Reinforced silica-carbon nanotube monolithic aerogels synthesised by rapid controlled gelation

This work introduces a new synthesis procedure for obtaining homogeneous silica hybrid aerogels with carbon nanotube contents up to 2.50 wt.%. The inclusion of nanotubes in the highly porous silica matrix was performed by a two-step sol–gel process, resulting in samples with densities below 80 mg/cm3. The structural analyses (N2 physisorption and SEM) revealed the hierarchical structure of the porous matrix formed by nanoparticles arranged in clusters of 100 and 300 nm in size, specific surface areas around 600 m2/g and porous volumes above 4.0 cm3/g. In addition, a relevant increase on the mechanical performance was found, and an increment of 50% for the compressive strength and 90% for the maximum deformation were measured by uniaxial compression. This reinforcement was possible thanks to the outstanding dispersion of the CNT within the silica matrix and the formation of Si–O–C bridges between nanotubes and silica matrix, as suggested by FTIR. Therefore, the original synthesis procedure introduced in this work allows the fabrication of highly porous hybrid materials loaded with carbon nanotubes homogeneously distributed in the space, which remain available for a variety of technological applications

Effect of the drying procedure on hybrid sono-aereogels for organic solvent remediation

Hybrid organic–inorganic aerogels are highly hydrophobic porous solids that avoid the brittleness and moisture adsorption of the standard silica aerogels. Superhydrophobic porous materials have attracted great interest because of their ability for selective absorption of organic solvents while repelling water, as excellent candidates for remediation techniques. This work shows a comparative of three drying procedures of DEDMS/TEOS (diethoxydimethylsilane/tetraethylorthosilicate) gels, namely, by supercritical CO2, by supercritical ethanol, and dried at ambient conditions. Supercritical CO2 and ambient drying produced superhydrophobic aerogels (θ > 150°), while supercritical ethanol drying produces denser aerogels with smaller both porous volume and specific surface area. Regarding the absorption of organic liquids, swelling is observed in all cases. Hexane had faster diffusion that obeyed Fick's law (∝t0.5) whereas liquid polydimethylsiloxane exhibited slower non-Fickian diffusion process (∝tn, n < 0.5

NiO nanowire-containing heat transfer nanofluids for CSP plants: Experiments and simulations to promote their application

Concentrating solar power (CSP) is considered a clean, renewable and sustainable energy with a significant potential to become an alternative to polluting fossil fuel-based technologies. Among CSP collectors, parabolic-trough collectors (PTC) are the most mature technology, representing nearly 90% of the currently installed collectors in CSP plants worldwide. In this technology, a heat transfer fluid (HTF) carries the thermal energy absorbed to a power block to produce electricity. Improving the thermal properties of the conventional HTF could lead to an improvement of the efficiency of CSP plants. In this sense, the use of nanofluids as the HTF in these plants can be a promising choice. Here, polycrystalline NiO nanowirecontaining nanofluids have been prepared using the conventional HTF used in CSP plants as the base fluid; that is, the eutectic and azeotropic mixture of biphenyl (26.5%) and diphenyl oxide (73.5%). The stability, rheological and thermal properties have been characterized, and an analysis of the performance of the nanofluids prepared in standard and volumetric absorbers have been carried out. The overall CSP system performance can be increased up to 34.8% using the nanofluid in a surface collector or up to 34.3% using the nanofluid in a volumetric collector, which are better than the predicted 28.5% using the conventional HTF in a standard surface collector, thanks to the improvements in thermal properties, both specific heat and thermal conductivity. Finally, from molecular dynamics simulations we determined that the mean free path of thermal vibrations is longer for monocrystalline NiO nanowires. Thus, the development of strategies for obtaining this kind of nanostructures is of great interest because they can further improve the efficiency of these nanofluids

Hydroxyl Groups Induce Bioactivity in Silica/Chitosan Aerogels Designed for Bone Tissue Engineering. In Vitro Model for the Assessment of Osteoblasts Behavior

Silica (SiO2)/chitosan (CS) composite aerogels are bioactive when they are submerged in simulated body fluid (SBF), causing the formation of bone-like hydroxyapatite (HAp) layer. Silica-based hybrid aerogels improve the elastic behavior, and the combined CS modifies the network entanglement as a crosslinking biopolymer. Tetraethoxysilane (TEOS)/CS is used as network precursors by employing a sol-gel method assisted with high power ultrasound (600 W). Upon gelation and aging, gels are dried in supercritical CO2 to obtain monoliths. Thermograms provide information about the condensation of the remaining hydroxyl groups (400-700 degrees C). This step permits the evaluation of the hydroxyl group's content of 2 to 5 OH nm(-2). The formed Si-OH groups act as the inductor of apatite crystal nucleation in SBF. The N-2 physisorption isotherms show a hysteresis loop of type H3, characteristic to good interconnected porosity, which facilitates both the bioactivity and the adhesion of osteoblasts cells. After two weeks of immersion in SBF, a layer of HAp microcrystals develops on the surface with a stoichiometric Ca/P molar ratio of 1.67 with spherulite morphology and uniform sizes of 6 mu m. This fact asserts the bioactive behavior of these hybrid aerogels. Osteoblasts are cultured on the selected samples and immunolabeled for cytoskeletal and focal adhesion expression related to scaffold nanostructure and composition. The initial osteoconductive response observes points to a great potential of tissue engineering for the designed composite aerogels

