Preparation and ablation properties of ZrC-SiC coating for carbon/carbon composites by solid phase infiltration

A novel ZrC-SiC coating was prepared on carbon/carbon (C/C) composites surface by solid phase infiltration and the ablation properties of the ZrC-SiC coated C/C composites under oxyacetylene flame were studied. The results show that the coating prepared on the condition of optimum process parameters exhibits dense surface and outstanding anti-ablation ability. After ablation for 20 s, the mass ablation rates of the coated C/C composites can be lowered to 2.36 × 10⁻³ g/s, 37.1% reduction compared with uncoated C/C composites. The oxide layer composed of ZrO₂ and SiO₂ acts as oxygen diffusion barrier and the evaporation of ZrO₂ and SiO₂ absorbs a great amount of heat from the flame and reduces the erosive attack on the coating.     

Suppression of through-the-thickness cracks in SiC coating on C/C composites

Two concepts are proposed to minimize coating cracks on the surface of C/C composites. The first idea of a multi-layered coating is based on the phenomenon that there exists a critical coating thickness below which no coating cracks appear. This phenomenon is experimentally and theoretically confirmed for a SiC coating. Thus, by alternately laminating thin SiC and carbon layers, coating-cracking is expected to be suppressed for a thick and dense coating. The second concept is the use of a fiber-reinforced coating. By the fiber reinforcement, the toughness of a ceramic coating should be improved. In this paper, both concepts are shown to be promising to reduce through-the-thickness coating cracks. In addition, problems especially related to oxidation behavior are discussed in relation with the two-coating systems.     

The influence of ablation products on the ablation resistance of C/C-SiC composites and the growth mechanism of SiO2 nanowires

Ablation under oxyacetylene torch with heat flux of 4186.8(10%kW/m2 for 20 s was performed to evaluate the ablation resistance of C/C-SiC composites fabricated by chemical vapor infiltration（CVI） combined with liquid silicon infiltration（LSI） process.The results indicated that C/C-SiC composites present a better ablation resistance than C/C composites without doped SiC.The doped SiC and the ablation products SiO₂ derived from it play key roles in ablation process.Bulk quantities of SiO₂ nanowires with diameter of 80 nm-150 nm and length of tens microns were observed on the surface of specimens after ablation.The growth mechanism of the SiO₂ nanowires was interpreted with a developed vapor-liquid-solid（VLS） driven by the temperature gradient.     

Ablation properties of carbon/carbon composites with tungsten carbide

The ablation properties and morphologies of carbon/carbon (C/C) composites with tungsten carbide (WC) filaments were investigated by ablation test on an arc heater and scanning electron microscopy. And the results were compared with those without tungsten carbide (WC) filaments tested under the same conditions. It shows that there is a big difference between C/C composites with and without WC filaments on both macroscopic and microscopic ablation morphologies and the ablation rates of the former are higher than the latter. It is found that the ablation process of C/C composites with WC filaments includes oxidation of carbon fibers, carbon matrices and WC, melting of WC and WO₃, and denudation of WC, WO₃ and C/C composites. Oxidation and melting of WC leads to the formation of holes in z directional carbon fiber bundles, which increases the coarseness of the ablation surfaces of the composites, speeds up ablation and leads to the higher ablation rate. Moreover, it is further found that the molten WC and WO₃ cannot form a continuous film on the ablation surface to prevent further ablation of C/C composites.     

高速气流对C/SiC复合材料激光烧蚀行为影响的实验研究

为了明确高速气流对C/SiC复合材料激光烧蚀行为的影响机制,开展了不同环境下强激光对C/SiC复合材料的烧蚀对比实验研究。利用激光器与高速风洞联合实验平台,完成了静态以及Ma 1.8,Ma 3.0,Ma 6.0气流环境下2D与3DN C/SiC复合材料激光烧蚀实验。结果表明,与静态环境相比,高速气流对C/SiC复合材料的激光烧蚀行为产生了显著的影响,气流的冲刷使得烧蚀坑呈现出更宽、更深、更光滑的变化趋势。随着气流速度的增长,线烧蚀速率与质量烧蚀速率逐渐增大,主要原因为当地静压降低引起的升华速率增大,以及动压增大引起的剥蚀速率增大。此外,通过实验对比了不同构型对C/SiC激光烧蚀行为的影响。结果表明：2D C/SiC复合材料由于厚度方向更低的导热能力、更低的孔隙率等原因,其在不同环境条件下抗烧蚀能力均强于3DN C/SiC复合材料。     

