Comportamiento Mecánico de Poliéster Insaturado Modificados con Poli(ε-Caprolactona) Reforzadas con Monmorillonita C30B

La dispersión de nanopartículas en el seno de una matriz polimérica es la base para la fabricación de los materiales denominados nanocompuestos. Una de las categorías de nanocompuestos que ha merecido especial atención en la última década es aquella en la que el nanorrefuerzo pertenece a la categoría de los silicatos laminares. Las propiedades únicas de estos materiales derivan del tamaño nanométrico de las partículas de silicato y de la elevada superficie de contacto polímero-nanosilicato que es posible alcanzar. En este trabajo se han preparado nanocompuestos fabricados con un nanosilicato laminar Cloisita 30B (C30B) perteneciente a la categoría de las montmorillonitas, orgánicamente modificada para favorecer su interacción con la matriz polimérica. Como matriz polimérica se ha utilizado una resina de poliéster de tipo isoftálico curada (UP) que ha sido modificada mediante la adición de un termoplástico, en concreto, poli (ε-caprolactona) (PCL) de dos pesos moleculares diferentes. La intención de la investigación es comparar el comportamiento de estos sistemas con el de sus análogos no reforzados, evaluando la influencia del nanorrefuerzo en el comportamiento mecánico y termomecánico

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 constan

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

Envejecimiento hidrotérmico en nanocompuestos epoxi/organoarcilla

Las dispersiones de organoarcillas como refuerzo en nanocompuestos de matriz polimérica han sido ampliamente estudiadas como una vía en la mejora de las propiedades (mecánicas, térmicas, de barrera frente a gases y disolventes e inflamabilidad). Una ventaja añadida es que se consigue una mejora de propiedades con la adición de una pequeña cantidad de refuerzo. En este trabajo se han preparado nanocompuestos basados en una matriz epoxi tipo DGEBA reforzada con dos organoarcillas, C30B e I.30E. Con el fin de mejorar la interfase matriz-refuerzo, también se han preparado nanocompuestos en los que las organoarcillas han sido previamente funcionalizadas a través del anclaje a la superficie de las mismas de un agente silano que contiene grupos reactivos con la matriz. Se ha realizado el estudio de la absorción de agua de estos nanocompuestos a temperatura constante hasta alcanzar el equilibrio de hinchamiento, determinando gravimétricamente la cantidad de agua absorbida en función del tiempo. El análisis de los resultados mediante el modelo de Fick y Langmuir nos ha permitido obtener los valores de los coeficientes de difusión (D). Los nanocompuestos han sido caracterizados mediante Difracción de Rayos X (DRX) y Calorimetría Diferencial de Barrido (DSC). Los valores de D obtenidos por el modelo de Fick son menores que los hallados a través del modelo de Langmuir, el cual se ajusta mejor a los valores experimentales. Como resultado y de acuerdo con la bibliografía, se ha observado que la presencia de las organoarcillas disminuyen el valor de D debido al camino tortuoso que ha de seguir el agua a través del nanocompuesto. Sin embargo, la presencia de grupos silano no mejora los resultados obtenidos del coeficiente de difusión para los nanocompuestos epoxi/organoarcilla

Rubber modified epoxy resins cured with piperidine

Glass transition temperatures (Tᵍ) of epoxy resins, diglycidyl ether of bisphenol-A cured with piperidine, have been measured by differential scanning calorimetry and dynamic mechanical thermal analysis in order to follow the curing process. Optimum cure conditions have been established as 3% PP at 120°C. Tᵍs of the neat epoxy system and those modified with 5 and 16% of a carboxyl-terminated reactive rubber copolymer of butadiene and acrylonitrile (CTBN) have been determined as a function of the cure time. Addition of 5% of CTBN does not modify the process, but the higher CTBN content accelerates the initial stage. Tᵍs after long cure times (Tᵍx) are lower for the modified systems than for the neat, showing that CTBN is not fully segregated. The amounts of CTBN dissolved in the epoxy crosslinked network have been estimated.The authors thank Dr A. J. Kinloch for advice in this investigation. We are grateful to CIBAGEIGY for kindly providing the samples. Financial support by the Comisión de lnvestigación Científica y Técnica is acknowledged (89/0435)

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 network

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

Betunes modificados con azufre: aditivos estabilizadores

En el presente trabajo se estudia la influencia de aditivos encaminados a conseguir la estabilidad de dichos betunes modificados. Mediante medidas de viscosidad y penetración se ha comprobado que la presencia combinada de diciclopentadieno + aminas, favorece la interacción del azufre con el betún por formación de polisulfuros. Asimismo, se ha analizado la influencia de inhibidores de radicales libre

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

Ternary nanocomposites: curing, morphology and mechanical properties of epoxy/thermoplastic/organoclay systems

The influence of two organically modified montmorillonites on the curing, morphology and mechanical properties of epoxy/poly(vinyl acetate)/organoclay ternary nanocomposites was studied. The organoclays and poly(vinyl acetate) (PVAc) provoked contrary effects on the epoxy curing reaction. Ternary nanocomposites developed different morphologies depending on the PVAc content, that were similar to those observed in the epoxy/PVAc binary blends. The organoclays were only located in the epoxy phase independently of the morphology. All nanocomposites showed intercalated structures with similar clay interlayer distances. Both PVAC and organoclays lowered the Tg of the epoxy phase, the presence of clays did not influence the Tg of the PVAc phase. The addition of the organoclays to the epoxy improved stiffness but lowered ductility while the adition of PVAc improved toughness although reduced stiffness of epoxy thermoset. Ternary nanocomposites exhibited optimal properties that combine the favourable effects of the clay and the thermoplastic