Non-isothermal cure and exfoliation of tri-functional epoxy-clay nanocomposites

The non-isothermal cure kinetics of polymer silicate layered nanocomposites based on a tri-functional epoxy resin has been investigated by differential scanning calorimetry. From an analysis of the kinetics as a function of the clay content, it can be concluded that the non-isothermal cure reaction can be considered to consist of four different processes: the reaction of epoxy groups with the diamine curing agent; an intra-gallery homopolymerisation reaction which occurs concurrently with the epoxy-amine reaction; and two extra-gallery homopolymerisation reactions, catalysed by the onium ion of the organically modified clay and by the tertiary amines resulting from the epoxy-amine reaction. The final nanostructure displays a similar quality of exfoliation as that observed for the isothermal cure of the same nanocomposite system. This implies that the intra-gallery reaction, which is responsible for the exfoliation, is not significantly inhibited by the extra-gallery epoxy-amine cross-linking reaction.Peer ReviewedPostprint (published version

A novel comparative study of different layered silicate clay types on exfoliation process and final nanostructure of trifunctional epoxy nanocomposites

© 2016. This version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/The effect of three different organically modified layered silicate clays (Nanomer I.30E, Cloisite 30B and Nanofil SE 3000) on the exfoliation process and on the thermal properties and nanostructure of cured trifunctional epoxy resin based nanocomposites was studied. Optical microscopy showed that the best and poorest qualities of clay distribution in the epoxy matrix were obtained with Nanofil SE 3000 and Nanomer I.30E, respectively. However, the isothermal differential scanning calorimetry scans show that, of the three systems, it is only the Nanomer clay that promotes intra-gallery reaction due to homopolymerisation, appearing as an initial rapid peak prior to the cross-linking reaction. This rapid intra-gallery reaction is not present in the curing curve for the Cloisite and Nanofil systems. This fact implies that the fully cured nanostructure of the Cloisite and Nanofil system is poorly exfoliated, which is confirmed by small angle X-ray scattering which shows a scattering peak for these systems at around 2.53°, corresponding to about 3.5 nm d-spacing.Peer ReviewedPostprint (author's final draft

Achieving high thermal conductivity in epoxy composites: Effect of boron nitride particle size and matrix-filler interface

For the thermal management of high watt density circuit layers, it is common to use a filled epoxy system to provide an electrically insulating but thermally conducting bond to a metal substrate. An epoxy-thiol system filled with boron nitride (BN), in the form of 2, 30 and 180 µm platelets, has been investigated with a view to achieving enhanced thermal conductivity. The effect of BN content on the cure reaction kinetics has been studied by differential scanning calorimetry and the thermal conductivity of the cured samples has been measured by the Transient Hot Bridge method. The heat of reaction and the glass transition temperature of the fully cured samples are both independent of the BN content, but the cure reaction kinetics is systematically affected by both BN content and particle size. These results can be correlated with the thermal conductivity of the cured systems, which is found to increase with both BN content and particle size. For a given BN content, the thermal conductivity found here is significantly higher than most others reported in the literature; this effect is attributed to a Lewis acid-base interaction between filler and matrix.Peer ReviewedPostprint (published version

Comparison of the nanostructure and mechanical performance of highly exfoliated epoxy-clay nanocomposites prepared by three different protocols

Three different protocols for the preparation of polymer layered silicate nanocomposites based upon a tri-functional epoxy resin, triglycidyl para-amino phenol (TGAP), have been compared in respect of the cure kinetics, the nanostructure and their mechanical properties. The three preparation procedures involve 2 wt% and 5 wt% of organically modified montmorillonite (MMT), and are: isothermal cure at selected temperatures; pre-conditioning of the resin-clay mixture before isothermal cure; incorporation of an initiator of cationic homopolymerisation, a boron tri-fluoride methylamine complex, BF3·MEA, within the clay galleries. It was found that features of the cure kinetics and of the nanostructure correlate with the measured impact strength of the cured nanocomposites, which increases as the degree of exfoliation of the MMT is improved. The best protocol for toughening the TGAP/MMT nanocomposites is by the incorporation of 1 wt% BF3·MEA into the clay galleries of nanocomposites containing 2 wt% MMT.Peer ReviewedPostprint (published version

Epoxy composites filled with boron nitride: cure kinetics and the effect of particle shape on the thermal conductivity

