Analytical and numerical study of the densification of carbon/carbon composites by a film-boiling chemical vapor infiltration process

The film-boiling chemical vapor infiltration (CVI) process is a fast process developed for composite material fabrication, and especially carbon/carbon composites. In order to help define optimal conditions, a local 1D model has been developed to study the densification front which establishes itself during the processing of a carbon/carbon fibrous preform. The model features heat conduction, precursor gas diffusion, densification reactions and structural evolution of the porous medium. The effects of total mass flux, Thiele modulus, porous medium geometry on front behavior parameters such as width, velocity and residual porosity are presented as semi-analytical correlations. An existence criterion is produced, which involves a minimal heat flux. Comparison between process-scale experiments and simulation is then possible by inserting the semi-analytical results achieved in the local study of the front into a light numerical model involving the entire preform. The model has been validated with respect to previous experimental and numerical data.     

Priority organic pollutants in the urban water cycle (Toulouse, France)

Application of the European Water Framework Directive requires Member States to have better understanding of the quality of surface waters in order to improve knowledge of priority pollutants. Xenobiotics in urban receiving waters are an emerging concern. This study proposes a screening campaign of nine molecular species of xenobiotics in a separated sewer system. Five sites were investigated over one year in Toulouse (France) using quantitative monitoring. For each sample, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, nonylphenols, diethelhexylphthalate, linear alkylbenzene sulphonates, methyl tert-butylether, total hydrocarbons, estradiol and ethinylestradiol were analysed. Ground, rain and roof collected water concentrations are similar to treated wastewater levels. Run-off water was the most polluted of the five types investigated, discharged into the aquatic environment. The wastewater treatment plant reduced xenobiotic concentrations by 66% before discharge into the environment. Regarding environmental quality standards, observed concentrations in waters were in compliance with standards. The results show that xenobiotic concentrations are variable over time and space in all urban water compartments.     

Complex geometry macroporous SiC ceramics obtained by 3D-printing,polymer impregnation and pyrolysis (PIP) and chemical vapor deposition (CVD)

We present here an original route for the manufacturing of SiC ceramics based on 3D printing, polymer impregnation and pyrolysis and chemical vapor deposition (CVD). The green porous elastomer structures were first prepared by fused deposition modeling (FDM) 3D-printing with a composite polyvinyl alcohol/elastomer wire and soaking in water, then impregnated with an allylhydridopolycarbosilane preceramic polymer. After crosslinking and pyrolysis, the polymer-derived ceramics were reinforced by CVD of SiC using CH₃SiCl₃/H₂ as precursor. The multiscale structure of the SiC porous specimens was examined by X-ray tomography and scanning electron microscopy analyses. Their oxidation resistance was also studied. The pure and dense CVD-SiC coating considerably improves the oxidation resistance.     

Monitoring Density and Temperature in C/C Composites Processing by CVI with Induction Heating

Carbon/carbon composites are processed by chemical vapor infiltration (CVI) with radio-frequency inductive heating, which leads to inside-out temperature gradients, suitable for the production of homogeneously densified pieces if properly controlled throughout the whole processing. We present here a 2D axisymmetrical case where a comprehensive numerical model is tested against experimental runs. The numerical thermal model takes into account induction heating, radiative, conductive, and convective effects, intermediate regime diffusion and densification reactions in the pores, and the evolution of the porous medium. The results are the time evolution of the temperature, concentration, and composite material density field, as well as the input power necessary to ensure a given maximal temperature in the preform. Experimental data are measurements of the temperature and density fields at various infiltration stages. Comparison between experience and simulation, yielding an useful agreement, shows that porosity becomes trapped inside the preform as densification proceeds, because of the progressive lowering of the temperature gradient steepness. The discrepancies between computations and experimental data rely on the only approximate knowledge of some quantities, principally the reaction kinetics, which are currently under investigation.     

Global and local characterization of the thermal diffusivities of SiCf/SiC composites with infrared thermography and flash method

Two types of SiC_f/SiC composites with different matrix quantities are prepared by CVR from pyrolyzed Carbon/resin composites. Experiments based on transient, space-resolved infrared thermography are developed; various assessment methods are implemented to measure simultaneously transverse and in-plane thermal diffusivities, globally and locally; the emphasis is set on the accuracy of the estimations. The material anisotropy is revealed and the influence of matrix volume fraction on the global thermal diffusivities is evaluated. Gradients of the properties are clearly visible in the samples, by use of the local analysis. The global heat conductivity values are discussed with respect to previous works.     

Methyldichloroborane evidenced as an intermediate in the chemical vapour deposition synthesis of boron carbide

The most recent ceramic-matrix composites (CMC) considered for long-life applications as thermostructural parts in aerospace propulsion contain, among others, boron-rich phases like boron carbide. This compound is prepared by thermal Chemical Vapour Infiltration (CVI), starting from precursors like boron halides and hydrocarbons. We present a study aiming at a precise knowledge of the gas-phase composition in a hot-zone LPCVD reactor fed with BCl3, CH4 and H2, which combines experimental and theoretical approaches. This work has brought strong evidences of the presence of Methydichloroborane (MDB, BCl2CH3) in the process. It is demonstrated that this intermediate, the presence of which had never been formally proved before, appears for processing temperatures slightly lower than the deposition temperature of boron carbide. The study features quantum chemical computations, which provide several pieces of information like thermochemical and kinetic data, as well as vibration and rotation frequencies, reaction kinetics computations, and experimental gas-phase characterization of several species by FTIR, for several processing parameter sets. The main results are presented, and the place of MDB in the reaction scheme is discussed.     

The film-boiling densification process for C/C composite fabrication: From local scale to overall optimization

The film-boiling densification process is an alternative of chemical vapor infiltration involving a strong thermal gradient. It allows to fabricate composite materials starting from a fibrous preform lying in a boiling hydrocarbon precursor, the cracking of which results in a solid deposit constituting the matrix of the carbon/carbon composite. A modelling approach is presented and validated with respect to experimental data. Then, the sensitivity of the process is studied with respect to various parameters. Optimization guidelines are proposed, in conjunction with a discussion on the densification front that characterizes the process. It is thus possible to evaluate the minimal amount of power required, while maintaining the quality of the produced material, i.e., its bulk density and homogeneity.     

A Brownian motion algorithm for tow scale modeling of chemical vapor infiltration

Chemical vapor infiltration (CVI) is a frequent processing method for the tailoring of high-quality ceramic–matrix composites. It involves rarefied gas transfer in a disordered fibrous array and heterogeneous deposition reactions. Optimization of CVI by experimental means is prohibited by important fabrication costs and duration; triggering the need for a numerical model. Our tow scale computational tool reproduces gas transport by an Itō-Taylor random walk scheme whilst chemical reaction is handled by a Monte Carlo routine. Numerical validations of the code with respect to analytical estimates are presented. Finally, applications to 3D images are depicted and the influence of operating conditions on matrix deposition is discussed.