Laser modified microstructures in ZrB2, ZrB2/SiC and ZrC

Microstructural evolution of spark plasma sintered ZrB₂, ZrB₂/20 vol.% SiC (ZS20) and ZrC ultra high temperature ceramics (UHTCs) during laser heating has been investigated. Laser heating at temperatures between 2000 and 3750 °C for up to 300 s, in air or vacuum, resulted in extensive bubble and crater formation on the surfaces of 10 mm diameter samples. However, even after exposure to ultra high temperatures, samples did not disintegrate. X-ray diffraction of exposed faces of ZrB₂ and ZS20 samples laser heated in air up to 2700 °C detected only crystalline zirconia. A wide range of morphologies, including nodules, needles, nanofibres and lamella, were observed. The surface of ZrC samples, laser heated in vacuum up to 3750 °C, were characterised by dendritic and eutectic morphologies. Other features associated with melting, such as solidification cracks and trapped porosity, were also observed. A complex array of mechanisms involving solid, liquid and vapour phases led to formation of these various morphologies including melting, oxidation, volatilisation and liquid flow     

Fabrication of graphene oxide reinforced plasma sprayed Al2O3 coatings

Graphene oxide (GO) reinforced Al₂O₃ ceramic coatings were prepared on the surface of medium carbon steel by plasma spraying. The microstructure of the raw materials and coatings were characterized and analyzed by XPS, XRD, Raman and SEM. The bonding strength of the coatings was studied using a scratch method. The wear resistance of the coatings was assessed by the sliding test. The results showed that, after adding GO, the porosity of the coating reduced by about 31%, the hardness increased by approximately 10%, the bonding strength improved by 250%, and the wear rate reduced by 81% (Load: 30 N) and 84% (Load: 60 N), respectively.     

The electromagnetic absorbing properties of plasma-sprayed TiC/Al2O3 coatings under oblique incident microwave irradiation

High performance absorbing coatings attract great interest because of the urgent demand for radar stealth technology. However, most reported absorbing coatings focused on the incident microwave were perpendicular to the surface of the coatings. Here, a kind of absorber of TiC/Al₂O₃ was prepared by plasma spraying method and the influence of TiC content and oblique incident microwave irradiation on the absorbing properties of TiC/Al₂O₃ were reported. The absorbing performance firstly increased and then decreased with increasing the TiC content due to the impedance matching and attenuation constant cannot match well at the same time. Meanwhile, compared with TE polarization, TM polarization of the plasma-sprayed TiC/Al₂O₃ coatings was more sensitive to the incident angle. This study demonstrates the feasibility of plasma-sprayed TiC/Al₂O₃ absorbing coatings for electromagnetic applications.     

Thermophysical and radiative properties of pressureless sintered SiC and ZrB2-SiC laminates

The evaluation of thermal and radiative properties of materials to be used as a hot part of thermal protection systems is a key issue for the design process of the HTC and UHTC components. Ceramic laminates with composition 100?vol%SiC and 80?vol%ZrB₂-20?vol%SiC were prepared by the tape casting technique and pressureless sintered. Thermal properties such as the thermal expansion coefficient, specific heat, thermal diffusivity and conductivity were measured; in addition the total emissivity was evaluated. A comparison of the thermal behavior of these two kinds of laminates is made. Moreover their possible integration in a unique structure is discussed.     

Fabrication and characterization of Yb2Si2O7-based composites as novel abradable sealing coatings