Chitosan-GPTMS-Silica Hybrid Mesoporous Aerogels for Bone Tissue Engineering

This study introduces a new synthesis route for obtaining homogeneous chitosan (CS)-silica hybrid aerogels with CS contents up to 10 wt%, using 3-glycidoxypropyl trimethoxysilane (GPTMS) as coupling agent, for tissue engineering applications. Aerogels were obtained using the sol-gel process followed by CO2 supercritical drying, resulting in samples with bulk densities ranging from 0.17 g/cm(3) to 0.38 g/cm(3). The textural analysis by N-2-physisorption revealed an interconnected mesopore network with decreasing specific surface areas (1230-700 m(2)/g) and pore sizes (11.1-8.7 nm) by increasing GPTMS content (2-4 molar ratio GPTMS:CS monomer). In addition, samples exhibited extremely fast swelling by spontaneous capillary imbibition in PBS solution, presenting swelling capacities from 1.75 to 3.75. The formation of a covalent crosslinked hybrid structure was suggested by FTIR and confirmed by an increase of four hundred fold or more in the compressive strength up to 96 MPa. Instead, samples synthesized without GPTMS fractured at only 0.10-0.26 MPa, revealing a week structure consisted in interpenetrated polymer networks. The aerogels presented bioactivity in simulated body fluid (SBF), as confirmed by the in vitro formation of hydroxyapatite (HAp) layer with crystal size of approximately 2 mu m size in diameter. In vitro studies revealed also non cytotoxic effect on HOB(R) osteoblasts and also a mechanosensitive response. Additionally, control cells grown on glass developed scarce or no stress fibers, while cells grown on hybrid samples showed a significant (p < 0.05) increase in well-developed stress fibers and mature focal adhesion complexes

ABP en laboratorios de Química Física Macromolecular

Archivo pdf destacando los criterios a seguir empleando la metodología ABP, los test de ideas previas, y proyectos a desarrollar en las sesiones prácticas.Se muestran el material docente elaborado y empleado en las prácticas de la asignatura Química Física Macromolecular del curso 2011/2012, empleando la metodología de Aprendizaje Basado en Problemas (ABP)Proyecto de Innovación y Mejora Docente PI1_12_01

New insights into organic–inorganic hybrid perovskite CH3NH3PbI3 nanoparticles. An experimental and theoretical study of doping in Pb2+ sites with Sn2+, Sr2+, Cd2+ and Ca2+

This paper presents the synthesis of the organic–inorganic hybrid perovskite, CH3NH3PbI3, doped in the Pb2+ position with Sn2+, Sr2+, Cd2+ and Ca2+. The incorporation of the dopants into the crystalline structure was analysed, observing how the characteristics of the dopant affected properties such as the crystalline phase, emission and optical properties. XRD showed how doping with Sn2+, Sr2+ and Cd2+ did not modify the normal tetragonal phase. When doping with Ca2+, the cubic phase was obtained. Moreover, DR-UV-Vis spectroscopy showed how the band gap decreased with the dopants, the values following the trend Sr2+ < Cd2+ < Ca2+ < CH3NH3PbI3 ≈ Sn2+. The biggest decrease was generated by Sr2+, which reduced the CH3NH3PbI3 value by 4.5%. In turn, cathodoluminescence (CL) measurements confirmed the band gap obtained. Periodic-DFT calculations were performed to understand the experimental structures. The DOS analysis confirmed the experimental results obtained using UV-Vis spectroscopy, with the values calculated following the trend Sn2+ ≈ Pb2+ > Cd2+ > Sr2+ for the tetragonal structure and Pb2+ > Ca2+ for the cubic phase. The electron localization function (ELF) analysis showed similar electron localizations for undoped and Sn2+-doped tetragonal structures, which were different from those doped with Sr2+ and Cd2+. Furthermore, when Cd2+ was incorporated, the Cd–I interaction was strengthened. For Ca2+ doping, the Ca–I interaction had a greater ionic nature than Cd–I. Finally, an analysis based on the non-covalent interaction (NCI) index is presented to determine the weak-type interactions of the CH3NH3 groups with the dopant and I atoms. To our knowledge, this kind of analysis with these hybrid systems has not been performed previously