Film stacking impregnation model for a novel net-shape thermoplastic composite preforming process

An impregnation model has been developed to evaluate the infiltration phenomena that occur during a novel near net shape preforming method. This process comprises automated deposition of thermoplastic resin and unidirectional (UD) carbon fibres to a pre-programmed stacking sequence, thereby forming tailored preforms for subsequent stamp-forming. Infiltration kinetics have been simulated to study the effect of different stacking scenarios, materials, and preconsolidation routes on the novel preforming process. Isothermal infiltration of a liquid thermoplastic polymer into a compressed UD fibre bed has been examined and the experimental results have been used to validate an infiltration model based on local fluid flow in compressible porous media. This enables simulation of infiltration in alternating matrix film and fibre layers, relating pressure, time, and temperature with the local fibre volume fraction, pressure, and liquid and solid velocities in the stacked material. For a given set of processing conditions, the model fibre volume fraction distribution prediction enables the optimum matrix stacking layer thicknesses to be determined. It was shown that infiltration is inhibited above a limiting pressure which leads to increased fibre bed compaction and hence decreased permeability.

Optimisation of low pressure processing for honeycomb sandwich structures

Sandra Sequeira Lopes Tavares

Vacuum-bag processing of honeycomb sandwich structures faces particular challenges compared to autoclave sandwich fabrication for aeronautics, a consequence of using, at the most, atmospheric pressure for their manufacturing. In particular, the adhesion of the skin to the honeycomb core is reduced and the skins tend to have higher values of porosity. On the other hand, autoclave processing is expensive, in particular for large structures, and a growing interest has been observed for vacuum-bag only processing of sandwich structures. During honeycomb sandwich cure, the skin represents a barrier to air flow between the honeycomb and the vacuum-bag so the air transport through the prepreg, adhesive and consumables or other additional materials may be a crucial factor to increase skin debulking, reduce void content and extract air from the honeycomb cells. The pressure inside the honeycomb is, therefore, a result of the through thickness permeability to air of the skins and vacuum pump work. The goal of this thesis is to develop methods for improving the low pressure processing of honeycomb sandwich structures by quantifying the through thickness air permeability of fibre reinforced composites during cure and analysing related processing issues and governing phenomena. An experimental method based on a falling pressure measurement was proposed to evaluate the through thickness air permeability of prepregs during cure, with two set-up variants. One concerns the measurement of the inherent air permeability and the other applies to processing conditions, implying the use of both consumables and vacuum-bag. The methods were successfully tested and fulfil the criterions used in soil science for the evaluation of the air permeability. Prepreg and adhesive permeabilities were determined separately and in skin combination. Prepreg permeability to air during cure varies between 10-19 m2 and 10-17 m2 and was found to depend on the evolution of the resin viscosity, which shifts from an initially immobile phase to a mobile one and then back to an immobile phase. The adhesive film was found to have very low initial permeability, at least two orders of magnitude lower than that of the prepreg. A range of initial skin through thickness air permeability could be achieved by perforating the prepreg plies, the adhesive layer, or a combination of both. An adhesive deposition method which results in the centre of honeycomb cells being free of adhesive was also tested. A corresponding range of achievable pressure was measured inside the honeycomb. The evolution of the through thickness permeability with the curing cycle was determined for each case. The adhesive layer was identified as the element that reduces the initial through thickness air permeability the most in skin manufacturing. This suggests that one of the ways of increasing the initial through thickness air permeability of the skin is to modify the permeability of the adhesive layer. The role of the resulting pressure inside the honeycomb on skin-core adhesion and skin quality was then evaluated. Skin permeability was found to control skin-core adhesion through the pressure drop in the honeycomb cells and potential outgassing of the adhesive layer. An optimal range of pressure inside the honeycomb was found to be between 40 kPa and 70 kPa. A process window is proposed for achieving the optimal pressure inside the honeycomb, as a function of the skin permeability and time of vacuum application. A semipreg alternating dry and resin impregnated areas along the fibre bed surface was also investigated as an alternative to prepreg in skin manufacturing. The semipreg through thickness air permeability before cure is approximately three orders of magnitude higher than that of a unidirectional prepreg impregnated with the same resin, thus allowing the reduction of air pressure in the honeycomb. A model was proposed for the air permeability change during cure, as dry areas get infiltrated. Due to resin pouring inside the honeycomb cells, this type of semipreg is viable as a skin only if combined with a material that has low permeability to resin, e.g., a prepreg. The resulting initial pressure in the honeycomb cells might then be tailored to specific needs. Finally, it was possible to produce sandwich samples combining a consolidation system, such as a prepreg, with an infiltration system, as wet lay-up or with a semipreg. The combination of a prepreg with a semipreg revealed to be a very practical and clean system, where it is possible to have the same resin in both materials. Moreover, it allows to tailor the initial honeycomb pressure as well as during cure, and to have the initial permeability assessed.