Ablation behaviors of carbon/carbon composites with C-SiC-TaC multi-interlayers

Carbon/carbon composites with C-SiC-TaC multi-interlayers were prepared by isothermal chemical vapor infiltration. The ablation behaviors of the composites were tested with an oxyacetylene flame. The mass loss rate increases markedly in the initial 10 s, then reaches a steady state or decreases slightly in 10–40 s; while after 40 s, the mass loss rate increases remarkably. A similar trend is observed in the linear loss rate, except that it begins to increase only after 60 s. After ablation for 5 s, the composite surface consists in black carbon fibers and white ceramic oxides. After 20 s, three different regions with different ablation behaviors are observed: central, transition and border. After 100 s, the composites are severely ablated and the shape is completely destroyed. A cross-section of the composites after ablation for 20 s shows three distinct regions: a rugged oxide layer, a smooth oxide layer and the matrix. The tantalum compounds have not been able to protect efficiently the material from constant oxide evolution, possibly because of a too large pore volume fraction.     

Converting ultrasonic induction heating deposited monetite coating to Na-doped HA coating on H2O2-treated C/C composites by a two-step hydrothermal method

a monetite coating on H₂O₂-treated C/C composites was prepared by ultrasonic induction heating (UIH) technology. Subsequently, this coating was subjected to an ammonia hydrothermal treatment to form a undoped hydroxyapatite (U-HA) coating. Finally, the as-prepared U-HA coating was placed in a NaOH solution and hydrothermally treated to produce the other hydroxyapatite (Na-HA) coating. The structure, morphology and chemical composition of the two HA coatings were characterized by XRD, FTIR, SEM and EDS, the adhesiveness and local mechanical properties, e.g. nanohardness and Young's modulus of the two HA coatings to C/C composites was evaluated by a scratch test and nanoindentation technique respectively. The results showed that the two HA coatings had the alike morphology and crystallization. But, compared with the U-HA coating, the Na-HA coating was doped with Na ions, and gave a Ca/P ratio close to a stoichiometric hydroxyapatite, and thus showed a higher nano-indentation value, Young's modulus, and larger bonding strength. These results verified the strengthened effect of Na ion in hydroxyapatite coating on carbon/carbon (C/C) composities.     

A SiC whisker-toughened SiC-CrSi2 oxidation protective coating for carbon/carbon composites

A SiC whisker-toughened SiC-CrSi₂ oxidation protective coating was prepared on the surface of C/C composites by a two-step technique of slurry and pack cementation. The oxidation protective ability and thermal stress resistance of the coating exhibit the trend of increase first and decrease afterwards as the SiCw content increases from 0 to 20 wt.%. The compound effect of SiCw and CrSi₂ on the oxidation protective ability of SiC coating is better than their individual ones.     

Microstructure and anti-oxidation property of CrSi2-SiC coating for carbon/carbon composites

To protect carbon/carbon (C/C) composites from oxidation, a new type of oxidation protective coating has been produced by a two-step pack cementation technique. XRD and SEM analysis show, the coating obtained by the first step pack cementation was a porous β-SiC structure, and a new phase of CrSi₂ was generated in the porous SiC coating after heat-treatment according to the second step pack cementation process. Oxidation test shows that, the weight loss of the SiC coated C/C is up to 11.26% after 5 h oxidation in air at 1773 K, and the weight loss of the CrSi₂-SiC coated C/C composites is only 4.15% after oxidation in air at 1773 K for 34 h. The oxidation of C/C composites was primarily due to the reaction of C/C matrix and oxygen diffusing through the penetrable cracks in the coating.     

Tungsten and iridium multilayered structure by DGP as ablation-resistance coatings for graphite

Oxidation protection of carbon material under ultra-high temperature is a serious problem. In this paper, a newly designed multilayer coating of W/Ir was produced onto the graphite substrate by double glow plasma. As comparison, the Ir single-layer coating on the graphite was also prepared. The ablation property and thermal stability of the coatings were studied at 2000 °C in an oxyacetylene torch flame. Ablation tests showed that the coated graphite substrates were protected more effectively by W/Ir multilayer coating than Ir single-layer coating. Ir single-layer coating after ablation kept the integrality, although there was a poor adhesion of the Ir coating to the graphite substrate because of the thermal expansion mismatch and the non-wetting of the carbon by Ir coating. The mass loss rate of the W/Ir-coated specimen after ablation was about 1.62%. The interface of W/Ir multilayer coating and the graphite substrate exhibited good adherence no evidence of delamination after ablation. W/Ir multilayer coating could be useful for protecting graphite in high-temperature application for a short time.     

