Propylene epoxidation over Ti/MCM-41 catalysts prepared by chemical vapor deposition

Ti-containing mesoporous catalysts were prepared by chemical vapor deposition (CVD) of TiCl₄ on silica MCM-41 in the 700–900 °C temperature range. These samples were characterized (with XRD, ICP, nitrogen adsorption, FT-IR, ESCA, and TEM) and evaluated for the epoxidation of propylene with two alkyl hydroperoxides. The increase of CVD temperature resulted in the decrease of titanium content, catalyst hydroxyl population, crystallinity, and surface area. Catalyst selectivity to the desired product – propylene oxide – was highly sensitive to the deposition temperature. The best Ti/MCM-41 catalyst was prepared at the temperature of 800 °C, which had the maximum propylene oxide yield of 94.3%.     

Ti-SBA-15介孔分子筛催化制备环氧橡胶籽油的研究

以橡胶籽油(RSO)为原料,采用非均相介孔分子筛催化剂Ti-SBA-15催化制备环氧橡胶籽油(ERSO),探讨了催化剂用量、氧化剂叔丁基过氧化氢(TBHP)用量、反应时间、反应温度等因素对环氧化反应的影响。结果表明,Ti-SBA-15介孔分子筛催化剂催化制备ERSO的最佳工艺条件为:催化剂Ti-SBA-15用量0.062%(摩尔分数,以RSO物质的量计),TBHP与RSO物质的量比为1.3:1,反应时间6 h,反应温度70℃,此条件下制备的ERSO环氧值为68.9 mmol/g,产物转化率为82.22%,双键转化率为69.93%。通过FT-IR对比分析,进一步证实了环氧基团的生成。     

Carbon/carbon composites prepared by chemical vapour deposition

This paper summarizes the results of the authors' work on composites prepared by chemical vapour deposition (CVD), using propylene as a source of carbon and various substrates (cellulose carbon, natural graphite, different grades of carbon fibres bonded by phenolic or CVD carbon). The equations relating

1. (i) open porosity P with infiltration rate (− dP/dt = kP).

2. (ii) apparent density of the composites d_app with P (d_app = nP + q).

3. (iii) composite properties Y with d_app (Y = ad_app^b) have been confirmed for the systems studied up to the highest composite densities attained. The constants k, n, q, a and b vary with infiltration conditions, nature of the substrate (involving bonding carbon in the skeleton), heat treatment (HT) conditions and geometrical factors.

For a given set of conditions, infiltration rate increases with temperature and the partial pressure of propylene, but decreases with residence time. Contrary to the composite properties, the kinetics of infiltration are not influenced by the nature of the substrate, except for the initial stage before the substrate is coated by the CVD carbon, but depends on the shape and size of open pores. The influence of the nature of the carbon used to bond the fibres may be of particular importance for composite properties, the latter being also influenced by the state of the surface of the fibres. Among the geometrical factors, the studied effect of fibre content has been found to strongly influence the infiltration rate, in agreement with predictions, as well as the composite properties. The influence of HT on composite properties can be explained by the resulting structural changes in the substrate and the matrix and by the effect of stress relaxation.

Mechanism of carbon nanotube growth from camphor and camphor analogs by chemical vapor deposition

Single walled nanotubes have been synthesized by chemical vapor deposition from camphor, camphor analogs (camphorquinone, norcamphor, norbornane, camphene, fenchone), and various other precursors (menthone, 2-decanone, benzene, methane). The high temperature conditions (865 °C) and Fe/Mo alumina catalyst used in the syntheses are archetypal conditions for the production of single walled carbon nanotubes. It has been shown that the mechanism of tube growth is unlikely to depend upon the production of reactive five- and six-member rings, as has been previously suggested. The results suggest that the presence of oxygen in the precursor does not significantly improve the quality of tubes by etching amorphous carbon: it is suggested that the control of the flux of the precursor to the catalyst is more important in the production of high quality tubes. There is, however, evidence for different distributions of tube diameter being produced from different precursors.     

