Chemical vapor deposition and infiltration processes of carbon materials

The chemical vapor deposition (CVD) and the chemical vapor infiltration (CVI) processes of carbon materials are reviewed starting from the historical aspects and including the latest developments in the preparation of C/C composites. Our presentation is based on an analysis of the different types of reactors, of the composite materials with different types of pyrocarbon as matrices and a comparison between the different processes. In particular, the classical isothermal-isobaric technique and temperature or pressure gradient reactors, which lead to a higher deposition efficiency, are compared. A complementary aspect is the structural and physical analysis of the deposited pyrocarbons: they are considered as reproducible metastable phases which are obtained under non-equilibrium thermodynamic conditions. The final relevant point concerns the relationship between the process parameters and the type of pyrocarbon. In particular, the so-called rough laminar microstructure, useful for most composite applications, is described.     

Analytical Modeling of Chemical Vapor Infiltration in Fabrication of Ceramic Composites

A model for chemical vapor infiltration is applied to the study of the growth of alumina from the chemical reaction among AlCl₃, H₂, and CO₂ within a SiC-fiber bundle which is situated in an isothermal hot-wall reactor. The pore space between the fibers is simulated by cylindrical capillary tubes. The model considers binary diffusion of CO₂ and H₂, chemical reaction on the inner surface of the tube, and deposition film growth. Furthermore, diffusion-controiled and chemical-reaction-controlled processes are taken into account to determine the dominating process in chemical vapor infiltration. Both molecular diffusion and Knudsen diffusion are considered sequentially in this model during the infiltration process. Based upon this model, the optimum processing conditions required for chemical vapor infiltration to form a SiC/Al₂O₃ composite can be predicted for different fiber preform systems.     

Numerical modeling of SiC by low-pressure chemical vapor deposition from methyltrichlorosilane

The development of functional relationships between the observed deposition rate and the experimental conditions is an important step toward understanding and optimizing low-pressure chemical vapor deposition (LPCVD) or low-pressure chemical vapor infiltration (LPCVI). In the field of ceramic matrix composites (CMCs), methyltrichlorosilane (CH₃SiCl₃, MTS) is the most widely used source gas system for SiC, because stoichiometric SiC deposit can be facilitated at 900℃-1300℃. However, the reliability and accuracy of existing numerical models for these processing conditions are rarely reported. In this study, a comprehensive transport model was coupled with gas-phase and surface kinetics. The resulting gas-phase kinetics was confirmed via the measured concentration of gaseous species. The relationship between deposition rate and 24 gaseous species has been effectively evaluated by combining the special superiority of the novel extreme machine learning method and the conventional sticking coefficient method. Surface kinetics were then proposed and shown to reproduce the experimental results. The proposed simulation strategy can be used for different material systems.     

Nickel ions removal from water by two different morphologies of induced CNTs in mullite pore channels as adsorptive membrane

In this study, chemical vapor deposition (CVD) method (with two proposed synthesis processes) was used for inducting two different morphologies of CNTs in mullite pore channels as a novel adsorptive membrane for nickel ions (Ni²⁺) removal from water. Cyclohexanol and ferrocene were used as carbon source and catalyst, respectively. The first proposed synthesis process involves coevaporation and pyrolysis of a mixed solution composed of cyclohexanol and ferrocene in a neutral atmosphere and the second involves sublimation and decomposition of ferrocene in a reactor individually and subsequently introduction of cyclohexanol as vapor to the reactor by a carrier gas during the reaction. Effects of synthesis parameters such as reaction time, catalyst content and reactor pressure on growth process, and structure and properties of the induced CNTs in pore channels of the mullite substrate were also investigated. Finally the optimized CNTs growth conditions for achieving a uniform distribution of the CNTs in the mullite pore channels were reported. The CNTs–mullite composite membranes prepared under the optimum conditions were oxidized with nitric acid and then successfully used as adsorptive membranes for nickel ions removal from water. Moreover, Langmuir and Freundlich isotherm models were used to describe adsorption behavior of nickel ions by the prepared adsorptive membrane.     

Influence of pressure, temperature and surface area/volume ratio on the texture of pyrolytic carbon deposited from methane

The kinetics of carbon deposition from methane were studied over broad ranges of pressures, temperatures and reciprocal surface area/volume ratios. Based on these results, it was possible to distinguish between a growth and a nucleation mechanism of carbon deposition and to select conditions for the preparation of well-defined samples for texture analysis by transmission electron microscopy and selected area electron diffraction. Maximal texture degrees were obtained at medium or high values of the above parameters, but never at low values, at which carbon formation is based on the growth mechanism and dominated by small linear hydrocarbons. High-textured carbon resulting from the growth mechanism is concluded to be formed from a gas phase with an optimum ratio of aromatic to small linear hydrocarbons, which supports the earlier proposed particle-filler model of carbon formation. High-textured carbon may also be formed from a gas phase dominated by polycyclic aromatic hydrocarbons (nucleation mechanism) provided that the residence time is sufficiently long that fully condensed, planar polycyclic aromatic hydrocarbons can be formed in the gas phase.     