EPFL2009

Strategies for faster impregnation in melt thermoplastic resin transfer molding process

Damiano Salvatori

Continuous fiber thermoplastic composites are potential substitutes of steel in structural automotive components, since they combine fiber strength and rigidity with ductility, potential recyclability and low density of the thermoplastic (TP) matrix. Resin transfer molding (RTM) is a process for composite production, involving direct impregnation of a reinforcing fabric in a closed rigid mold with a liquid resin. The duration of the impregnation step is directly proportional to the resin viscosity and inversely proportional to the fabric in-plane permeability. As a result, the high viscosity of melt thermoplastic resins (mTP) generally precludes their use in RTM, in particular to reach production volumes in line with the automotive sector. However, recent development of high-fluidity (HF) TPs, with medium range viscosity (10-50 Pa s) opens new possibilities for mTP-RTM. The goal of this thesis is to explore strategies to enhance the impregnation kinetics in mTP-RTM with HFTP by further increasing the fabric in-plane permeability. The effect of modified fabric architectures was investigated through experiments allowing visualization of flow propagation and permeability measurement using model fluids on a modified non-crimp fabric. A saturated permeability of ca 10-9 m2 for 46 vol% fibers was measured. The mesoscopic pore-space of the compacted fabrics was imaged with X-ray Tomography, and analyzed to propose permeability predictions based on the large channels geometry, which agreed well with the experimental results. Capillary effects were assessed over a broad range of capillary numbers (from 4.10-5 to 0.4) by direct comparison of unsaturated and saturated permeability. Permeability in these dual-scale fabrics is governed by viscous flow in the meso-channels. As a result, provided that the capillary number exceeds a threshold value, their permeability can be rather accurately measured by carrying out unsaturated measurements, neglecting micro-flow and capillary effects. Further improvement up to 10-8 m2 for 46 vol% fibers was achieved by introducing a flow-enhancing structure, made by polymer 3D-printing in the core of a woven fabric stack. The resulting flow was markedly dual-scale, going first very quickly in the core and later through the fabric. Optimized impregnation time was obtained by pulling vacuum prior to injection, letting the fluid flow within the core to the outlet, which is then closed, and finally continue the injection through thickness to complete saturation. A proof of concept with epoxy resin showed that a poly(latic acid) spacer led to an increased bending stiffness of 20%, but strong reinforcement gradients. Using a sacrificial spacer made of polycaprolactone, which melted during resin cure (80°C) allowed full fabric relaxation and a more homogeneous fibers distribution. Finally, these findings were applied to the development of a mTP-RTM mold to produce plates with HF polyamide 6 matrix. An 11 cm-long plate with 46 vol% glass fibers was impregnated in 7 min (1 min in the core, 6 min through the fabric) using high temperature spacers compared to more than 45 min without, also with improved bending stiffness by 26%. This concept is conceivably scalable to larger parts, since the bottleneck of the whole process is transferred to the saturation step. A preliminary cost analysis was carried out to evaluate the scalability of this technique as compared to alternative compression TP-RTM or a baseline epoxy RTM process.

