Nanostructured silica based xerogels and aerogels are prepared by sol–gel technology, using methyltrimethoxysilane as precursor. The influence of the drying method and conditions on the microstructure of the obtained materials is investigated, since the drying stage has a critical influence on their porosity. Two types of drying methods were used: atmospheric pressure drying (evaporative), to produce xerogels, and supercritical fluids drying, to obtain aerogels. Although the supercritical fluids drying technique is more expensive and hazardous than the atmospheric pressure drying, it is well known that aerogels are less dense than the xerogels due to less pore shrinkage. However, the ideal situation would be to use atmospheric pressure drying in conditions that minimize the pore collapse. Therefore, in this work, different temperature cycles for atmospheric pressure drying and two heating rates for the supercritical fluids drying are tested to study the gels' shrinkage by analyzing the density and porosity properties of the final materials. The best materials obtained are aerogels dried with the lower heating rate (∼80 °C/h), since they exhibit very low bulk density (∼50 kg/m3), high porosity (95%)—mainly micro and mesopores, high surface area (∼500 m2/g), moderate flexibility and a remarkable hydrophobic character (>140°). It was proved that the temperature cycles of atmospheric pressure drying can be tuned to obtain xerogels with properties comparable to those of aerogels, having a bulk density only ∼15 kg/m3 higher. All the synthesized materials fulfill the requirements for application as insulators in Space environments.
Atom transfer radical polymerization (ATRP) of 2-(dimethylamino)ethyl methacrylate (DMAEMA) with a mixed transition metal catalytic system consisting of Fe(0) and small amounts of CuBr2/PMDETA (N,N,N′,N′′,N′′-pentamethyldiethylenetriamine) in water–isopropanol mixtures at 60 °C and 25 °C is reported and compared with commonly used CuBr/PMDETA-mediated ATRP systems. The obtained kinetics of polymerization showed that, in addition to the environmental attractiveness of this catalytic system, Fe/Cu mixed transition metal mediated ATRP of a DMAEMA monomer provides a significantly improved control of polymer chain growth, forming PDMAEMA of low dispersity values at all conversions. The controlled character of ATRP of DMAEMA was confirmed by the linear increase of molecular weights with monomer conversion, narrow molecular weight distributions, and re-initiation/chain extension experiments. The molecular structure of the obtained polymer(s) was confirmed by 1H nuclear magnetic resonance spectroscopy and matrix-assisted laser desorption ionization time-of-flight mass spectroscopy. ATRP of DMAEMA was also extended to synthesis of functional bio-relevant polymers with cholesterol and poly(ethylene glycol) segments.
Life cycle assessment is a methodology to assess environmental impacts associated with a product or system/process by accounting resource requirements and emissions over its life cycle. The life cycle consists of four stages: material production, manufacturing, use, and end-of-life. This study highlights the need to conduct life cycle assessment (LCA) early in the new product development process, as a means to assess and evaluate the environmental impacts of (nano)enhanced carbon fibre-reinforced polymer (CFRP) prototypes over their entire life cycle. These prototypes, namely SleekFast sailing boat and handbrake lever, were manufactured by functionalized carbon fibre fabric and modified epoxy resin with multi-walled carbon nanotubes (MWCNTs). The environmental impacts of both have been assessed via LCA with a functional unit of ‘1 product piece’. Climate change has been selected as the key impact indicator for hotspot identification (kg CO2 eq). Significant focus has been given to the end-of-life phase by assessing different recycling scenarios. In addition, the respective life cycle inventories (LCIs) are provided, enabling the identification of resource hot spots and quantifying the environmental benefits of end-of-life options.
The manufacturing process in thermoset-based carbon fiber-reinforced polymers (CFRPs) usually requires a curing stage where the material is transformed from a gel state to a monolithic solid state. During the curing process, micro-residual stresses are developed in the material due to the different chemical–thermal–mechanical properties of the fiber and of the polymer, reducing the mechanical performance of the composite material compared to the nominal performance. In this study, computational micromechanics is used to analyze the micro-residual stresses development and to predict its influence on the mechanical performance of a pre-impregnated unidirectional CFRP made of T700-fibers and an aeronautical grade epoxy. The numerical model of a representative volume element (RVE) was developed in the commercial software Abaqus® and user-subroutines are used to simulate the thermo-curing process coupled with the mechanical constitutive model. Experimental characterization of the bulk resin properties and curing behavior was made to setup the models. The higher micro-residual stresses occur at the thinner fiber gaps, acting as triggers to failure propagation during mechanical loading. These micro-residual stresses achieve peak values above the yield stress of the resin 55 MPa, but without achieving damage. These micro-residual stresses reduce the transverse strength by at least 10%, while the elastic properties remain almost unaffected. The numerical results of the effective properties show a good agreement with the macro-scale experimentally measured properties at coupon level, including transverse tensile, longitudinal shear and transverse shear moduli and strengths, and minor in-plane and transverse Poisson’s ratios. A sensitivity analysis was performed on the thermal expansion coefficient, chemical shrinkage, resin elastic modulus and cure temperature. All these parameters change the micro-residual stress levels and reduce the strength properties.