Chemical Vapor Infiltration Rates of ZrO2 into MoSi2 Porous Bodies and Comparison with Model Calculation

Zirconia (ZrO₂) was chemical vapor infiltrated (CVI) into a partially sintered MoSi₂ body (preform) by using zirconium n -propoxide (Zr(OC₃H₇)₄) as a gas precursor. Infiltration distances at different conditions were compared with the calculated results. Chemical vapor deposition (CVD) film growth rates of ZrO₂ were measured, and the data were incorporated into the model calculations. Two models were used to analyze the observed infiltration distances. Initially a conventional model assuming a pore with constant radius (SP model) was used. With this model, it was possible to predict the approximate infiltration distance. However, the model cannot predict pore closure and the infiltration distances for a variety of CVI conditions. Secondly, a newly proposed model (PC model) from a previous paper was applied to calculate the infiltration distance. Using this model, it was possible to predict the occurrence of pore closure or the formation of the deposition layer on the preform surface.     

Chemistry and kinetics of chemical vapor deposition of pyrocarbon: VI. influence of temperature using methane as a carbon source

The chemical vapor deposition of carbon from methane was investigated at an ambient pressure of about 100 kPa, a methane partial pressure of 10 kPa and temperatures ranging from 1050–1125°C. Carbon deposition rates and compositions of the gas phase as a function of residence time have been determined using a substrate with a surface area/reactor volume ratio of 40 cm⁻¹. Increasing temperatures lead to strongly increasing deposition rates, decreasing partial pressures of ethane and increasing partial pressures of ethene, ethine and benzene. The overall activation energy of carbon deposition, determined from the initial deposition rates at a residence time versus zero amounts to 446 kJ/mol as compared to 431.5, 448 and 452.5 kJ/mol reported in earlier papers. Two possible rate-limiting steps are discussed, namely dissociation of methane, which is favored in the earlier papers, and dissociation of carbon–hydrogen surface complexes.     

高性能C/C复合材料制备工艺研究

对制备C/C复合材料的化学气相渗透工艺进行了系统的实验研究,着重分析了热解碳的沉积过程。研究表明,在化学气相渗透的初始阶段,热解碳主要在碳纤维表面沉积,并与碳纤维之间形成了界面结合;随后,热解碳的沉积继续填充碳纤维预制体内部的气孔。这一过程有助于缓解纤维与陶瓷基体之间的界面应力。研究表明,通过调节热解碳的沉积时间可以得到具有一定密度梯度的C/C复合材料。     

Evolution prediction of coal-nitrogen in high pressure pyrolysis processes

A pyrolysis model which can describe the effects of pressure on the evolution of coal-nitrogen has been constructed based on the FLASHCHAIN^® model in order to relate the gas release mechanism under high pressure conditions to the polymer reactions in coal. Various kinds of nitrogen-containing gaseous species in the evolved volatiles and their secondary decomposition and coupling processes have been also clarified by considering the elementary reactions of pyrrole-type nitrogen as the primary type of bound nitrogen in the first evoluted heavy species (tar vapor). The results show that the recombination reactions of metaplast are activated in a coal by the increase in pressure, resulting in a lesser amount of tar vapor and more intermediate chars. Thus, the conversion ratio of coal-nitrogen to gaseous volatile-nitrogen increases with the increase of pressure and N-gas converted from the fuel-N is much larger than the tar-N, and becomes more significant in high pressure conditions. Due to the chemical kinetics of the gas phase reactions, a shift in the distributions of tar-N vapor and gas-N with the increase of pressure can be predicted, and larger amounts of H₂CCHCN and bipyrrole gases are rapidly formed through three-body reactions, while HCN gas decreases greatly compared with the reaction at normal pressures. The changes of gas composition are in close agreement with the experimental results.     

