Direct growth of carbon nanotubes on carbon fibers: Effect of the CVD parameters on the degradation of mechanical properties of carbon fibers

Grafting carbon nanotubes (CNTs) directly on carbon fibers represents a promising approach in order to strengthen the weak interface between carbon fibers and polymer matrix in carbon fiber reinforced polymer composites (CFRCs). We have carried out direct growth of CNTs on carbon fibers by using two different catalytic chemical vapor deposition (CVD) processes, namely the conventional CVD process based on catalytic thermal decomposition of ethylene and the oxidative dehydrogenation reaction between acetylene and carbon dioxide. The effect of various CVD growth parameters, such as temperature, catalyst composition and process gas mixture, was for the first time systematically studied for both processes and correlated with the mechanical properties of carbon fibers derived from single-fiber tensile tests. The growth temperature was found to be the most critical parameter in the presence of catalyst particles and reactive gasses for both processes. The oxidative dehydrogenation reaction enabled decreasing CNT growth temperature as low as 500 C and succeeded to grow CNTs without degradation of carbon fiber's mechanical properties. The Weibull modulus even increased indicating partial healing of present defects during the CVD process. The new insights gained in this study open a way towards simple, highly reproducible and up-scalable process of grafting CNTs on carbon fibers without inducing any damages during the CVD process. This represents an important step towards CNT-reinforced CFRCs with higher damage resistance. (C) 2014 Elsevier B.V. All rights reserved.

Nanofibres de carbone sur filtre métallique comme support catalytique structuré

Pascal Tribolet

The main objectives of this work are 2-fold : The development of a novel type of composite material based on carbon nanofibers supported on sintered metal fibers filters (CNF/SMF) and to explore the use of this material as a catalytic support for a model reaction: selective hydrogenation of acetylene. The advantages of this novel support are: Due to carbon nanofibers, it combines a graphitic structure with a high specific surface area without microporosity. Supported carbon nanofibers can be used in a fixed bed reactor without very high pressure drop. Combination of two materials with high thermal conductivity gives a composite which keeps this property. It is suitable for highly exo/endothermic reactions, diminishing temperature gradients in the catalytic bed. The synthesis of carbon nanofibers on SMF filters was carried out by ethane catalytic decomposition at 655°C directly on metallic filters. An oxidation of SMF followed by a reduction in H2 create surface roughness, leading to a larger area for CNF nucleation. The CNF formation mechanism includes several steps: it starts with carbon deposition on metallic surface followed by its diffusion into the metal leading to carbides formation. When the limit of carbon solubility is attained, a layer of carbon is formed on the surface of metallic fibers. High tension within the bulk metal leads to carbide dissociation and by phase separation to graphite formation, which pushes the metallic particles through the carbon layer. Nickel, stainless steel an Inconel (an alloy of mainly nickel, iron and chromium) filters were used. The latter gave the highest uniformity of the carbon nanofibers layer showing an excellent mechanical stability. In order to control carbon deposition on the filters, a formal kinetic analysis of the decomposition reaction was undertaken. Partial orders of 1 for ethane, -2 for hydrogen and an apparent activation energy of 235 kJ/mol were obtained. The observed kinetics suggests strongly that the C – C bond scission is the rate determining step and not carbon diffusion into the metal which is often reported in the literature. The synthesis procedures like time on stream and reaction temperature were optimized: 1 hour of a mixture C2H6:H2:Ar (3:17:80) decomposition over SMFInconel at 655°C lead to ∼6% of carbon, leading to a CNF layer of 1 µm thickness covering the metallic fibers entirely. This material presents a high specific surface area (22.2 m2/g) and a low pressure drop for the gas flowing through. The carbon nanofibers have a diameter between 20 and 50 nm and a crystalline structure with platelets morphology where the graphene layers are stacked one above the other. Their surface is composed almost exclusively of carbon and hydrogen. Amongst the multiple possible applications of this novel composite material, its use as a catalyst support was assessed. Selective hydrogenation of acetylene was carried out over palladium supported on CNF/SMF and compared with commercial supports (ACF, EGF and AGF). The activated carbon fibers cloth (ACF) led to a Pd activity at least twice as E-type glass fibers tissue (EGF) or EGF covered by an alumina layer (AGF). Reaction kinetics was studied for Pd/ACF, leading to acetylene and hydrogen partial orders of -0.5 and 2.4, respectively and apparent activation energy of 50 kJ/mol. The negative partial order for C2H2 suggests high adsorption strength of this compound compared to other reagents on palladium. This particularity allows Pd to be selective. Hydrogenations are known to be structure sensitive. Therefore the catalyst activity for the model reaction depends on Pd particle size. It increases for large particle sizes. The control of this parameter was a priority. Variations of the palladium precursor, of the support and catalyst treatment were carried out. Micro-wave plasma was used since it is fast and has low energy consumption allowing chemically modifying the carbon support surface and activating catalyst after impregnation. This controls not only palladium sintering, but also decomposes tetraaminopalladate more efficiently, resulting in a catalyst activity of one order of magnitude higher. In order to control the palladium deposition on CNF/SMFInconel composite, it is important to have surface functional groups. The activation of carbon nanofibers was carried out with a 4 hours treatment in a boiling aqueous solution of hydrogen peroxide. This led to an amount on surface oxygen containing groups, per mass of carbon, higher than in ACF. Palladium particle size on the composite was controlled by support activation, the use of several metal precursors or different loadings or by a thermal treatment in argon at 500°C. Optimisation of the procedure allowed to obtain in a controlled way an average palladium particle sizes between 3.6 and 25 nm. The activity and selectivity towards ethylene of Pd/CNF/SMFInconel were observed to be higher compared to palladium supported on activated carbon, alumina or barite. Graphitic nature of carbon nanofibers, leading to strong metal-support interaction, was accounted as responsible for these improvements. The high thermal conductivity of the composite CNF/SMF ensured good heat transfer released due to the exothermicity of the reaction and allowed to work close to isothermal conditions in the catalytic bed. Finally it can be concluded, that for the first time carbon nanofibers synthesis was carried out in one step on sintered metal fibers filters, resulting in a novel structured composite material combining different specific properties and having promising potential applications.