Ceramic matrix composites (CMCs) have gradually replaced superalloys for use in hot sections of aero-engines to meet the requirements for increasingly high engine temperatures. However, the abradable sealing coatings (ASCs) commonly applied to superalloys are not suitable for CMCs owing to factors such as the difference in the coefficient of thermal expansion, therefore it is necessary to develop a new system suitable for CMCs. Yb₂Si₂O₇ exhibits good high-temperature phase stability and relatively low hardness and may be a suitable material for ASCs. In the present study, Yb₂Si₂O₇-based composite coatings with different hexagonal boron nitride (hBN) contents (0, 5, 10, and 15 wt%) were deposited by air plasma spray (APS), and the microstructure, mechanical properties, and abradability of the coatings were characterized. The results showed that the system of Yb₂Si₂O₇ combined with hBN exhibits lower hardness, lower friction coefficient, higher wear rate, and smaller IDR value than the pure Yb₂Si₂O₇ coating and is appropriate for use in ASCs. However, excessive hBN caused severe wear of the coatings. The relevant wear mechanisms of the coatings were analysed, and this study may provide guidelines for the development of ASCs suitable for CMCs.     

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.     

Phase and microstructure evolution in plasma sprayed Yb2Si2O7 coatings

Yb₂Si₂O₇ coatings were deposited on Si/SiC substrates by atmospheric plasma spray (APS). The different power and plasma chemistries used in this work produced mainly amorphous crack-free coatings with compositions shifted to lower SiO₂ content with higher power and H₂ flow. Differences in microstructure and thermomechanical properties (crystallization behavior, thermal expansion coefficient and thermal conductivity) of as-deposited and thermally treated coatings were directly related to the evolution from amorphous to crystalline phases. A Yb₂SiO₅ metastable phase was identified after thermal treatments at temperatures ～ 1000 °C that transformed to its stable isomorph at 1220 °C. This transformation, followed by the growth of the crystal cell volume, promoted the coating expansion and the “healing” of microcracks present in the amorphous as-sprayed coating.     

Ablation behavior of C/SiC with YSZ and ZrB2 coatings under high-energy laser irradiation

Carbon fiber-reinforced silicon carbide (C/SiC) composites are important candidates for laser protection materials. In this study, ablation mechanism of C/SiC coated with ZrO₂/Mo and ZrB₂–SiC/ZrO₂/Mo under laser irradiation was studied. ZrB₂–SiC multiphase ceramic and ZrO₂ ceramic were successfully coated on C/SiC composite by atmospheric plasma spraying technology with Mo as transition layer. Phase evolution and morphology of composite were investigated by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Moreover, ablation behavior of the composite was investigated by laser confocal microscopy. Results showed that ablation mechanism of C/SiC composite was controlled by phase transformation, thermal reaction, and thermal diffusion, with solid–liquid transition of ZrB₂ and ZrO₂ being dominant factor. Endothermic reaction and good thermal diffusivity of coatings were also important factors affecting ablation performance. Reflectivity effect of ZrO₂ coating was limited under high-energy laser irradiation. Compared with ZrO₂/Mo single-phase-monolayer coating, designed ZrB₂–SiC/ZrO₂/Mo coating showed better ablation performance, and breakdown time of C/SiC increased from 10 to 40 s. The depletion of liquid phase in molten pool was identified as an important factor responsible for rapid failure of C/SiC. The coating failed when the entire liquid phase was consumed within molten pool, followed by rapid damage of C/SiC substrate. Results of this study can provide theoretical guidance and research ideas for design and application of laser protective materials.     

Effect of microstructure and mechanical properties on wear behavior of plasma-sprayed Cr2O3-YSZ-SiC coatings

In this study, the microstructure and mechanical properties of the atmospheric plasma-sprayed Cr₂O₃ (C), Cr₂O₃-20YSZ (CZ), and Cr₂O₃-20YSZ-10SiC (CZS) coatings were evaluated and also compared with each other, so as to explain the coatings wear behavior. Microstructural evaluations included X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) equipped with energy dispersive X-ray spectroscopy (EDX) and porosity measurements. Mechanical tests including bonding strength, fracture toughness, and micro-hardness tests were used to advance our understanding of the correlation between the coatings properties and their wear behavior. The sliding wear test was conducted using a ball-on-disk configuration against an alumina counterpart at room temperature. Addition of multimodal YSZ and subsequent SiC reinforcements to the Cr₂O₃ matrix resulted in an increase in the fracture toughness and Vickers micro-hardness, respectively. It was found that the composite coatings had comparable coefficients of friction with pure Cr₂O₃ coatings. When compared with the C coating, the CZ and CZS composite coatings with higher fracture toughness exhibited superior wear resistance. Observation of the wear tracks of the coatings indicated that the lower wear rates of the CZ and CZS coatings were due to the higher plastic deformation of the detached materials. In fact, improvement in the wear resistance of the composite coatings was attributed to a phase transformation toughening mechanism associated with tetragonal zirconia which created more ductile tribofilms during the wear test participated in filling the pores of coatings.     