Kinetic modeling of tungsten silicide chemical vapor deposition from WF6 and Si2H6: Determination of the reaction scheme and the gas-phase reaction rates

Kinetic studies were carried out on tungsten silicide (WSi_x) chemical vapor deposition from WF₆/Si₂H₆ in a hot-wall type tubular reactor, focusing on the axial distributions of step coverage and composition ratio. The growth-rate profile within the tubular reactor showed exponential decay, which suggests first-order reaction kinetics. The silicon content of the film increased downstream in the reactor, but the step coverage quality was independent of axial position. The reactive sticking probabilities obtained from the step coverage profile were about 0.33. Two reaction models were investigated to explain these experimental results. The first model is a parallel deposition model, in which W-containing species and Si-containing species are depositing separately. The other model is a consecutive reaction model, in which W-species and Si-species react in the gas phase to form intermediate species containing W and Si. Considering these plausible kinetic mechanisms, consecutive reactions in the gas phase to form W and Si containing species were found to be the controlling factor in the WF₆/Si₂H₆ process. These gas-phase homogeneous reaction-rate constants of the WF₆/Si₂H₆ process were obtained from axial distribution of film composition ratio based on this kinetic model, and the activation energy is about 25 kJ/mol.     

流化床-化学气相沉积技术在先进核燃料制备中的应用进展

流化床-化学气相沉积（FB-CVD）技术是化工流化床技术和材料化学气相沉积制备技术的交叉耦合,兼有流化床处理量大、传热快、温度均匀以及化学气相沉积温度调节范围广、产物丰富多样等优点,其在先进核燃料制备中有着重要的应用,但随着先进核燃料“质”和“量”的不断发展要求,现有的FB-CVD技术有许多方面亟待完善。本文回顾了作者课题组利用流化床-化学气相沉积在高温气冷堆TRISO核燃料颗粒、先进核燃料包覆颗粒、核燃料示踪颗粒、基体SiC纳米颗粒、SiC@Al₂O₃复合纳米颗粒等方面的研究进展,阐述了基本方法、实验过程和典型研究结果,并分析了流化床-化学气相沉积过程中遇到的实际问题。指出了FB-CVD技术未来发展方向,主要涉及反应器规模化放大和连续性生产、孔口沉积消除及温区控制、粉体制备中的纳米颗粒连续收集、新型反应器及工艺设计等方面,具体包括高密度颗粒稳定流化放大准则、床层局部温区控制以及分区流化床结构设计等。     

分子吸收光谱在半导体薄膜化学气相沉积中的应用

在化学气相沉积(CVD)生长半导体薄膜过程中,反应前体的浓度测量对于了解反应机理至关重要。紫外-可见吸收光谱和红外光谱是测量半导体薄膜CVD生长中分子浓度的主要工具,特别是可以实现气体浓度的原位测量。本文介绍了CVD中紫外-可见吸收光谱的测量系统,以及它们在测量Ⅲ～Ⅴ族气体浓度和确定在不同条件下化学反应路径中的应用。包括常见金属有机物等气体的吸收特征,紫外-可见吸收光谱在不同温度和压力下CVD过程中InN、GaN薄膜生长中的应用。本文也介绍了红外光谱分析方法在CVD中的应用,包括不同条件下TMG和NH₃气相反应机理的分析、SiC薄膜的元素成分分析以及GaN薄膜的气相反应速率的确定。     

Catalyst deactivation in CVD synthesis of carbon nanotubes

A computational fluid dynamics (CFD) model with multistep chemical reactions was applied to predict the yield of multiwalled carbon nanotubes produced from our xylene-based chemical vapor deposition (CVD) reactor. Two-step xylene decomposition in the gas phase and catalytic decomposition of hydrocarbons to nanotubes on the growth surfaces were adopted based on exhaust-gas composition measurements. Using the experimentally obtained exhaust-gas concentrations, we conducted inverse calculations to determine apparent rate constants of the catalytic surface reactions. During the CVD process, catalyst deactivation was observed probably due to carbon formation on the catalyst surface. Its effect on the apparent rate constant was empirically correlated with a simple exponential equation. Applying the CFD model, we predicted the local yielding rate of nanotubes along the axis of the reactor. The total yield was then computed by integrating the local yielding rate over the growth surfaces and compared favorably (∼95%) with the experimental results. The proposed model is expected to help researchers optimize the process parameters to achieve the maximum nanotube yield.     

Catalytic Routes Towards Single Wall Carbon Nanotubes

Single wall carbon nanotubes (SWCNT) have become a strategic material in the area of nanotechnologies nowadays, and catalytic chemical vapor deposition seems to be the most promising technique in view of an industrial‐scale production. However, the selective catalytic production of single wall carbon nanotubes is still a challenge, since catalytic systems performances both in terms of selectivity and activity are still relatively low. One of the main challenges for the catalytic growth of SWCNT is the control of the catalyst nanoparticles size distribution along the high temperatures required by the process. This article provides a comprehensive overview of the state of the art of the strategies that have been followed to selectively grow single wall carbon nanotubes. It focuses on catalysts preparation and activity/selectivity and on the growth mechanism of these nanostructures. Particular attention is given to the identification of the parameters that control the selectivity of the reaction, such as the choice of the metal/support couple, the particle’s sizes, and the chemical vapor deposition conditions.     

