Morteros de cemento con nano-adiciones de sílice, hierro y alúmina

A lo largo de los últimos años, la ingeniería de la construcción ha seguido una tendencia creciente en lo que se refiere a la exigencia de altas prestaciones en los materiales empleados en obra, siendo el hormigón el material por excelencia. Es bien conocido que la capacidad de mejora de las prestaciones de los materiales está estrechamente ligada al desarrollo tecnológico existente en ese tiempo. En la actualidad, de entre todos los avances tecnológicos, cabe destacar la nanotecnología, ciencia que trabaja con elementos de tamaño 109 y que en los últimos años está siendo el motor de las investigaciones en el campo de la construcción. De entre todas las nano-adiciones existentes cabe destacar la nano-sílice, estudiada por numerosos investigadores y que goza de un gran número de artículos científicos. En cambio, existen otras nano-adiciones que no han tenido tanta aceptación o se encuentran en un segundo plano, como son la nano-hierro y la nano-alúmina. Es por tanto objeto de este Trabajo Fin de Máster: estudiar el efecto de la incorporación en diferentes proporciones de nano-adiciones de sílice, hierro y alúmina a un mortero de cemento convencional, mediante una campaña experimental realizada en el seno del Departamento de Ingeniería de la Construcción de la ETSICCP de la Universidad Politécnica de Madrid.

Morteros de cemento con nano-adiciones de hierro y sílice

Cada vez más, el hormigón tiene unas aplicaciones estructurales que demandan unos requisitos de resistencia y durabilidad difíciles de alcanzar siguiendo dosificaciones convencionales. Este contexto, de una mayor exigencia y desempeño del hormigón, es el epicentro de numerosas investigaciones que persiguen mejorar las características de los hormigones a través del uso de adiciones. Dentro de este marco de investigación, los últimos avances se encuentran vinculados al desarrollo de la nanotecnología, concretamente al uso de adiciones de tamaño nanométrico. La presente investigación queda enmarcada dentro de un Trabajo Fin de Máster y persigue la evaluación de los efectos a nivel microestructural y macroestructural del efecto de adiciones de tamaño nanométrico de hierro y sílice en proporciones variables a morteros de cemento. Para ver estas posibles mejoras, se comparará cuantitativamente con un mortero convencional de referencia. Para poder realizar dicha evaluación, se realizará una campaña experimental que incluye ensayos de resistencia, porosimetría, análisis térmico diferencial y resistividad. Una vez realizados los ensayos se ha procedido a analizar los resultados y a partir de ellos se han obtenido conclusiones acerca del desempeño de las nano adiciones en la matriz cementícia, así como de sus efectos en términos de resistencia y durabilidad principalmente. Finalmente, y dado que la investigación se encuentra acotada en el tiempo al ser un proyecto final de máster, se proponen unas líneas de investigación futuras con el fin de poder profundizar más en los procesos microestructurales que rigen el comportamiento de estas partículas en la matriz cementícia y con el propósito también de poder explicar resultados que no hayan podido quedar suficientemente resueltos a través del presente trabajo.

Sol-gel TiO2 nanoparticles prompt photocatalytic cement for pollution degradation

TiO2 nanoparticles (TiO2NPs) prepared by the sol–gel method have been incorporated to cement paste with the aim of creating a photocatalytic system capable of compensating, through degradation of hazardous molecules, the envi- ronmental impact associated to the production of the clinker. Doping was carried out at different mass ratios with TiO2NPs precursor solutions within a fresh ce- ment paste, which was then characterized using scanning electron microscopy (SEM). The photocatalytic performance was evaluated by the degradation of Methylene Blue (MB) using a 125W UV lamp as irradiating source. Main cement properties such as hydration degree and C-S-H content are affected by TiO2NPs doping level. Cement containing TiO2NPs exhibited an increasing photocatalytic activity for increasing doping, while the pure cement paste control could hardly degrade MB. The kinetics of the system where also studied and their second order behavior related to microstructural aspects of the system.