Initiated chemical vapor deposition of polyvinylpyrrolidone-based thin films

Initiated chemical vapor deposition (iCVD) is used for the first time to deposit a non-acrylic carbon-based polymer, polyvinylpyrrolidone (PVP). PVP is known for its hydrophilicity and biocompatibility, and its thin films have found many applications in the biomedical community, one of which is as antibiofouling surfaces. From vapors of 1-vinyl-2-pyrrolidone (VP) and tert-butyl peroxide (TBPO), iCVD produces PVP thin films that are spectroscopically identical to bulk PVP without using any solvents. iCVD works by selectively fragmenting gaseous TBPO with heat to create radicals for initiation of polymerization. This selectivity ensures that the monomer VP does not disintegrate to form species that do not conform to the structure of PVP. Fourier-transform infrared (FTIR), nuclear magnetic resonance, and X-ray photoelectron spectroscopy (XPS) show full retention of the hydrophilic pyrrolidone functional group. Number-average molecular weights range between 6570 and 10,200 g/mol. The addition of ethylene glycol diacrylate (EGDA) vapor to the reaction mixture creates a cross-linked copolymer between VP and EGDA. Films with different degrees of cross-linking can be made depending on the partial pressures of the species. Methods for quantifying the relative incorporation of VP and EGDA using FTIR and XPS are introduced. The film with the lowest degree of cross-linking has a wetting angle of 11°, affirming its high hydrophilicity and iCVD's ability to retain functionality.     

HfB2 coating on C/C composites prepared by chemical vapor deposition: Thermodynamics and experimental investigation

A thermodynamic calculation on the HfB₂ coating prepared by chemical vapor deposition (CVD) through HfCl₄-BCl₃-H₂-Ar system was performed, together with the relevant verification experiments. The calculation results indicated that HfB₂ coating could be obtained above 900 °C with the ratios of BCl₃/HfCl₄ and H₂/HfCl₄ higher than 1 and 12, respectively. The experimental results demonstrated that the deposition temperature, H₂ and BCl₃ flow rates had significant effects on the grain size, growth rate and phase composition of HfB₂ coatings. A dense and uniform HfB₂ coating was prepared at 1150 °C with a BCl₃/HfCl₄ ratio of 3 and a H₂/HfCl₄ ratio of 20, whose mass and linear ablation rates were 15.61 mg/s and 15.58 μm/s under oxyacetylene flame.     

化学气相沉积PPy/UHMWPE纤维的研究

采用化学气相沉积制备了聚吡咯/超高相对分子质量聚乙烯(PPy/UHMWPE)纤维,测试了不同氧化剂浓度、不同沉积时间和温度下PPy/UHMWPE纤维的表面剪切强度,用扫描电镜、动态热机械分析仪、傅立叶变换红外光谱仪分析了PPy/UHMWPE纤维的表面形态、热机械性能和复合材料官能团的变化。结果表明:PPy均匀分布在UHMWPE纤维表面,UHMWPE纤维与PPy之间无化学键作用而是分子间作用力;随着氧化剂三氯化铁浓度的增加和吡咯沉积时间的延长,PPy/UHMWPE纤维表面剪切强度先增大后减小;随着处理温度的升高,PPy/UHMWPE纤维表面剪切强度先增大,当处理温度超过85℃时,其剪切强度则减小。     

CVD法可控制备碳包覆金属纳米复合材料

以Fe质量分数分别为0.3%、1.6%、3.3%和5.2%的氯化钠担载铁为催化剂,化学气相沉积法催化裂解乙炔400℃下进行反应,系统探讨了碳包覆金属纳米颗粒的可控制备。通过扫描电子显微镜和高分辨透射电子显微镜对产物进行了表征,结果表明,w(Fe)=0.3%的催化剂制备的样品粒径在20～50 nm,平均直径约为30 nm;w(Fe)=1.6%的催化剂制备的样品粒径在35～60 nm,平均直径约为49 nm;而w(Fe)=3.3%和5.2%的催化剂制备的样品粒径差别不大,在40～100 nm,平均粒径约为65 nm。所制备的碳包覆金属纳米颗粒具有清晰的同心石墨壳层结构,并存在一定的结构缺陷。     

Morphologies and growth mechanisms of zirconium carbide films by chemical vapor deposition

Zirconium carbide films were grown on graphite slices by chemical vapor deposition using methane, zirconium tetrachloride, and hydrogen as precursors. The growth rate of zirconium carbide films as a function of temperature was investigated. The morphologies of these films at different temperatures were also observed by scanning electron microscopy. The results indicated that the deposition of zirconium carbide was dominated by gas nucleation at temperatures below 1523 K, and by surface process at temperatures higher than 1523 K. By comparison of the deposition activation energies for zirconium carbide and deposited carbon, it was determined that the carbon deposition was the controlled process during the growing of zirconium carbide films. The effect of temperatures on the morphologies of zirconium carbide films was also discussed, based on the carbon deposition process.     

