Preparation and characterization of polyester resin-layered silicate containing reactive groups

Polymer nanocomposites, specifically nanoclay-reinforced polymers, have attracted great interest as matrix materials for high temperature composite applications. Nanocomposites require relatively low dispersant loads to achieve significant property enhancements. These enhancements are mainly a consequence of the interfacial effects that result from dispersing the silicate nanolayers in the polymer matrix and the high in-plane strength, stiffness and aspect ratio of the lamellar nanoparticles. The montmorillonite (MMT) clay, modified with organic onium ions with long alkyl chains as Cloisites, has been widely used to obtain nanocomposites. The presence of reactive groups in organic onium ions can form chemical bonds with the polymer matrix which favours a very high exfoliation degree of the clay platelets in the nanocomposite (1,2)

Influence of the epoxy/amine stoichiometry on the thermomechanical properties of nanocomposites based on high Tg epoxy and organophilic clays.

In layered silicate-epoxy nanocomposites organic modification of the silicates makes them compatible with the epoxy which intercalates into the clay galleries. The effect of clay dispersion on epoxies of high Tg is not clear. Decreases of the epoxy Tg have been frequently reported. The presence of clay may cause stoichiometry imbalances that conduces to the formation of imperfect networks

Thermal behaviour of bitumen modified by sulphur addition

The most frequent use of bitumen is as binder for pavement applications. The effect of sulphur addition on the properties of the bitumen has been extensively studied several decades ago. Recently, there is a renewed interest in researching the behaviour of sulphur-bitumen combination, because off 1.The future availability of bitumen may be limited and 2. The beneficial consumption of great amounts of sulphur compounds from petroleum refining is advisable. The addition of sulphur to bitumen provokes the beginning of chemical reactions depending on the sulphur content and heating temperature. At heating temperatures T< 140 ºC liquid sulphur reacts with naphthenic-aromatic fraction forming polysulphides. At temperatures above 150 ºC dehydrogenization reactions with emission of hydrogen sulfide take place and naphthenic-aromatic molecules are transformed into asphaltenes. Therefore, the addition of sulphur to bitumen provokes changes in the chemical structure of the bitumen. The objective of this work is to analyze, the thermal behaviour of sulphur-bitumen mixtures of different composition (0-35 %wt sulphur content) prepared at 130 and 140 ºC, by means of differential scanning calorimetry (DSC). Besides, the volatile emissions of the mixtures at high temperature have been estimated from loss weight measurements as a function of stored time

Propiedades de nanocompuestos de matriz termoestable con nuevos organosilicatos laminares

En este trabajo se han preparado nanocompuestos de matriz polímero termoestable del tipo poliéster insaturado y epoxídica utilizando como refuerzo nanosilicatos laminares que se han modificado específicamente para mejorar la interacción con la matriz. En concreto se han modificado montmorillonitas con cationes orgánicos reactivos con la matriz de poliéster insaturado. Asimismo se han silanizado montmorillonitas comerciales orgánicamente modificadas con el objetivo de formar enlaces químicos con la matriz epoxídica. En ambos nanocompuestos se han estudiado las propiedades termo- mecánicas pudiendo comprobar la efectividad de los nuevos organosilicatos.

Compatibilidad de Betunes Modificados con SBS en Función de la Estructura del Betún

Los betunes modificados con polímeros (BMP) son ampliamente utilizados en la pavimentación de carreteras sometidas a gran afluencia de vehículos y a condiciones extremas de temperatura. La presencia de polímero en contacto con el betún amplía notablemente el intervalo de temperaturas en las que el betún mantiene sus prestaciones. En general los betunes modificados con polímero presentan un aumento significativo de la resistencia a la deformación permanente en el intervalo de elevadas temperaturas, sin que su compo rtamiento sufra deterioro a bajas temperaturas. Cuando un polímero se añade al betún tiene lugar su hinchamiento a partir de las moléculas de aromáticos ligeros presentes en el betún. A bajas concentraciones de polímero, aparece una morfología bifásica en la que una fase rica en polímero se dispersa en una matriz malténica enriquecida en asfaltenos. La existencia de esta estructura bifásica es la llave que controla la mejora en las propiedades de los BMP en relación al betún puro. En la literatura existen muchos trabajos dedicados a investigar las propiedades y morfología de los BMP, sin embargo en pocos se hace referencia a la influencia de la estructura del betún. Este trabajo está enfocado a relacionar la estructura/composición del betún con la compatibilidad del sistema SBS/betún/azufre. Para ello se han elegido cuatro betunes de distinta procedencia denominados, A17, A500, M18, M170, que mezclados convenientemente han sido utilizados en la preparación de betún modificado con SBS y vulcanizado con azufre. La fracción en peso de SBS, en relación al contenido de betún, ha sido del 3%. Se han determinado propiedades tales como viscosidad, penetración y temperatura anillo-bola, así como la estabilidad en almacenamiento a elevada temperatura. Finalmente la estabilidad de estos sistemas se ha analizado en función de la estructura y la composición de los betunes utilizados en su preparación

Compatibilidad de Betunes Modificados con SBS: Influencia de la Estructura del Betún

El presente trabajo se centra en el estudio de la influencia de la estructura/composición del betún sobre la compatibilidad del sistema betún/SBS. Cuatro betunes denominados A17, A570, M18 y M172, provenientes de dos crudos distintos han sido seleccionados, y sus mezclas han sido utilizadas para preparar betunes modificados con contenidos de SBS respecto al betún del 3% en peso. Con objeto de establecer las prestaciones de los betunes modificados se han realizado medidas de viscosidad, penetración y temperatura de reblandecimiento en función del tiempo de almacenamiento a temperaturas elevadas. Finalmente la estabilidad de los sistemas modificados se discute en términos de la estructura y composición de los betunes utilizados en su preparación.