Mejora de las propiedades de materiales a base de cemento que contienen TiO2 : propiedades autolimpiantes

Los altos niveles de emisión de contaminantes en las grandes ciudades son causa principal de la suciedad y deterioro de la imagen estética de las edificaciones que las conforman y de la mala calidad del aire. Indudablemente, lo primordial es reducir al máximo dichas emisiones, y hoy en día ya se tratan de reducir por debajo de los límites tolerables a la salud, pero esta reducción sigue siendo insuficiente ante el deterioro estético de los edificios que requieren de intervenciones periódicas de limpieza con el consiguiente gasto. El trabajo trata de investigar y acotar los mecanismos fotocatalíticos por los que el TiO2 confiere propiedades autolimpiantes, descontaminantes y antifúngicos en materiales a base de cemento. Se trata de definir la influencia de la concentración de TiO2 y los mecanismos de activación fotocatalítica mediante luz visible y luz ultra violeta; implementación hidrófoba de la superficie; rendimientos autolimpiantes, descontaminantes y su duración e influencia en las propiedades mecánicas de la matriz. En primer lugar se revisa la situación actual en las investigaciones sobre las propiedades autolimpiantes que el TiO2 desarrolla sobre diversos materiales. A partir de ahí se han definido los procedimientos y dosificaciones teóricas más adecuadas para poder experimentar en el laboratorio, y poder discutir los resultados. Para poder evaluar la influencia del TiO2 en los materiales a base de cemento se han realizado una serie de probetas de mortero de cemento con diferentes concentraciones de TiO2 que se comparan con otras realizadas con un mortero convencional de referencia. Se realiza una campaña experimental que incluye: ensayos de resistencia, porosimetría, análisis y térmico diferencial, para evaluar su influencia en la estructura interna; ensayos de ángulo de escurrimiento, ángulo de contacto y auto limpieza, sin y con activación del TiO2 bajo rayos UV para poder evaluar el mecanismo fotocatalítico y el incremento de actividad de la auto limpieza. Una vez realizados los ensayos se ha procedido a analizar los resultados y a partir de ellos se han obtenido conclusiones acerca de la influencia del TiO2 en la matriz cementícia, así como de sus efectos en términos de auto limpieza. Finalmente, se proponen unas líneas de investigación futuras con el fin de poder profundizar más en la evaluación del rendimiento de los procesos fotocatalíticos que rigen su comportamiento y en el análisis de otros materiales que produzcan el del mismo efecto en la superficie cementícia y con el propósito también de poder explicar fenómenos que hayan podido quedar insuficientemente tratados en el presente trabajo.

Comparison of push-in and push-out tests for measuring interfacial shear strength in nano-reinforced composite materials

The influence of the carbon nanotubes (CNTs) content on the fiber/matrix interfacial shear strength (IFSS) in glass/fiber epoxy composites was measured by means of push-in and push-out tests. Both experimental methodologies provided equivalent values of the IFSS for each material. It was found that the dispersion of CNTs increased in IFSS by 19% in average with respect to the composite without CNTs. This improvement was reached with 0.3 wt.% of CNTs and increasing the CNT content up to 0.8 wt.% did not improve the interface strength.

Effect of nano-Si2O and nano-Al2O3 on cement mortars for use in agriculture and livestock production

The effect of nano-silica, nano-alumina and binary combinations on surface hardness, resistance to abrasion and freeze-thaw cycle resistance in cement mortars was investigated. The Vickers hardness, the Los Angeles coefficient (LA) and the loss of mass in each of the freeze–thaw cycles to which the samples were subjected were measured. Four cement mortars CEM I 52.5R were prepared, one as control, and the other three with the additions: 5% nano-Si, 5% nano-Al and mix 2.5% n-Si and 2.5% n-Al. Mortars were tested at 7, 28 and 90 d of curing to determine compression strength, total porosity and pore distribution by mercury intrusion porosimetry (MIP) and the relationship between the CSH gel and Portlandite total by thermal gravimetric analysis (TGA). The capillary suction coefficient and an analysis by a scanning electron microscope (SEM) was made. There was a large increase in Vickers surface hardness for 5% n-Si mortar and a slight increase in resistance to abrasion. No significant difference was found between the mortars with nano-particles, whose LA was about 10.8, classifying them as materials with good resistance to abrasion. The microstructure shows that the addition of n-Si in mortars refines their porous matrix, increases the amount of hydrated gels and generates significant changes in both Portlandite and Ettringite. This produced a significant improvement in freeze–thaw cycle resistance. The effect of n-Al on mortar was null or negative with respect to freeze–thaw cycle resistance.