EPFL2018

Release kinetics of volatiles from smectite clay minerals

Pascal Clausen

The focus of this thesis was on the mechanisms of release of volatile molecules from smectite clay minerals. The weight loss was monitored by thermogravimetry, differential calorimetry, and mass spectrometry under isothermal conditions and under ramp temperature conditions. Modeling of the clay-volatile release systems was performed with the help of finite element method calculations at the macroscopic level and ab initio calculations at the molecular level. A first comparison between finite element method simulations and experimental data for the evaporation of bulk volatile liquids under a convective gas flow showed the calculations to be in good agreement with experiments. Results of the simulations were used to develop a semi-analytical model explaining the dependence of the evaporation on the total pressure, the carrier gas flow, the temperature, and material constants. In particular, its temperature dependence could be approximated to good accuracy by an Arrhenius-type equation derived from the semi-analytical model. Differential calorimetry measurements of the heats of vaporization showed equilibrium conditions at the surface of the liquids to be satisfied. The same approach was extended to the release of model volatiles (water, ethanol, ethyl acetate and toluene) from smectite clays. At high coverage, the release was found to be close to that for the bulk liquids. Its decrease with time followed the behaviour observed in the respective curves of the gas/condensed phase partition coefficients, the equilibrium desorption isotherms. Equilibrium condition at the surface of the sample was evidenced by a comparison between the measured heats of vaporization and the equilibrium desorption isotherms. The differences observed in the measured equilibrium desorption isotherms of the volatile on the smectite clays could be rationalized by the use of ab initio calculations of the binding of the volatiles on the surface of a sodium smectite clay. At low coverage, the differences could be attributed to their differences in binding energies with the clay counter ions, which could be explained in terms of the chemical nature of the interacting species. At high coverage, the differences could be related to the properties of the bulk liquids, because high coverage corresponds to high activities of the volatiles on the clay samples. The differences observed in the measured rates of release of the volatiles from the smectite clays could be rationalized by the use of finite element calculations and the semi-analytical model developed for the bulk liquids, taking as input parameters the measured equilibrium desorption isotherms, that determines the volatile gas phase concentration at the surface of the sample. The slower rates of release of ethanol and ethyl acetate from the smectite clay, compared to water, could be explained from their differences in their equilibrium desorption isotherms from the clay, though diffusion effects also played a minor role. However, the slower rate of release of toluene, compared to water, could only be explained by its slow diffusion in the smectite clay. Diffusion effects were found to be enhanced with an increase in the size of the aggregate, such that, in addition to the binding strength of the counter ions, the swelling capacity of the clay, allowing the clay to clump, was also found to be an important factor for the controlled release of volatiles from the clay. Ion-exchange of the clay with lithium cations was found to be optimal in terms of ionic strength of the cation and swelling capacity, as compared to other metallic cations and small organic cations. This clay modification was tested on the release of malodorous compounds determined in cat urine by mass spectrometry and sniffing experiments. The smectite clay modified by ion-exchange with lithium cations showed improved controlled release of volatile organic compounds found in cat urine, compared to the sodium smectite, and improved clumping capacity compared to the calcium smectite. The calcium smectite clay used by Nestlé Purina could be modified by column exchange with lithium cations in high quantities. However the potential toxicity of the lithium is unknown. Additional information was obtained by ab initio calculations on the interaction of water with the smectite. The calculations of the binding of one to six water molecules on the surface of a sodium clay showed the water molecules bind to the cation and form hydrogen bonds between each other and with the clay oxygens, leading to the formation of different configurations for the same number of water molecules on the clay surface. With an increase in the number of water molecules on the surface of the clay, intermolecular interaction between the water molecules became gradually more important than sodium-water interactions. The binding energy was also found to be dependent on the location of the charge substitution in the clay (tetrahedral or octahedral) and to the formation of hydrogen bonds between the water molecule and a basal oxygen linked to a tetrahedral replacement. With an increase in the number of water molecules bound to one counter ion, the sodium counter ion was found to move away from the clay surface. The dynamic calculations of water molecules in the clay interlayer showed both the water molecules and the cations to be mobile. The average diffusion coefficient of the water molecules was reduced compared to that of bulk water, due to restrictions imposed by both the clay platelets and the counter ions. The structure of the water molecules showed to be similar to that of bulk water with a preferential orientation of their hydroxyl group almost perpendicular to the clay surface. The difference in the state of order of the water molecules around the sodium cation was interpreted as a symptom of hysteresis as observed in the measured equilibrium sorption isotherm.

EPFL2009

Optimisation of low pressure processing for honeycomb sandwich structures

Sandra Sequeira Lopes Tavares

EPFL2009

Release kinetics of volatiles from smectite clay minerals

Pascal Clausen

EPFL2009

Strategies for faster impregnation in melt thermoplastic resin transfer molding process

Damiano Salvatori

EPFL2018