Spontaneous infiltrations of compound systems of Y2O3, Sm2O3, RE2O3, Al2O3 and AIN in SiC ceramics

Silicon carbide ceramics (SiC) are used in different applications in the engineering area due to the excellent properties, mainly in high temperatures. They are usually obtained by liquid-phase sintering enabling to form volatile products and, consequently, defects. The present work aims at studying the obtention of SiC ceramics by spontaneous infiltration using a eutectic composition of the Al₂O₃/Y₂O₃, AlN/Y₂O₃, Al₂O₃/Sm₂O₃, AlN/Sm₂O₃, Al₂O₃/RE₂O₃ and AlN/RE₂O₃ systems. RE₂O₃ is the concentrate of the rare-earth oxide obtained from Xenotime ore. Infiltration tests were carried out in argon atmosphere, graphite crucibles, in several temperatures near the melting point of each system, varying from 2.5 to 60 min. It was observed that Al₂O₃/Y₂O_3, Al₂O₃/Sm₂O₃, AlN/Sm₂O₃ and Al₂O₃/RE₂O₃ systems do not infiltrate appropriately and the AlN/Y₂O₃ and AlN/RE₂O₃ systems infiltrated spontaneously more than 20 mm; however, the first one presented a higher degree of infiltration, approximately 97%.     

High temperature oxidation resistance of Y2O3 modified ZrB2-SiC coating for carbon/carbon composites

To protect carbon/carbon (C/C) composites from oxidation at high temperature, Y₂O₃ modified ZrB₂-SiC coating was fabricated on C/C composites by atmospheric plasma spraying. The microstructure and chemical composition of the coatings were characterized by SEM, EDS, and XRD. Experiment results showed that the coating with 10 wt% Y₂O₃ presented a relatively compact surface without evident holes and cracks. No peeling off occurred on the interface between the coating and substrate. The ZSY10 coating underwent oxidation at 1450 °C for 10 h with a mass loss of 5.77%, while that of ZS coating was as high as 16.79%. The existence of Y₂O₃ played an important role in inhibiting the phase transition of ZrO₂, thus avoiding the cracks caused by the volume expansion of the coating. Meanwhile, Y₂SiO₅ and ZrSiO₄ had a similar coefficient of thermal expansion (CTE), which could relieve the thermal stress inside the coating. The ceramic phases Y₂SiO₅, Y₂Si₂O₇ and ZrSiO₄ with high thermal stability and low oxygen permeability reduced the volatilization of SiO₂.     

摩擦喷射电沉积制备Ni-Al2O3纳米复合镀层

采用摩擦喷射电沉积工艺制备了N i-A l2O3纳米复合镀层。研究了电压、镀液中纳米颗粒含量、镀液喷射速度、镀笔相对运动速度等工艺参数对镀层沉积速度以及镀层中纳米颗粒含量的影响。结果表明,电压对镀层沉积速度影响较大,电压、镀液中纳米颗粒含量对复合含量的影响较大。扫描电镜及能谱测试显示,该纳米复合镀层表面较为平整、致密,纳米颗粒在镀层中呈均匀弥散分布,含量在2%~5%。     