EPFL2006

Surface-bound nanostructures

Kyumin Lee

This thesis looks at surface-bound nanowires and nanoparticles, the mechanical and the metrological properties of which are of practical importance in the realization of nanometer-scale electronics. Atomic force microscope (AFM) was the main instrument of research. By bending suspended carbon nanotube structures with the AFM, the Young's modulus of carbon nanotubes has been measured. An efficient new technique that involves an ac-dielectrophoresis preparation of carbon nanotubes on v-groove GaAs substrates and a force-curve measurement of the stiffness has been devised. The Young's modulus of a batch of multiwall carbon nanotubes grown by a single chemical vapor deposition (CVD) process shows a strong diameter dependence, indicating that the small catalyst particles produce crystalline tubes, while the thicker particles produce low-quality tubes with an abundance of structural defects. The experimental result is a strong evidence for the metastable-catalyst growth model of carbon nanotubes in CVD — the growth kinetics of carbon nanotubes is determined by the catalyst's liquid skin, which is more stable for smaller catalysts. As the nanotube study highlighted the importance of the size of catalyst nanoparticles, the topic of accurate nanoparticle sizing by dynamic AFM was then investigated. The measured size of a surface-bound nanoparticle was found to vary with imaging parameters, and a theoretical modeling showed that the non-contact — intermittent-contact mode switching can lead to discrepancies. Experimental results confirmed that the mode switching indeed causes the largest error in size measurements. A discrepancy also exists between the all-non-contact-mode and all-intermittent-contact-mode cases, and this anomaly could be explained by the effects of particle-substrate deformation and capillary forces. Nanoparticles were prepared on surfaces by boiling colloid drops on hot surfaces, a new technique developed for the uniformly dispersed deposition of colloidal nanoparticles and nanowires. Our experiments suggest that the actual deposition occurs through the smooth dewetting of liquid microdrops at elevated temperatures. The method is applicable on a wide range of surfaces and materials. Finally, a general haptic interface for the AFM was realized. The interface can be implemented on different AFM models with little effort, and it supports both the contact- and dynamic-AFM operations. Manipulation of gold nanoparticles has been carried out by raster scanning at different dynamic AFM setpoints, a promising approach for a quantitative study of the nanoparticle-substrate friction.

EPFL2008

Synthesis, characterization and macroscopic manipulation of carbon nanotubes

Csilla Mikó

This thesis describes the synthesis, characterisation and macroscopic manipulation of carbon nanotubes. Two interconnected aspects were investigated: (i) growth of carbon nanotubes by catalytic chemical vapour deposition of acetylene and (ii) assembly and reinforcement of macroscopic carbon nanotube fibres. The first part describes a systematic study of the growth of carbon nanotubes by chemical vapour deposition. In particular, the effect of the growth parameters, such as catalyst composition, catalyst carrier, temperature, and retention time, on the yield and quality of CNTs was investigated. It was found that Fe2Co is the most active catalyst in the bimetallic family of Fe1-ξCoξ, whereas deviation from this ideal compound was identified as poisoning the catalytic reaction. Furthermore, the CaCO3 support was found to be an additional source of carbon. This chemical reaction was explained by the decomposition of CaCO3, which produces CO2 groups that react with acetylene to result in carbon for the growth of CNTs. Hence, it was discovered that carbonate supports are not only acting as an inert support to avoid the coarsening of catalyst particles but as an additional source of reactant during the growth. In the second part, macroscopic, oriented fibres were assembled from CNTs in order to exploit their excellent mechanical properties. Electrical as well as mechanical properties were measured. Although both semiconducting and metallic CNTs are present in the starting material, electrical measurements on the macroscopic ropes of CNTs revealed a hopping-like conductance of the fibres. Measurements of mechanical properties have pointed out that these fibres lack the strength of an individual nanotube. The main problem is the weak van der Waals interaction between the tubes which lead the tubes to slide easily along their axes. This problem was addressed by irradiation experiments: Pure covalent carbon-carbon bonds were established in CNT fibres by a low dose of electron and ultraviolet irradiation resulting in an enhancement of the shear modulus between the tubes. Moreover, electrical measurements have demonstrated that a low dose of electron irradiation can significantly increase the shear modulus via cross-linking of CNTs in the fibre, but a high electron dose disorders the graphitic structure and results in a loss of the intrinsically high Young's modulus of the individual tubes. In contrast to electrons, the ultraviolet photons do not displace carbon atoms in the nanotube, therefore the reinforcement can be achieved by keeping the graphitic structure of the tubes intact.

EPFL2005