TectoRNA: modular assembly units for the construction of RNA nano-objects

Structural information on complex biological RNA molecules can be exploited to design tectoRNAs or artificial modular RNA units that can self-assemble through tertiary interactions thereby forming nanoscale RNA objects. The selective interactions of hairpin tetraloops with their receptors can be used to mediate tectoRNA assembly. Here we report on the modulation of the specificity and the strength of tectoRNA assembly (in the nanomolar to micromolar range) by variation of the length of the RNA subunits, the nature of their interacting motifs and the degree of flexibility of linker regions incorporated into the molecules. The association is also dependent on the concentration of magnesium. Monitoring of tectoRNA assembly by lead(II) cleavage protection indicates that some degree of structural flexibility is required for optimal binding. With tectoRNAs one can compare the binding affinities of different tertiary motifs and quantify the strength of individual interactions. Furthermore, in analogy to the synthons used in organic chemistry to synthesize more complex organic compounds, tectoRNAs form the basic assembly units for constructing complex RNA structures on the nanometer scale. Thus, tectoRNA provides a means for constructing molecular scaffoldings that organize functional modules in three-dimensional space for a wide range of applications.

Biossensores de pH, ureia e glicose utilizando a microeletrônica de filmes finos de AZO e TIO2

Este trabalho apresenta o desenvolvimento de biossensores de pH, ureia e glicose, utilizando óxidos como plataforma para a parte seletiva. Os filmes finos de óxidos condutores foram produzidos por diferentes técnicas de deposição, como spin-coat, dip-coat, spray-pyrolysis e casting. Os materiais fabricados foram AZO e TiO2, ambos depositados sobre substratos de FTO, ITO ou vidro hidroflilizado. O número de camadas foi variado para cada técnica e as caracterizações morfológicas e estruturais foram feitas por MEV, DRX e FTIR. As caracterizações elétricas foram feitas por EGFET e voltametria cíclica. Os filmes foram testados como sensores de pHs na faixa de 2 a 8. O filme depositado com AZO em substrato de FTO pela técnica de spray-pyrolysis apresentou melhor resposta, com sensibilidade de 31,7 mV/pH entre toda a faixa de pHs do 2 ao 8. Já para os filmes de TiO2, o filme produzido por dip-coat com 5 camadas em substrato de FTO apresentou sensibilidade de 37,8 mV/pH entre a faixa de pHs de 2 a 8. Paralelamente, os filmes tiveram suas superfícies funcionalizadas com proteínas como urease ou glicose oxidase. Neste caso, os dispositivos foram testados entre as concentrações de 5 a 200 mg/dL de ureia e glicose. Como biossensor de ureia, o filme de TiO2 depositado por spin-coat com 5 camadas em substrato de FTO apresentou a maior sensibilidade, com valor 3,32 mV/(mg/dL) entre as concentrações de 5 a 120 mg/dL. Para os filmes estudados como biossensores de glicose, o melhor resultado também foi obtido pelo filme de TiO2 depositado por spin-coat com 5 camadas em substrato de FTO, apresentando sensibilidade em torno de 6,18 mV/(mg/dL) entre as concentrações de 5 a 200 mg/dL. Alguns resultados encontrados foram iguais ou melhores aos encontrados na literatura vigente, mesmo que os dispositivos ainda são passíveis de otimização.

