15 results on '"Hutchinson, John"'
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2. Thermal analysis of polymer layered silicate nanocomposites: Identification of nanostructure development by DSC
- Author
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Shiravand, Fatemeh, Fraga, Iria, Cortés, Pilar, Calventus, Yolanda, and Hutchinson, John M.
- Published
- 2014
- Full Text
- View/download PDF
3. Epoxy-Thiol Systems Filled with Boron Nitride for High Thermal Conductivity Applications.
- Author
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Hutchinson, John M., Román, Frida, and Folch, Adrià
- Subjects
- *
BORON nitride , *EPOXY compounds , *THIOLS , *THERMAL conductivity , *AGGLOMERATES (Chemistry) , *DIFFERENTIAL scanning calorimetry - Abstract
An epoxy-thiol system filled with boron nitride (BN), in the form of 80 μm agglomerates, 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 (DSC) 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 not: with increasing BN content, the reaction first advances and is then delayed, this behaviour being more pronounced than for the same system with 6 μm BN particles, investigated previously. This dependence on BN content is attributed to the effects of heat transfer, and the DSC results can be correlated with the thermal conductivity of the cured systems, which is found to increase with both BN content and BN particle size. For a given BN content, the values of thermal conductivity obtained are significantly higher than many others reported in the literature, and achieve a value of over 4.0 W/mK for a BN content of about 40 vol %. [ABSTRACT FROM AUTHOR]
- Published
- 2018
- Full Text
- View/download PDF
4. Study of the Molecular Dynamics of Multiarm Star Polymers with a Poly(ethyleneimine) Core and Poly(lactide) Multiarms.
- Author
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Román, Frida, Colomer, Pere, Calventus, Yolanda, and Hutchinson, John M.
- Subjects
POLYLACTIC acid ,POLYETHYLENEIMINE ,ELECTRIC conductivity ,STAR-branched polymers ,DIFFERENTIAL scanning calorimetry - Abstract
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 (T
g A), 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 α-relaxations and the Vogel-Fulcher-Tammann parameters of the β-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 -relaxation is associated with local motions of the -OH groups of the poly(lactide) chains, the α-relaxation with motions of the main chain of poly(lactide), the β-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. [ABSTRACT FROM AUTHOR]- Published
- 2017
- Full Text
- View/download PDF
5. A novel comparative study of different layered silicate clay types on exfoliation process and final nanostructure of trifunctional epoxy nanocomposites.
- Author
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Shiravand, Fatemeh, Hutchinson, John M., and Calventus, Yolanda
- Subjects
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SILICATES , *EPOXY resins , *CLAY , *NANOCOMPOSITE materials , *DIFFERENTIAL scanning calorimetry , *COMPARATIVE studies , *THERMOPHYSICAL properties - Abstract
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. [ABSTRACT FROM AUTHOR]
- Published
- 2016
- Full Text
- View/download PDF
6. Molecular Mobility in Hyperbranched Polymers and Their Interaction with an Epoxy Matrix.
- Author
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Román, Frida, Colomer, Pere, Calventus, Yolanda, and Hutchinson, John M.
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GLASS transitions ,POLYETHYLENEIMINE ,EPOXY resins ,DYNAMIC mechanical analysis ,POLYMERS - Abstract
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,βand 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 β- and α-relaxations. In DMA measurements, both α- and β-relaxations are observed in all systems and in both the uncured and fully cured systems, similar to the behaviour identified by DRS. [ABSTRACT FROM AUTHOR]
- Published
- 2016
- Full Text
- View/download PDF
7. Highly exfoliated nanostructure in trifunctional epoxy/clay nanocomposites using boron trifluoride as initiator.
- Author
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Hutchinson, John M., Shiravand, Fatemeh, Calventus, Yolanda, Fernández ‐ Francos, Xavier, and Ramis, Xavier
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CHEMICAL peel ,NANOSTRUCTURED materials ,FUNCTIONAL groups ,BORON trifluoride ,EPOXY resins ,HOMOPOLYMERIZATIONS - Abstract
ABSTRACT 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 (BF
3 ·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. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014, 131, 40020. [ABSTRACT FROM AUTHOR]- Published
- 2014
- Full Text
- View/download PDF
8. A New Epoxy-Based Layered Silicate Nanocomposite Using a Hyperbranched Polymer: Study of the Curing Reaction and Nanostructure Development.