Catalytic Routes Towards Single Wall Carbon Nanotubes

Single wall carbon nanotubes (SWCNT) have become a strategic material in the area of nanotechnologies nowadays, and catalytic chemical vapor deposition seems to be the most promising technique in view of an industrial-scale production. However, the selective catalytic production of single wall carbon nanotubes is still a challenge, since catalytic systems performances both in terms of selectivity and activity are still relatively low. One of the main challenges for the catalytic growth of SWCNT is the control of the catalyst nanoparticles size distribution along the high temperatures required by the process. This article provides a comprehensive overview of the state of the art of the strategies that have been followed to selectively grow single wall carbon nanotubes. It focuses on catalysts preparation and activity/selectivity and on the growth mechanism of these nanostructures. Particular attention is given to the identification of the parameters that control the selectivity of the reaction, such as the choice of the metal/support couple, the particle's sizes, and the chemical vapor deposition conditions.     

Nucleation stability of diamond nanowires inside carbon nanotubes: A thermodynamic approach

Aiming at synthesis diamond nanowires, a simple thermodynamic approach was performed with respect to the effect of nanosize-induced additional pressure on the Gibbs free energy of critical nuclei to elucidate diamond nucleation inside carbon nanotubes upon chemical vapor deposition, based on the carbon thermodynamic equilibrium phase diagram. Notably, these analysis showed that the diamond nucleation would be preferable inside a carbon nanotube due to the effect of surface tension induced by the nanosize curvature of the carbon nanotube and diamond critical nuclei, compared with diamond nucleation on the flat surface of a silicon substrate. Meanwhile, the metastable phase region of diamond nucleation would be driven into a new stable phase region in the carbon thermodynamic equilibrium phase diagram by the effect of nanosize-induced additional pressure. Eventually, we predicted that carbon nanotubes would be an effective path to grow diamond nanowires by chemical vapor deposition.     

Chemical vapor deposition of pyrolytic carbon on carbon nanotubes: Part 1. Synthesis and morphology

The chemical vapor deposition of the pyrocarbon from a CH₄+H₂ mixture is investigated using nanofilamentous substrates. The process consists of growing carbon nanotubes via a catalytic process, which then are thickened by pyrolytic carbon deposition to reach diameters in the nanometer to micrometer range. A key characteristic of the experimental reactor used was the long length of its isothermal zone, preceded (and followed) by a low thermal gradient zone. This allowed us to investigate the role of the variation of the local gas phase composition, which depends on the post-cracking secondary reactions, and on the quantity and quality of the deposited carbon. The ‘time of flight’ of the reactive species was found to be a leading parameter in the pyrolytic carbon deposition process. Various nanometric and micrometric morphologies, several of which are new, were synthesised and found constituted with an association of different sub-morphologies. The various morphologies, that can be sorted following a factor of morphological complexity, were investigated by scanning electron microscopy.     

Single-step route to diamond-nanotube composite

Candle wax was used as a precursor for the production of a diamond-nanotube composite in a single step. The composite films were fabricated by sulfur-assisted hot-filament chemical vapor deposition technique. The morphology of the composite films was analyzed by scanning electron microscopy and transmission electron microscopy. Raman spectra of the films show characteristic diamond band at 1,332 cm⁻¹, D-band around 1,342 cm⁻¹, and graphitic G-band around 1,582 cm⁻¹. The electron energy-loss spectroscopy recorded at the carbon K-edge region shows signature features of diamond and carbon nanotube in the fabricated material. The ability to synthesize diamond-nanotube composites at relatively low temperatures by a single-step process opens up new possibilities for the fabrication of nanoelectronic devices.     

Selective formation of carbon nanotubes over Co-modified beta zeolite by CCVD

Multiwall carbon nanotubes containing carbon-zeolite composite materials have been obtained by ethylene catalytic chemical vapor deposition (CCVD) on Co-modified beta zeolite powder. High carbon selectivity to nanotubes was achieved. The combined physical characterisation through several techniques, such as TEM, HRTEM, SEM, XRD, N₂ adsorption-desorption, allows to determine the geometric characteristics of nanotubes and their dependence of catalyst and synthesis conditions.