Determination of Retained B2O3 Content in ZrB2‐30 vol% SiC Oxide Scales

The composition of the borosilicate glass layer formed during oxidation of ZrB₂‐30 vol% SiC was determined to elucidate the extent of B₂O₃ retention in the oxide during high‐temperature oxidation. Oxidation was conducted in stagnant air at 1300°C, 1400°C, and 1500°C for times between 100 and 221 min. Specimens were characterized using mass change and scanning electron microscopy. After oxidation, the borosilicate glass layer was dissolved from the specimens sequentially with deionized H₂O and HF acid, to analyze the glass composition using inductively coupled plasma optical emission spectrometry. It was found that the average B₂O₃ content in the glass scale ranged from 23 to 47 mol%. Retained B₂O₃ content in the bulk of the glass decreased with increasing temperature, confirming increased volatility with temperature. Boron depth profiles were also obtained in the near surface region using X‐ray photoelectron spectroscopy and energy dispersive spectroscopy. The measured B concentrations were used to estimate the B₂O₃ concentration profile and B diffusion coefficients in the borosilicate glass. Implications for the ZrB₂‐SiC oxidation process are discussed.     

Fabrication and post heat treatment of 0.5Pb (Mg1/3Nb2/3)O3-0.5Pb(Zr0.48Ti0.52)O3 coatings by supersonic plasma spray

Pb(Mg_1/3Nb_2/3)O₃-Pb(Z_r0.48Ti_0.52)O₃ coatings were obtained by supersonic plasma spray. With subsequent heat treatment, compact structure and typical tetragonal phase were obtained, and therefore dielectric performance (ε_r ≈ 915 at ambient temperature) have been significantly improved. The reason for successfully promote the properties is attributed the elimination of defects, amorphous and pyrochlore phase. Detail analyses were conducted on the variation of defects (pores and micro-cracks) and phase (amorphous, pyrochlore) of coatings after treated at elevated temperature. With the analyses, the existence of pyrochlore phase and ZrO₂ are attributed to the incongruent melting behavior. Inhibition of grain growth is attributed to the accumulation of ZrO₂ in the grain boundary. The results also suggest the subsequent change from pseudocubic to tetragonal at elevated temperature.     

Oxidation behaviors and mechanisms of Yb2O3-doped silicon coatings fabricated by vacuum plasma spray

Environmental barrier coatings (EBCs) have been widely studied for the protection of ceramic matrix composites (CMCs). The phase transition of silica thermal growth oxide (TGO) has been proved to be an important factor for the durability of EBCs. Yb₂O₃ could react with SiO₂ TGO and form silicate which may improve the stability of TGO and prolong the service life of EBCs. In the present work, Si coatings doped with different contents of Yb₂O₃ were fabricated by vacuum plasma spray. The oxidation behaviors of the composite coatings were evaluated at 1350 °C and compared with the pure Si coating. The evolution of phase composition and microstructure of mixed thermal growth oxide (mTGO) was characterized in detail. The results showed that the newly formed oxidation product, namely Yb₂Si₂O₇, could reduce the vertical cracks in mTGO layer and the mTGO/coating interface cracks, leading to a better binding performance of the mTGO layer. The oxidation mechanisms of the Yb₂O₃-doped Si coatings were analyzed based on microstructure and phase composition observations.     

Effect of B4C content and annealing on complex permittivity and microwave-absorption properties of B4C/Al2O3 coatings

The B₄C/Al₂O₃ coatings were fabricated by air plasma spraying technology, and their complex permittivity and microwave absorption properties in the X-band were investigated before and after annealing (500 °C/2 h). Both the real and imaginary parts of the complex permittivity of the coatings decreased after annealing, which can be attributed to the weakening of polarization relaxation intensity and the reduction of electrical conductivity caused by the escape of carbon atoms. In addition, the density of B₄C/Al₂O₃ coatings decreased from 3.01 to 2.16 g/cm³ with increasing B₄C content. The B₄C/Al₂O₃ coatings exhibit a minimum reflection loss (RL) value of ?39.58 dB and the effective absorption bandwidth (RL＜?10 dB, EAB) covers 1.9 GHz at a thickness of 1.6 mm. After annealing, the above coatings still had an EAB of 1 GHz. Therefore, the B₄C/Al₂O₃ coatings can be considered as a promising microwave-absorption candidate with good high-temperature microwave-absorbing performance and low density.     