Synthesis of carbon nanosheets by inductively coupled radio-frequency plasma enhanced chemical vapor deposition

An ultrathin sheet-like carbon nanostructure, carbon nanosheet, has been effectively synthesized with CH₄ diluted in H₂ by an inductively coupled radio-frequency plasma enhanced chemical vapor deposition. Nanosheets were obtained without catalyst over a wide range of deposition conditions and on a variety of substrates, including metals, semiconductors and insulators. Scanning electron microscopy shows that the sheet-like structures stand on edge on the substrate and have corrugated surfaces. The sheets are 1 nm or less in thickness and have a defective graphite structure. Raman spectra show typical carbon features with D and G peaks at 1350 and 1580 cm⁻¹, respectively. The intensity ratio of these two peaks, I(D)/I(G), increases with methane concentration or substrate temperature, indicating that the crystallinity of the nanosheets decreases. Infrared and thermal desorption spectroscopies reveal hydrogen incorporation into the carbon nanosheets.     

Microstructure and ablation property of gradient ZrCSiC modified C/C composites prepared by chemical liquid vapor deposition

Chemical liquid vapor deposition was adopted to fabricate gradient ZrCSiC modified C/C composites, and the microstructure and ablation resistance were studied. Results displayed the content of SiC decreased from the composites edge to the center but that of ZrC increased, indicating SiC and ZrC ceramics have the gradient distribution in the composites. The gradient composites possessed a low CTE and high thermal conductivity. The low CTE restricted the formation and expansion of defects, which could slow the oxygen diffusion in the composites. The high thermal conductivity could transfer the heat quickly in ablation process, which reduced the heat accumulation on the ablation surface and weakened the thermal erosion. Therefore, the gradient composites possessed an outstanding anti-ablation property at two heat fluxes. Compared with the uniformed distribution composites, the linear and mass ablation rates of the gradient composites decreased by 60.9% and 66.7% at heat flux of 2.38 MW/m² and decreased by 55.9% and 67.2% at heat flux of 4.18 MW/m². Because of the gradient distribution, porous ZrO₂ coating, ZrO₂SiO₂ coating and SiO₂ coating with SiO₂ nanowires were generated on the ablation center, ablation transition zone and ablation edge, respectively. These coatings isolated the sample surface from the flame and inhibited the transport of oxygen into the sample inner.     

Local chemical vapor deposition of carbon nanofibers from photoresist

The addition of nanofeatures to carbon microelectromechanical system (C-MEMS) structures would greatly increase surface area and enhance their performance in miniature batteries, super-capacitors, electrochemical and biological sensors. Negative photoresist posts were patterned on a Au/Ti contact layer by photolithography. After pyrolyzing the photoresist patterns to carbon patterns, graphitic nanofibers were observed near the contact layer. The incorporation of carbon nanofibers in C-MEMS structures via a simple pyrolysis of modified photoresist was investigated. Both experimental results considered to consist of a local chemical vapor deposition mechanism. The method represents a novel, elegant and inexpensive way to equip carbon microfeatures with nanostructures, in a process that could possibly be scaled up to the mass production of many electronic and biological devices.     

Growth of sculptured polymer submicronwire assemblies by vapor deposition

We have grown helical nanowire assemblies of parylene C, thereby demonstrating that polymeric sculptured thin films (STFs) can be fabricated by a combination of physical and chemical vapor deposition processes. The deposition method is explained in detail and electron micrographs of 200-400 nm size sculptured thin film of parylene are given. The shapes of the submicron and nanowire assemblies can be engineered so that the polymeric STF acts as a template for preferential attachment of biomolecules.     