Storage stability of SBS/sulfur modified bitumens at high temperature: influence of bitumen composition and structure

Polymer modified bitumens, PMBs, are usually prepared at high temperature and subsequently stored for a period of time, also at high temperature. The stability of PMBs, in these conditions, has a decisive influence in order to obtain the adequate performances for practical applications. In this article the attention is focused in the analysis of the factors that determine the stability of styrene–butadiene–styrene copolymer (SBS)/sulfur modified bitumens when the mixtures are maintained at high temperature. Bitumens from different crude oil sources were used to prepare SBS/sulfur modified bitumens. Changes in the values of viscosity, softening point, as well as in the morphology of PMB samples, stored at 160 °C, were related to the bitumen chemical composition and to the amount of asphaltene micelles present in the neat bitumen used in their preparation El trabajo se centra en el estudio de la influencia de la estructura /composición del betún sobre la compatibilidad del sistema betún/SBS. Cuatro betunes provenientes de dos crudos distintos se seleccionaron y sus mezclas se utilizaron para preparar betunes modificados con contenidos de SBS del 3% en peso

Jasmonate-dependent modifications of the pectin matrix during potato development function as a defense mechanism targeted by Dickeya dadantii virulence factors

The plant cell wall constitutes an essential protection barrier against pathogen attack. In addition, cell-wall disruption leads to accumulation of jasmonates (JAs), which are key signaling molecules for activation of plant inducible defense responses. However, whether JAs in return modulate the cell-wall composition to reinforce this defensive barrier remains unknown. The enzyme 13-allene oxide synthase (13-AOS) catalyzes the first committed step towards biosynthesis of JAs. In potato (Solanum tuberosum), there are two putative St13-AOS genes, which we show here to be differentially induced upon wounding. We also determine that both genes complement an Arabidopsis aos null mutant, indicating that they encode functional 13-AOS enzymes. Indeed, transgenic potato plants lacking both St13-AOS genes (CoAOS1/2 lines) exhibited a significant reduction of JAs, a concomitant decrease in wound-responsive gene activation, and an increased severity of soft rot disease symptoms caused by Dickeya dadantii. Intriguingly, a hypovirulent D. dadantii pel strain lacking the five major pectate lyases, which causes limited tissue maceration on wild-type plants, regained infectivity in CoAOS1/2 plants. In line with this, we found differences in pectin methyl esterase activity and cell-wall pectin composition between wild-type and CoAOS1/2 plants. Importantly, wild-type plants had pectins with a lower degree of methyl esterification, which are the substrates of the pectate lyases mutated in the pel strain. These results suggest that, during development of potato plants, JAs mediate modification of the pectin matrix to form a defensive barrier that is counteracted by pectinolytic virulence factors from D. dadantii.

Influence of different organoclays on the curing, morphology, and dynamic mechanical properties of an epoxy adhesive

The thermal, mechanical, and adhesive properties of nanoclay-modified adhesives were investigated. Two organically modified montmorillonites: Cloisite 93A (C93A) and Nanomer I.30E (I.30E) were used as reinforcement of an epoxy adhesive. C93A and I.30E are modified with tertiary and primary alkyl ammonium cations, respectively. The aim was to study the influence of the organoclays on the curing, and on the mechanical and adhesive properties of the nanocomposites. A specific goal was to compare their behavior with that of Cloisite30B/epoxy and Cloisite15A/ epoxy nanocomposites that we have previously studied. Both C30B and C15A are modified with quaternary alkyl ammonium cations. Differential scanning calorimetry results showed that the clays accelerate the curing reaction, an effect that is related to the chemical structure of the ammonium cations. The three Cloisite/nanocomposites showed intercalated clay structures,the interlayer distance was independent of the clay content. The I.30E/epoxy nanocomposites presented exfoliated structure due to the catalytic effect of the organic modifier. Clay-epoxy nanocompo-sites showed lower glass transition temperature (Tg) and higher values of storage modulus than neat epoxy thermoset, with no significant differences between exfoliated or intercalated nanocom-posites. The shear strength of aluminum joints using clay/epoxy adhesives was lower than with the neat epoxy adhesive. The wáter aging was less damaging for joints with I.30E/epoxy adhesive.

Unsaturated polyester-poly(epsilon-caprolactone) hybrid nanocomposites: Thermal-mechanical properties

This paper reports on the thermal behavior and mechanical properties of nanocomposites based on unsaturated polyester resin (UP) modified with poly(ɛ-caprolactone) (PCL) and reinforced with an organically modified clay (cloisite 30B). To optimize the dispersion of 30B and the mixing of PCL in the UP resin, two different methods were employed to prepare crosslinked UP–PCL-30B hybrid nanocomposites. Besides, two samples of poly(ɛ-caprolactone) of different molecular weight (PCL2: Mn = 2.103g.mol−1 and PCL50: Mn = 5.104g.mol−1) were used at several concentrations (4, 6, 10 wt%). The 30B concentration was 4 wt% in all the nanocomposites. The morphology of the samples was studied by scanning electron microscopy (SEM). The analysis of X-ray patterns reveals that intercalated structures have been found for all ternary nanocomposites, independently of the molecular weight, PCL concentration and the preparation method selected. A slight rise of the glass transition temperature, Tg, is observed in UP/PCL/4%30B ternary nanocomposites regarding to neat UP. The analysis of the tensile properties of the ternary (hybrid) systems indicates that UP/4%PCL2/4%30B nanocomposite improves the tensile strength and elongation at break respect to the neat UP while the Young modulus remains constant