LiFePO4/C composites derived from precipitated FePO4 precursor: effects of mixing processes

Grinding, general incipient wetness and competitive incipient wetness were investigated on the preparation of LiFePO₄/C (LFP) composites from precipitated FePO₄ precursor. This article focuses on the fundamental details of mixing processes for LFP production, of which the literature is sparse. The structure features of LiFePO₄/C composites were analyzed by X-ray diffraction (XRD), while the morphologies were characterized by field emission scanning electron microscopy (FESEM). The electrochemical performances were studied by galvanostatic charge/discharge measurements. Both mixing processes and lithium sources are capable of affecting the electrochemical performances by altering the crystallinity, the quality of carbon coating, or even the impurity formation of LiFePO₄/C composites. Liquid alkalis caused the formation of impurities and mild decrease of crystallinity, whereas competitive cations did not produce impurities but significantly decreased the crystallinity of LiFePO₄/C composites.     

Electro-oxidation of ethylene glycol on PtSn/C and PtSnNi/C electrocatalysts

A PtSn/C electrocatalyst with a Pt–Sn molar ratio of 50:50 and A PtSnNi/C electrocatalyst with a Pt–Sn–Ni molar ratio of 50:40:10 were prepared by alcohol-reduction process using ethylene glycol as solvent and reducing agent. The electrocatalysts were characterized by energy dispersive X-ray, X-ray diffraction, and cyclic voltammetry. The electro-oxidation of ethylene glycol was studied by cyclic voltammetry and chronoamperometry using the thin porous coating technique. PtSnNi/C electrocatalyst showed a superior performance compared to PtSn/C electrocatalysts in the potential range of interest for a direct ethylene glycol fuel cell.     

C/C复合材料的光谱发射率研究

采用模压成型法制备了不同类型的C/C复合材料,测试了其法向光谱发射率的变化.结果表明,短切碳纤维增强的C/C复合材料,其法向光谱发射率在整个2 500～13 000 nm的测试波段内普遍要高于碳布增强复合材料样品.短切碳纤维结构的相对松散,单位体积内物质的粒子数相对较少,这增加了电磁波的穿透深度,从而使得样品的法向光谱发射率较高,热辐射特性较好.纤维预制体和C/C复合材料样品的法向光谱发射率测试对比可知,两种不同碳材料的微结构差异使得树脂碳的法向光谱发射率优于纤维碳.利用Raman光谱对不同碳物质进行物相分析表明,树脂碳以sp3和sp2杂化态碳原子的混合结构使其内部产生的局域振动模式较多,这也是样品法向光谱发射率较高,热辐射特性较好的原因.     

Influence of preparation technology on the microstructure and anti-oxidation property of SiC-Al2O3-mullite multi-coatings for carbon/carbon composites

Oxidation protective SiC-Al₂O₃-mullite multi-coatings for carbon/carbon (C/C) composites were prepared with a two-step pack cementation process. The influence of preparation temperature and SiO₂/Al₂O₃ ratio of the pack powder on the phase, microstructure and oxidation resistance of the multi-coatings were investigated. It showed that the multi-coatings that contained mullite could be produced at 1700-1800 °C. A denser coating surface was acquired with the decrease of SiO₂/Al₂O₃ ratio in the pack chemistries while a little damnification to the interface of the coating and C/C substrate. The as-prepared coating could effectively protect C/C composites from oxidation at 1600 °C for 81 h.     

Micro patterning of fused silica by laser ablation mediated by solid coating absorption

Precise patterning by laser ablation requires sufficient absorption. For weak absorbers like fused silica indirect methods using external absorbers have been developed. A novel approach using a solid SiO absorber coating is described. Irradiation by an ArF excimer laser (wavelength 193 nm) is leading to ablation of the coating and, at sufficiently high fluence, of the fused silica substrate. The remaining coating in the unexposed areas is removed afterwards by large area irradiation. The fluence threshold for substrate ablation using a 28 nm thick absorber layer is about 1.1 J/cm². Single pulse ablation rates of up to 800 nm and a surface roughness of R _a<5 nm are obtained. High resolution grating patterns with 400 nm period and a modulation depth of 80 nm are possible. The process can be described as controlled plasma mediated ablation.     

Evolution of zirconia coating layer on rutile TiO2 surface and the pigmentary property

Zirconia-coated rutile TiO₂ composites were prepared by the chemical liquid deposition method starting from rutile TiO₂ and ZrOCl₂. The amorphous zirconia coating layers were anchored at the TiO₂ surface via Zr-O-Ti bond. The formation of continuous and dense zirconia coating layers was dependent on the pH value of the reaction solution and the mole ratio of ZrOCl₂ to TiO₂. As compared to the naked rutile TiO₂, the water dispersibility, whiteness, brightness, and relative light scattering index of the zirconia-coated rutile TiO₂ composites were increased.     

