prepared from the fused magnesia powder, the rheological property of the slurry of the filter PM was improved via the finer and uniformly distributed nano-sized Mg(OH)₂ particles generated by the hydration of the porous magnesia powder, which not only optimized the macropore structure but also promoted the growth of the sintering neck between the microparticles of the skeleton. Therefore, the MgO filter skeleton with a microporous structure was obtained, which elevated the strength and thermal shock resistance of the filter PM. According to the immersion tests with the molten steel, both filters significantly reduced the number of inclusions with size < 5 µm² in the molten steel as well as their total oxygen contents, and the filter PM had better purification efficiency than the filter FM. The reason for the better purification efficiency of the filter PM was related to its smaller micro-sized pores, larger surface roughness, and certain high-temperature liquid phase in their skeletons. In general, the porous magnesia powder resulted in higher compressive strength, better thermal shock resistance and superior purification efficiency on the molten steel of the filter compared with the fused magnesia powder.     

The effect of high temperature on the residual mechanical performance of concrete made with recycled ceramic coarse aggregates

This paper presents an experimental study on the residual mechanical properties of concrete with recycled ceramic coarse aggregate (RCCA) after exposure to elevated temperatures. Four concrete mixes were produced: a control concrete and three concrete mixes with replacement ratios of 20, 50 and 100% of natural aggregate (NA) by RCCA. The specimens were subjected to temperatures of 200, 400 and 600°C, for a period of 60 min. After cooling down to room temperature, the following concrete properties were evaluated: (i) compressive strength; (ii) splitting tensile strength; (iii) modulus of elasticity; (iv) ultrasonic pulse velocity (UPV); and (v) water absorption by immersion. At ambient temperature, as expected, the replacement of NA by RCCA resulted in a performance reduction of concrete. After exposure to elevated temperature, in general, the results obtained indicated an improvement of the residual relative mechanical properties of the mixes with RCCA, particularly after exposure to 400 and 600°C. However, exposure to the highest temperature (600°C) tended to cause spalling in concrete mixes containing RCCA. Significant linear correlations were observed between the residual compressive strength of all concrete mixes and both the UPV and the water absorption by immersion. Copyright © 2014 John Wiley & Sons, Ltd.     

Study on the Thermal Stability and Stabilization Mechanism of a Novel Thermal Stabilizer for Rigid Poly (Vinyl Chloride)

A novel thermal stabilizer for rigid poly (vinyl chloride) has been examined. Its high stabilizing efficiency is detected by the extent of discoloration and the mass loss rate of the degraded samples when compared with some of reference stabilizers. A higher stabilizing efficiency is produced as the novel thermal stabilizer is mixed with different co-stabilizers. The study results for thermo oxidative stability of the degraded samples with novel thermal stabilizer have shown that the novel thermal stabilizer can prevent or delay the thermal oxidative degradation of PVC. A probable stabilization mechanism for the novel thermal stabilizer has been proposed.     

Self-propagating high temperature synthesis (SHS) of porous Si3N4-based ceramics with considerable dimensions and study on mechanical properties and oxidation behavior

The aim of present work is to fabricate porous Si₃N₄ ceramics with considerable dimensions and homogeneous microstructure by self-propagating high temperature synthesis (SHS) using Si, Si₃N₄ diluent and Y₂O₃ as raw materials. The results indicate that Si₃N₄ diluent with coarse particle sizes and appropriate β-phase content is beneficial to obtain porous Si₃N₄ ceramics with homogeneous microstructure and excellent mechanical property by controlling the shrinkage inside the sample. The produced Si₃N₄ ceramics possessed excellent flexural strength of 168 MPa～259 MPa, and high Weibull modulus of 11.0～17.2. Additionally, BN and SiC are added as second phase to modify the properties of Si₃N₄-based ceramics. Optimum flexural strength of 170 MPa and 137 MPa were obtained with 10 wt.% addition of BN and SiC respectively. After oxidation at 1100 °C～1300 °C, second phase-doped Si₃N₄ ceramics also presented higher residual strength than pure Si₃N₄ ceramics.     

High-temperature oxidation behavior of monolithic Zr3[Al(Si)]4C6 and its composite incorporating 30vol% ZrB2-SiC: Providing a basis for broadening the service temperature

To provide a basis for the high-temperature oxidation of ultra-high temperature ceramics (UHTCs), the oxidation behavior of Zr₃[Al(Si)]₄C₆ and a novel Zr₃[Al(Si)]₄C₆-ZrB₂-SiC composite at 1500 °C were investigated for the first time. From the calculation results, the oxidation kinetics of the two specimens follow the oxidation dynamic parabolic law. Zr₃[Al(Si)]₄C₆ exhibited a thinner oxide scale and lower oxidation rate than those of the composite under the same conditions. The oxide scale of Zr₃[Al(Si)]₄C₆ exhibited a two-layer structure, while that of the composite exhibited a three-layer structure. Owing to the volatilization of B₂O₃ and the active oxidation of SiC, a porous oxide layer formed in the oxide scale of the composite, resulting in the degradation of its oxidation performance. Furthermore, the cracks and defects in the oxide scale of the composite indicate that the reliability of the oxide scale was poor. The results support the service temperature of the obtained ceramics.     

A comparative study on the effect of carbon-based and ceramic additives on the properties of fiber reinforced polymer matrix composites for high temperature applications

Ablative composites have been in use for thermal protection of space vehicles for decades. Carbon-phenolic composites have proven to perform exceptionally well in these applications. However with development in aerospace industry their performance needs improvement. In this field, different carbon-based and ceramic additives have been introduced into ablative composite systems. This review article gives a comparative analysis of researches done in this field in the recent past. Density, ablative, thermal and mechanical properties of ablative composites with different ultra-high temperature ceramic particles i.e. ZrSi₂, Cenosphere, nano-SiO₂, BN etc. and carbon-based nanoparticles i.e. CNTs, nano-Diamonds, Graphene oxide etc. used as additives, have been compared and discussed. Emphasis is put on carbon-phenolic composite systems although some epoxy matrix systems have also been discussed for comparison.     

Modeling of a Tubular‐SOFC: The Effect of the Thermal Radiation of Fuel Components and CO Participating in the Electrochemical Process

A mathematical model based on first principles is developed to study the effect of heat and electrochemical phenomena on a tubul solid oxide fuel cell (SOFC). The model accounts fordiffusion, inherent impedance, transport (momentum, heat and mass transfer) processes, internal reforming/shifting reaction, electrochemical processes, and potential losses (activation, concentration, and ohmic losses). Thermal radiation of fuel gaseous components is considered in detail in this work in contrast to other reported work in the literature. The effect of thermal radiation on SOFC performance is shown by comparing with a model without this factor. Simulation results indicate that at higher inlet fuel flow pressures and also larger SOFC lengths the effect of thermal radiation on SOFC temperature becomes more significant. In this study, the H₂ and CO oxidation is also studied and the effect of CO oxidation on SOFC performance is reported. The results show that the model which accounts for the electrochemical reaction ofCO results in better SOFC performance than other reported models. This work also reveals that at low inlet fuel flow pressures the CO and H₂ electrochemical reactions are competitive and significantly dependent on the CO/H₂ ratio inside the triple phase boundary.