影响化学气相沉积多晶硅致密料比例的因素

改良西门子法生产多晶硅还原工艺是高纯的三氯氢硅和氢气在还原炉内发生化学气相沉积反应,得到固态多晶硅,多晶硅根据表观质量,分为致密料、玉米料、珊瑚料。目前,国内多晶硅生产以大型还原炉为主,对成本控制具有明显优势,但存在的问题是多晶硅致密料比例较低。本文通过对还原炉反应温度控制、进料喷嘴布置、反应配比等因素的分析研究,得出了提高还原炉化学气相沉积多晶硅致密料比例的方法、思路。     

Low-temperature synthesis of graphene on Cu using plasma-assisted thermal chemical vapor deposition

Plasma-assisted thermal chemical vapor deposition (CVD) was carried out to synthesize high-quality graphene film at a low temperature of 600°C. Monolayer graphene films were thus synthesized on Cu foil using various ratios of hydrogen and methane in a gaseous mixture. The in situ plasma emission spectrum was measured to elucidate the mechanism of graphene growth in a plasma-assisted thermal CVD system. According to this process, a distance must be maintained between the plasma initial stage and the deposition stage to allow the plasma to diffuse to the substrate. Raman spectra revealed that a higher hydrogen concentration promoted the synthesis of a high-quality graphene film. The results demonstrate that plasma-assisted thermal CVD is a low-cost and effective way to synthesis high-quality graphene films at low temperature for graphene-based applications.     

Influence of catalytic particle size on the performance of fluidized-bed chemical vapor deposition synthesis of carbon nanotubes

In this paper, the impacts of catalytic particle size on the overall reactor performance for carbon nanotubes (CNTs) production using a fluidized-bed chemical vapor deposition (FBCVD) process have been studied. Six different particle size fractions (10-20 μm, 20-53 μm, 53-75 μm, 75-100 μm, 100-200 μm, and 200-300 μm) were selected. It was observed that the smaller the catalytic particle diameter, the greater the carbon deposition efficiency and the greater CNT synthesis selectivity. The 10-20 μm catalytic particles exhibited 30% higher carbon deposition efficiency than the 200-300 μm catalytic particles. The selectivity toward CNTs formation was also approximately 100%. These observations could be explained by the fact that when the diameter of the catalytic particle gets smaller, the breakthrough capacities during frontal diffusion will be bigger due to a shorter diffusion path length within the particle. Moreover, the fine particles ensured high interstitial velocity which subsequently enhances the heat and mass transfer, and consequently improves the CVD reaction.     

Effects of carbon film roughness on growth of carbon nanotip arrays by plasma-enhanced hot filament chemical vapor deposition

Carbon nanotip arrays were grown from carbon films deposited on silicon substrates by plasma-enhanced hot filament chemical vapor deposition. The carbon films were characterized by the atomic force microscopy and micro-Raman spectrometry and the carbon nanotip arrays were investigated by micro-Raman spectrometry, scanning electron microscopy and X-ray photon spectroscopy. The results indicate that both carbon films and carbon nanotips are made of polyaromatic carbon with turbostratic structure. Carbon films possess various roughnesses, which greatly influence the nanotip growth rate. The theory related to plasma and sputtering effect is used to discuss the results.     

Continuous deposition of carbon nanotubes on a moving substrate by open-air laser-induced chemical vapor deposition

Continuous deposition of carbon nanotubes under open-air conditions on a moving fused quartz substrate is achieved by pyrolytic laser-induced chemical vapor deposition. A CO₂ laser is used to heat a traversing fused quartz rod covered with bimetallic nanoparticles. Pyrolysis of hydrocarbon precursor gas occurs and subsequently gives rise to rapid growth of a multi-wall carbon nanotube forest on the substrate surface. A “mushroom-like” nanotube pillar is observed, where a random orientation of carbon nanotubes is located at the top of the pillars while the growth is more aligned near the base. The typical carbon nanotube deposition rate achieved in this study is approximately 50 μm/s. At high power laser irradiation, various carbon microstructures are formed as a result of excessive formation of amorphous carbon on the substrate. High-resolution transmission and scanning electron microscopy, and X-ray energy-dispersive spectrometry are used to investigate the deposition rate, microstructure, and chemical composition of the deposited carbon nanotubes.