Texture structure and ablation behavior of TaC coating on carbon/carbon composites

TaC coatings with hybrid, (2 0 0) and (2 2 0) texture structure were prepared on carbon/carbon (C/C) composites by isothermal chemical vapor deposition with TaCl₅-Ar-C₃H₆ system. The residual stress, hardness and ablation behaviors of the different coatings were characterized by Raman spectra, nano-indentation and oxyacetylene flame ablation machine respectively. Results shown tensile stress exists in the TaC coatings and increases when texture orientation turns from hybrid to (2 2 0) and (2 0 0), while nano-indentation hardness of the coatings also obeys the same trend. The deposited coatings could improve the ablation-resistance properties of C/C composites effectively. The texture structure also had great effects on the ablation properties and ablation morphologies of the coatings. The mass ablation rate obviously decreases when the texture structure changes from hybrid orientation to (2 0 0) and (2 2 0) orientations. The hybrid orientation and (2 0 0) texture coatings exhibit coarse oxide morphologies with crater or some breakage existed; while the (2 2 0) texture coating shows dense, molten oxide morphology. The main ablation behaviors of the hybrid, (2 0 0) and (2 2 0) texture TaC coatings are oxidation and particle denudation and block denudation, oxidation and block denudation, oxidation and mechanical erosion and block denudation, respectively.     

Femtosecond laser ablation characteristics of nickel-based superalloy C263

Femtosecond laser (180 fs, 775 nm, 1 kHz) ablation characteristics of the nickel-based superalloy C263 are investigated. The single pulse ablation threshold is measured to be 0.26±0.03 J/cm² and the incubation parameter ξ=0.72±0.03 by also measuring the dependence of ablation threshold on the number of laser pulses. The ablation rate exhibits two logarithmic dependencies on fluence corresponding to ablation determined by the optical penetration depth at fluences below ∼5 J/cm² (for single pulse) and by the electron thermal diffusion length above that fluence. The central surface morphology of ablated craters (dimples) with laser fluence and number of laser pulses shows the development of several kinds of periodic structures (ripples) with different periodicities as well as the formation of resolidified material and holes at the centre of the ablated crater at high fluences. The debris produced during ablation consists of crystalline C263 oxidized nanoparticles with diameters of ∼2–20 nm (for F=9.6 J/cm²). The mechanisms involved in femtosecond laser microprocessing of the superalloy C263 as well as in the synthesis of C263 nanoparticles are elucidated and discussed in terms of the properties of the material.     

葡萄糖催化氧化反应用Pd-Co/C催化剂的XPS研究

活性炭为载体，制备了Pd/C、Pd-Co/C催化剂，并进行了活性评价和XPS表征。在Pd-Co／C催化剂上反应3h后，葡萄糖的转化率达92％，选择性为94％，较Pd/C催化剂有显著提高。Co的添加及焙烧过程改变了Pd/C催化剂的表面组成及结构，提高了贵金属Pd在催化剂表面的分散程度，有利于Pd的还原，使Pd-Co/C催化剂表现出良好的催化活性和选择性。     

Preparation of ZrC nano-particles reinforced amorphous carbon composite coating by atmospheric pressure chemical vapor deposition

To eliminate cracks caused by thermal expansion mismatch between ZrC coating and carbon-carbon composites, a kind of ZrC/C composite coating was designed as an interlayer. The atmospheric pressure chemical vapor deposition was used as a method to achieve co-deposition of ZrC and C from ZrCl₄-C₃H₆-H₂-Ar source. Zirconium tetrachloride (ZrCl₄) powder carrier was especially made to control accurately the flow rate. The microstructure of ZrC/C composite coating was studied using analytical techniques. ZrC/C coating shows same morphology as pyrolytic carbon. Transmission electron microscopy (TEM) shows ZrC grains with size of 10-50 nm embed in turbostratic carbon. The formation mechanism is that the growth of ZrC crystals was inhibited by surrounding pyrolytic carbon and kept as nano-particles. Fracture morphologies imply good combination between coating and substrate. The ZrC crystals have stoichiometric proportion near 1, with good crystalline but no clear preferred orientation while pyrolytic carbon is amorphous. The heating-up oxidation of ZrC/C coating shows 11.58 wt.% loss. It can be calculated that the coating consists of 74.04 wt.% ZrC and 25.96 wt.% pyrolytic carbon. The average density of the composite coating is 5.892 g/cm³ by Archimedes’ principle.