Thermally conducting and electrically insulating materials have been prepared by filling an epoxy–thiol system with boron nitride (BN) particles of different shapes (platelets and agglomerates) and sizes (from 2 to 180 µm), and hence with different specific surface areas. The cure kinetics has been studied by differential scanning calorimetry in both non-isothermal and isothermal modes, and it has been shown that there is a systematic dependence of the cure kinetics on the BN content, the cure reaction generally being retarded by the addition of the BN particles. For filler loadings greater than about 30 vol%, the retardation of the cure, in both isothermal and non-isothermal mode, appears also to decrease as the specific surface area decreases. For the smallest (2 µm) platelets, which have a significantly higher specific surface area (10 m2 g-1), the retardation is particularly pronounced, and this aspect is rationalized in terms of the activation energy and frequency factor of the reaction. The thermal conductivity of the cured epoxy–thiol–BN composites has been measured using the transient hot bridge method and is found to increase in the usual way with increasing BN content for all the particle types and sizes. For the platelets, the thermal conductivity increases with increasing particle size, mirroring the effect of BN content on the cure kinetics. The agglomerates, though, give the highest values of thermal conductivity, contrary to what might be expected in the light of their specific surface areas. Scanning electron microscopy of the fracture surfaces of the cured composites has been used to show that the interface between epoxy matrix and filler particles is better for the agglomerates. This, together with the reduced interfacial area, explains their higher thermal conductivity.Postprint (published version

Study of the molecular dynamics of multiarm star polymers with a poly(ethyleneimine) core and poly(lactide) multiarms

© 2017 by the authors; licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).Multiarm star polymers, denoted PEIx-PLAy and containing a hyperbranched poly(ethyleneimine) (PEI) core of different molecular weights x and poly(lactide) (PLA) arms with y ratio of lactide repeat units to N links were used in this work. Samples were preconditioned to remove the moisture content and then characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and dielectric relaxation spectroscopy (DRS). The glass transition temperature, Tg, is between 48 and 50 °C for all the PEIx-PLAy samples. The dielectric curves show four dipolar relaxations: γ, β, α, and α′ in order of increasing temperature. The temperatures at which these relaxations appear, together with their dependence on the frequency, allows relaxation maps to be drawn, from which the activation energies of the sub-Tg γ- and β-relaxations and the Vogel–Fulcher–Tammann parameters of the α-relaxation glass transition are obtained. The dependence of the characteristic features of these relaxations on the molecular weight of the PEI core and on the ratio of lactide repeat units to N links permits the assignation of molecular motions to each relaxation. The γ-relaxation is associated with local motions of the –OH groups of the poly(lactide) chains, the β-relaxation with motions of the main chain of poly(lactide), the α-relaxation with global motions of the complete assembly of PEI core and PLA arms, and the α′-relaxation is related to the normal mode relaxation due to fluctuations of the end-to-end vector in the PLA arms, without excluding the possibility that it could be a Maxwell–Wagner–Sillars type ionic peak because the material may have nano-regions of different conductivityPeer ReviewedPostprint (published version

Highly exfoliated nanostructure in trifunctional epoxy/clay nanocomposites using boron trifluoride as initiator

Epoxy/clay nanocomposites based upon a trifunctional epoxy resin, triglycidyl p-amino phenol (TGAP), have been prepared by intercalating an initiator of cationic homopolymerization, a boron trifluoride monoethylamine (BF3·MEA) complex, into the montmorillonite clay galleries before the addition of the TGAP and the curing agent, 4,4-diamino diphenyl sulfone (DDS), and effecting the isothermal curing reaction. The BF3·MEA enhances the intragallery cationic homopolymerization reaction, which occurs before the extragallery cross-linking reaction of the TGAP with the DDS, and which hence contributes positively to the mechanism of exfoliation of the clay. The effects of isothermal cure temperature and of BF3·MEA content have been studied, in respect of both the reaction kinetics, monitored by differential scanning calorimetry, and the nanostructure, as identified by small-angle X-ray scattering and transmission electron microscopy. It is shown that the use of BF3·MEA in this way as an initiator of intragallery homopolymerization significantly improves the degree of exfoliation in the cured nanocomposites.The authors are grateful to Huntsman Corporation for the epoxy resin and curing agent. This work was supported financially by MINECO Project MAT2011-27039-C03 and the Generalitat de Catalunya (2009-SGR-1512). FS is grateful for a grant from the Agència de Gestió d'Ajuts Universitaris i de Recerca (AGAUR), FI-DGR 2011 and XF-F acknowledges the contract JCI-2010-06187.Peer ReviewedPostprint (author's final draft