Synthesis of high surface area TiO2 nanoparticles by mild acid treatment with HCl or HI for photocatalytic propene oxidation

Nanostructured TiO2 photocatalysts with small crystalline sizes have been synthesized by sol-gel using the amphiphilic triblock copolymer Pluronic P123 as template. A new synthesis route, based on the treatment of TiO2 xerogels with acid-ethanol mixtures in two different steps, synthesis and extraction-crystallization, has been investigated, analyzing two acids, hydrochloric and hydriodic acid. As reference, samples have also been prepared by extraction-crystallization in ethanol, being these TiO2 materials amorphous and presenting higher porosities. The prepared materials present different degrees of crystallinity depending on the experimental conditions used. In general, these materials exhibit high surface areas, with an important contribution of microporosity and mesoporosity, and with very small size anatase crystals, ranging from 5 to 7 nm. The activity of the obtained photocatalysts has been assessed in the oxidation of propene in gas phase at low concentration (100 ppmv) under a UVA lamp with 365 nm wavelength. In the conditions studied, these photocatalysts show different activities in the oxidation of propene which do not depend on their surface areas, but on their crystallinity and band gap energies, being sample prepared with HCl both during synthesis and in extraction-crystallizations steps, the most active one, with superior performance than Evonik P25.

Development of novel nano-biocomposite antioxidant films based on poly (lactic acid) and thymol for active packaging

Novel nano-biocomposite films based on poly (lactic acid) (PLA) were prepared by incorporating thymol, as the active additive, and modified montmorillonite (D43B) at two different concentrations. A complete thermal, structural, mechanical and functional characterization of all nano-biocomposites was carried out. Thermal stability was not significantly affected by the addition of thymol, but the incorporation of D43B improved mechanical properties and reduced the oxygen transmission rate by the formation of intercalated structures, as suggested by wide angle X-ray scattering patterns and transmission electron microscopy images. The addition of thymol decreased the PLA glass transition temperature, as the result of the polymer plasticization, and led to modification of the elastic modulus and elongation at break. Finally, the amount of thymol remaining in these formulations was determined by liquid chromatography (HPLC-UV) and the antioxidant activity by the DPPH spectroscopic method, suggesting that the formulated nano-biocomposites could be considered a promising antioxidant active packaging material.

Nano-biocomposite films with modified cellulose nanocrystals and synthesized silver nanoparticles

Ternary nano-biocomposite films based on poly(lactic acid) (PLA) with modified cellulose nanocrystals (s-CNC) and synthesized silver nanoparticles (Ag) have been prepared and characterized. The functionalization of the CNC surface with an acid phosphate ester of ethoxylated nonylphenol favoured its dispersion in the PLA matrix. The positive effects of the addition of cellulose and silver on the PLA barrier properties were confirmed by reductions in the water permeability (WVP) and oxygen transmission rate (OTR) of the films tested. The migration level of all nano-biocomposites in contact with food simulants were below the permitted limits in both non-polar and polar simulants. PLA nano-biocomposites showed a significant antibacterial activity influenced by the Ag content, while composting tests showed that the materials were visibly disintegrated after 15 days with the ternary systems showing the highest rate of disintegration under composting conditions.

Combined effects of cellulose nanocrystals and silver nanoparticles on the barrier and migration properties of PLA nano-biocomposites

Poly(lactic acid) (PLA)-based high performance nano-biocomposites were prepared to be used in active food packaging. Pristine (CNC) and surfactant modified cellulose nanocrystals (s-CNC) with silver (Ag) nanoparticles were used as the matrix modifiers. Binary and ternary systems were prepared. Morphological investigations revealed the good distribution of silver nanoparticles in PLA ternary systems. The combination of s-CNC and Ag nanoparticles increased the barrier effect of the produced films while the results of overall migration for the PLA nano-biocomposites revealed that none of the samples exceeded the overall migration limit, since results were well below 60 mg kg−1 of simulant.