Effect of sintering temperature on electrical properties of SiC/ZrB2 ceramics

SiC/20?wt% ZrB₂ composite ceramics were fabricated via pressureless solid phase sintering in argon atmosphere at different temperature. The effect of sintering temperature on microstructure, electrical properties and mechanical properties of SiC/ZrB₂ ceramics was investigated. Electrical resistivity exhibits twice significant decreases with increasing sintering temperature. The first decrease from 1900?°C to 2000?°C is attributed to the obvious decrease of continuous pore channels in as-sintered materials. The second decrease from 2100?°C to 2200?°C results from the improvement of carbon crystallization and the disappearance of amorphous layers enveloping ZrB₂ grains. Additionally, the increase of sintered density with increasing temperature caused greatly advance of flexural strength, elastic modulus and Vickers hardness. But excessive temperature is detrimental to flexural strength because of SiC grain growth.     

Fabrication and electromagnetic interference shielding effectiveness of Ti3Si(Al)C2 modified Al2O3/SiC composites

A dense alumina fiber reinforced silicon carbide matrix composites (Al₂O₃/SiC) modified with Ti₃Si(Al)C₂ were prepared by a joint process of chemical vapor infiltration, slurry infiltration and reactive melt infiltration. The conductive Ti₃Si(Al)C₂ phase introduced into the matrix modified the microstructure of Al₂O₃/SiC. The refined microstructure was composed of conductive phase, semiconductive phase and insulating phase, which led to admirable electromagnetic shielding properties. Electromagnetic interference shielding effectiveness (EMI SE) of Al₂O₃/SiC and Ti₃Si(Al)C₂ modified Al₂O₃/SiC were investigated over the frequency range of 8.2–12.4 GHz. The EMI SE of Al₂O₃/SiC-Ti₃Si(Al)C₂ exhibited a significant increase from 27.6 to 42.1 dB compared with that of Al₂O₃/SiC. The reflection and absorption shielding effectiveness increased simultaneously with the increase of the electrical conductivity.     

Ablation resistance and mechanism of ZrC-SiC-Yb2O3 ternary composite coatings fabricated by vacuum plasma spray

In this work, ZrC-SiC-Yb₂O₃ ternary composite coatings with different contents of Yb₂O₃ (0, 5, 15 and 30 wt.%) were fabricated by vacuum plasma spray and the anti-ablation property above 2000 °C was evaluated. The results showed that the microstructures of the oxide scales were changed with different Yb₂O₃ contents and then greatly modified the ablation resistant property of the composite coatings. The composite coating with 15 wt.% Yb₂O₃ exhibited the best ablation resistance. The disappearance of SiC-depleted layer and formation of ZrC_xO_y were observed. The mechanism of Yb₂O₃ on the oxidation products and ablation behaviors of ZrC-SiC system was analyzed.     

过渡金属改性的Pt／n-Al2O3在肉桂醛加氢反应中的催化性能

用NaBH4作还原剂,制备了中性氧化铝（n-Al2O3）负载的Pt-M（M=Fe,Co,Ni,Cu,Mn,Sn）双金属催化剂。考察了过渡金属及反应条件对Pt-M／n·Al2O3催化肉桂醛加氢制肉桂醇的影响。结果表明,Fe改性的Pt／n-Al2O3对催化肉桂醛加氢制肉桂醇具有较好的催化性能,当Pt-Fe／n—Al2O3（中性）催化剂中Pt、Fe的含量均为0．3％时,在70℃,2MPa氢气条件下反应1．5h,肉桂醛的转化率为100％,肉桂醇选择性高达84．8％。