Remarkable Thermal Conductivity of Epoxy Composites Filled with Boron Nitride and Cured under Pressure.

This work demonstrates that the application of even moderate pressures during cure can result in a remarkable enhancement of the thermal conductivity of composites of epoxy and boron nitride (BN). Two systems have been used: epoxy-thiol and epoxy-diamine composites, filled with BN particles of different sizes and types: 2, 30 and 180 µm platelets and 120 µm agglomerates. Using measurements of density and thermal conductivity, samples cured under pressures of 175 kPa and 2 MPa are compared with the same compositions cured at ambient pressure. The thermal conductivity increases for all samples cured under pressure, but the mechanism responsible depends on the composite system: For epoxy-diamine composites, the increase results principally from a reduction in the void content; for the epoxy-thiol system with BN platelets, the increase results from an improved matrix-particle interface; for the epoxy-thiol system with BN agglomerates, which has a thermal conductivity greater than 10 W/mK at 44.7 vol.% filler content, the agglomerates are deformed to give a significantly increased area of contact. These results indicate that curing under pressure is an effective means of achieving high conductivity in epoxy-BN composites.

Densification: A Route towards Enhanced Thermal Conductivity of Epoxy Composites.

When an amorphous polymer is cooled under pressure from above its glass transition temperature to room temperature, and then the pressure is released, this results in a densified state of the glass. This procedure applied to an epoxy composite system filled with boron nitride (BN) particles has been shown to increase the density of the composite, reduce its enthalpy, and, most importantly, significantly enhance its thermal conductivity. An epoxy-BN composite with 58 wt% BN platelets of average size 30 µm has been densified by curing under pressures of up to 2.0 MPa and then cooling the cured sample to room temperature before releasing the pressure. It is found that the thermal conductivity is increased from approximately 3 W/mK for a sample cured at ambient pressure to approximately 7 W/mK; in parallel, the density increases from 1.55 to 1.72 ± 0.01 g/cm3. This densification process is much more effective in enhancing the thermal conductivity than is either simply applying pressure to consolidate the epoxy composite mixture before curing or applying pressure during cure but then removing the pressure before cooling to room temperature; this last procedure results in a thermal conductivity of approximately 5 W/mK. Furthermore, it has been shown that the densification and corresponding effect on the thermal conductivity is reversible; it can be removed by heating above the glass transition temperature and then cooling without pressure and can be reinstated by again heating above the glass transition temperature and then cooling under pressure. This implies that a densified state and an enhanced thermal conductivity can be induced even in a composite prepared without the use of pressure.

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.

Study of Hyperbranched Poly(ethyleneimine) Polymers of Different Molecular Weight and Their Interaction with Epoxy Resin.

Two different commercial hyperbranched poly(ethyleneimine)s (HBPEI), with molecular weights (MW) of 800 and 25,000 g/mol, and denoted as PEI800 and PEI25000, respectively, as well as the mixtures with a Diglycidyl Ether of Bisphenol-A (DGEBA) epoxy resin, have been studied using thermal analysis techniques (DSC, TGA), dielectric relaxation spectroscopy (DRS), and dynamic mechanical analysis (DMA). Only a single glass transition is observed in these mixtures by DSC. DRS of the HBPEIs shows three dipolar relaxations: γ, ß, and α. The average activation energy for the γ-relaxation is similar for all HBPEIs and is associated with the motion of the terminal groups. The ß-relaxation has the same average activation energy for both PEI800 and PEI25000; this relaxation is attributed to the mobility of the branches. The α-relaxation peak for all the HBPEIs is an asymmetric peak with a shoulder on the high temperature side. This shoulder suggests the existence of ionic charge trapped in the PEI. For the mixtures, the γ- and ß-relaxations follow the behaviour of the epoxy resin alone, indicating that the epoxy resin dominates the molecular mobility. The α-relaxation by DRS is observed only as a shoulder, as a consequence of an overlap with conductivity effects, whereas by DMA, it is a clear peak.

Study of the Molecular Dynamics of Multiarm Star Polymers with a Poly(ethyleneimine) Core and Poly(lactide) Multiarms.

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, ß, 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 ß-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 ß-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 conductivity.

Molecular Mobility in Hyperbranched Polymers and Their Interaction with an Epoxy Matrix.

The molecular mobility related to the glass transition and secondary relaxations in a hyperbranched polyethyleneimine, HBPEI, and its relaxation behaviour when incorporated into an epoxy resin matrix are investigated by dielectric relaxation spectroscopy (DRS) and dynamic mechanical analysis (DMA). Three systems are analysed: HBPEI, epoxy and an epoxy/HBPEI mixture, denoted ELP. The DRS behaviour is monitored in the ELP system in three stages: prior to curing, during curing, and in the fully cured system. In the stage prior to curing, DRS measurements show three dipolar relaxations: γ, ß and α, for all systems (HBPEI, epoxy and ELP). The α-relaxation for the ELP system deviates significantly from that for HBPEI, but superposes on that for the epoxy resin. The fully cured thermoset displays both ß- and α-relaxations. In DMA measurements, both α- and ß-relaxations are observed in all systems and in both the uncured and fully cured systems, similar to the behaviour identified by DRS.

A New Epoxy-Based Layered Silicate Nanocomposite Using a Hyperbranched Polymer: Study of the Curing Reaction and Nanostructure Development.

Polymer layered silicate (PLS) nanocomposites have been prepared with diglycidyl ether of bisphenol-A (DGEBA) epoxy resin as the matrix and organically modified montmorillonite (MMT) as the clay nanofiller. Resin-clay mixtures with different clay contents (zero, two, five and 10 wt%) were cured, both isothermally and non-isothermally, using a poly(ethyleneimine) hyperbranched polymer (HBP), the cure kinetics being monitored by differential scanning calorimetry (DSC). The nanostructure of the cured nanocomposites was characterized by small angle X-ray scattering (SAXS) and transmission electron microscopy (TEM), and their mechanical properties were determined by dynamic mechanical analysis (DMA) and impact testing. The results are compared with an earlier study of the structure and properties of the same DGEBA-MMT system cured with a polyoxypropylene diamine, Jeffamine. There are very few examples of the use of HBP as a curing agent in epoxy PLS nanocomposites; here, it is found to enhance significantly the degree of exfoliation of these nanocomposites compared with those cured with Jeffamine, with a corresponding enhancement in the impact energy for nanocomposites with the low clay content of 2 wt%. These changes are attributed to the different cure kinetics with the HBP, in which the intra-gallery homopolymerization reaction is accelerated, such that it occurs before the bulk cross-linking reaction.

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 methyl amine 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.