Improving the Photoelectrochemical Response of TiO2 Nanotubes upon Decoration with Quantum-Sized Anatase Nanowires

TiO2 nanotubes (NTs) have been widely used for a number of applications including solar cells, photo(electro)chromic devices, and photocatalysis. Their quasi-one-dimensional morphology has the advantage of a fast electron transport although they have a relatively reduced interfacial area compared with nanoparticulate films. In this study, vertically oriented, smooth TiO2 NT arrays fabricated by anodization are decorated with ultrathin anatase nanowires (NWs). This facile modification, performed by chemical bath deposition, allows to create an advantageous self-organized structure that exhibits remarkable properties. On one hand, the huge increase in the electroactive interfacial area induces an improvement by 1 order of magnitude in the charge accumulation capacity. On the other hand, the modified NT arrays display larger photocurrents for water and oxalic acid oxidation than bare NTs. Their particular morphology enables a fast transfer of photogenerated holes but also efficient mass and electron transport. The importance of a proper band energy alignment for electron transfer from the NWs to the NTs is evidenced by comparing the behavior of these electrodes with that of NTs modified with rutile NWs. The NT-NW self-organized architecture allows for a precise design and control of the interfacial surface area, providing a material with particularly attractive properties for the applications mentioned above.

Photocatalytic oxidation of propene in gas phase at low concentration by optimized TiO2 nanoparticles

In the present study, nanocrystalline titanium dioxide (TiO2) was prepared by sol–gel method at low temperature from titanium tetraisopropoxide (TTIP) and characterized by different techniques (gas adsorption, XRD, TEM and FTIR). Variables of the synthesis, such as the hydrolyzing agent (acetic acid or isopropanol) and calcination temperatures (300–800 °C), were analyzed to get uniform size TiO2 nanoparticles. The effect that these two variables have on the structure of the resultant TiO2 nanoparticles and on their photocatalytic activity is investigated. The photocatalytic activities of TiO2 nanoparticles were evaluated for propene oxidation at low concentration (100 ppmv) under two different kinds of UV light (UV-A ∼ 365 nm and UV-C ∼ 257.7 nm) and compared with Degussa TiO2 P-25, used as reference sample. The results show that both hydrolyzing agents allow to prepare TiO2 nanoparticles and that the hydrolyzing agent influences the crystalline structure and its change with the thermal treatments. Interestingly, the prepared TiO2 nanoparticles possess anatase phase with small crystalline size, high surface area and higher photocatalytic activity for propene oxidation than commercial TiO2 (Degussa P-25) under UV-light. Curiously, these prepared TiO2 nanoparticles are more active with the 365 nm source than with the 257.7 nm UV-light, which is a remarkable advantage from an application point of view. Additionally, the obtained results are particularly good when acetic acid is the hydrolyzing agent at both wavelengths used, possibly due to the high crystallinity, low anatase phase size and high surface oxygen groups’ content in the nanoparticles prepared with it, in comparison to those prepared using isopropanol.

Spherical activated carbon as an enhanced support for TiO2/AC photocatalysts

Titanium dioxide nanoparticles prepared in situ by sol–gel method were supported on a spherical activated carbon to prepare TiO2/AC hybrid photocatalysts for the oxidation of gaseous organic compounds. Additionally, a granular activated carbon was studied for comparison purposes. In both types of TiO2/AC composites the effect of different variables (i.e., the thermal treatment conditions used during the preparation of these materials) and the UV-light wavelength used during photocatalytic oxidation were analyzed. The prepared materials were deeply characterized (by gas adsorption, TGA, XRD, SEM and photocatalytic propene oxidation). The obtained results show that the carbon support has an important effect on the properties of the deposited TiO2 and, therefore, on the photocatalytic activity of the resulting TiO2/AC composites. Thus, the hybrid materials prepared over the spherical activated carbon show better results than those prepared over the granular one; a good TiO2 coverage with a high crystallinity of the deposited titanium dioxide, which just needs an air oxidation treatment at low-moderate temperature (350–375 °C) to present high photoactivity, without the need of additional inert atmosphere treatments. Additionally, these materials are more active at 365 nm than at 257.7 nm UV radiation, opening the possibility of using solar light for this application.