- Author
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Cortés, Pilar, Fraga, Iria, Calventus, Yolanda, Román, Frida, Hutchinson, John M., and Ferrando, Francesc
- Subjects
BINDING agents ,ELECTRON microscopy ,EPOXY resins ,SYNTHETIC gums & resins ,TRANSMISSION electron microscopy - Abstract
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. [ABSTRACT FROM AUTHOR]
- Published
- 2014
- Full Text
- View/download PDF
9. Intra- and extra-gallery reactions in tri-functional epoxy polymer layered silicate nanocomposites.
- Author
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Hutchinson, John M., Shiravand, Fatemeh, and Calventus, Yolanda
- Subjects
CHEMICAL peel ,EPOXY resins ,POLYMERIZATION ,TRANSMISSION electron microscopy ,EXOTHERMIC reactions - Abstract
Achieving a high degree of exfoliation in epoxy-based polymer layered silicate (PLS) nanocomposites is crucial to their successful industrial application, but has hitherto proved elusive. In this work, a system is presented which shows significant promise in this respect. The isothermal cure of PLS nanocomposites based upon a tri-functional epoxy resin (TGAP) has been studied by DSC, and displays two exothermic peaks. The first peak, very rapid, relates to a homopolymerization reaction within the intra-gallery regions, while the second peak reflects the bulk crosslinking reaction. The occurrence of the intra-gallery reaction before the bulk reaction enhances the degree of exfoliation in the cured nanocomposite. Furthermore, pre-conditioning the resin/clay mixture before adding the curing agent and effecting the isothermal cure also allows a greater extent of intra-gallery reaction to occur before the extra-gallery epoxy-amine reaction. Consequently, this system results in a high degree of exfoliation, as revealed by transmission electron microscopy. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013 [ABSTRACT FROM AUTHOR]
- Published
- 2013
- Full Text
- View/download PDF
10. Isothermal and non-isothermal cure of a tri-functional epoxy resin (TGAP): A stochastic TMDSC study
- Author
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Hutchinson, John M., Shiravand, Fatemeh, Calventus, Yolanda, and Fraga, Iria
- Subjects
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EPOXY resins , *STOCHASTIC processes , *AMINO acids , *CALORIMETRY , *CHEMISTRY experiments , *GLASS transition temperature , *DEVITRIFICATION - Abstract
Abstract: The isothermal cure of a highly reactive tri-functional epoxy resin, tri-glycidyl para-amino phenol (TGAP), with diamino diphenyl sulphone (DDS), at two different cure temperatures T c has been studied by both conventional differential scanning calorimetry (DSC) and by a stochastic temperature modulated DSC technique, TOPEM. From a series of isothermal cure experiments for increasing cure times, the glass transition temperature T g as a function of isothermal cure time is determined by conventional DSC from a second (non-isothermal) scan, and the vitrification time t v is obtained as the time at which T g = T c. In parallel, TOPEM experiments at the same T c lead directly to the determination of t v from the sigmoidal change in the quasi-static heat capacity. It is not possible to identify the glass transition temperature of the fully cured system, T g∞, in a third scan by conventional DSC. In contrast, with TOPEM a second (non-isothermal) scan at 2K/min after the isothermal cure gives rise to three separate transitions: devitrification of the partially cured and vitrified material; almost immediate vitrification as the T g of the system again rises; finally another devitrification, at a temperature approximating closely to T g∞. Thus with TOPEM it is possible to obtain a calorimetric measure of the glass transition temperature of this fully cured system. [Copyright &y& Elsevier]
- Published
- 2012
- Full Text
- View/download PDF
11. Remarkable Thermal Conductivity of Epoxy Composites Filled with Boron Nitride and Cured under Pressure.
- Author
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Moradi, Sasan, Román, Frida, Calventus, Yolanda, Hutchinson, John M., and Bayraktar, Emin
- Subjects
THERMAL conductivity ,THERMAL conductivity measurement ,EPOXY resins ,BORON nitride - Abstract
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. [ABSTRACT FROM AUTHOR]
- Published
- 2021
- Full Text
- View/download PDF
12. Densification: A Route towards Enhanced Thermal Conductivity of Epoxy Composites.
- Author
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Moradi, Sasan, Román, Frida, Calventus, Yolanda, and Hutchinson, John M.
- Subjects
THERMAL conductivity ,GLASS transition temperature ,EPOXY resins ,BORON nitride ,ENTHALPY - Abstract
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/cm
3 . 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. [ABSTRACT FROM AUTHOR]- Published
- 2021
- Full Text
- View/download PDF
13. Achieving High Thermal Conductivity in Epoxy Composites: Effect of Boron Nitride Particle Size and Matrix-Filler Interface.
- Author
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Moradi, Sasan, Calventus, Yolanda, Román, Frida, and Hutchinson, John M
- Subjects
THERMAL conductivity ,BORON nitride ,PARTICLES ,HEAT of reaction ,EPOXY resins ,GLASS transition temperature - Abstract
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. [ABSTRACT FROM AUTHOR]
- Published
- 2019
- Full Text
- View/download PDF
14. Isothermal curing of polymer layered silicate nanocomposites based upon epoxy resin by means of anionic homopolymerisation.
- Author
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Román, Frida, Calventus, Yolanda, Colomer, Pere, and Hutchinson, John M.
- Subjects
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SILICATES , *EPOXY resins , *ADDITION polymerization , *HOMOPOLYMERIZATIONS , *POLYMER clay , *DIELECTRICS - Abstract
Highlights: [•] The nanocomposite with low content of clay displayed improved thermal properties. [•] The vitrification was observed in the isothermal curing. [•] Dielectric relaxations outside and inside of the clay galleries were detected. [Copyright &y& Elsevier]
- Published
- 2013
- Full Text
- View/download PDF
15. Identification of nanostructural development in epoxy polymer layered silicate nanocomposites from the interpretation of differential scanning calorimetry and dielectric spectroscopy
- Author
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Román, Frida, Calventus, Yolanda, Colomer, Pere, and Hutchinson, John M.
- Subjects
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DEVITRIFICATION , *DIELECTRIC relaxation , *NANOCOMPOSITE materials , *DIFFERENTIAL scanning calorimetry , *EPOXY compounds , *POLYMERIZATION - Abstract
Abstract: The effect of nanoclay on the non-isothermal cure kinetics of polymer layered silicate nanocomposites based upon epoxy resin is studied by calorimetric techniques (DSC and TGA) and by dielectric relaxation spectroscopy (DRS) in non-isothermal cure at constant heating rate. The cure process takes place by homopolymerisation, initiated anionically using 3wt% dimethylaminopyridine (DMAP), and the influence of the nanoclay content has been analysed. Interesting differences are observed between the nanocomposites with 2wt% and 5wt% clay content. At low heating rates, these samples vitrify and then devitrify during the cure. For the sample with 2wt% clay, the devitrification is accompanied by a thermally initiated homopolymerisation, which can be identified by DRS but not by DSC. The effect of this is to improve the exfoliation of the nanocomposite with 2wt% clay, as verified by transmission electron microscopy, with a corresponding increase in the glass transition temperature. These observations are interpreted in respect of the nanocomposite preparation method and the cure kinetics. [Copyright &y& Elsevier]
- Published
- 2012
- Full Text
- View/download PDF
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