References of "Thomassin, Jean-Michel"
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See detailDouble thermo-responsive hydrogels from poly(vinylcaprolactam) containing diblock and triblock copolymers
Thomassin, Jean-Michel ULg; Mathieu, Kevin ULg; Kermagoret, Anthony ULg et al

in Polymer Chemistry (2015), 6(10), 1856-1864

The thermally-induced gelation and gel properties of concentrated aqueous solutions of double thermoresponsive poly(N-vinylamide)-based di- and triblock copolymers are studied by rheology. The copolymers ... [more ▼]

The thermally-induced gelation and gel properties of concentrated aqueous solutions of double thermoresponsive poly(N-vinylamide)-based di- and triblock copolymers are studied by rheology. The copolymers under investigation, prepared by cobalt-mediated radical polymerization and coupling reactions, are composed of poly(vinylcaprolactam) (PNVCL) blocks and of a statistical poly(vinylcaprolactam-stat-vinylpyrrolidone) segment with a cloud point temperature (TCP) higher than that of PNVCL. Heating the di- and triblock solutions beyond the first phase transition temperature favors gel formation while heating above the second TCP leads to opaque gels without macroscopic demixing. Moduli of the triblock hydrogels are systematically higher than those of the corresponding diblocks, even above the second transition. Rheological data suggest distinct micellar structures for each copolymer architecture: densely packed micelles of diblocks and 3-D networks of bridged micelles for triblocks. Strain sweep experiments also emphasize the positive effect of the micelle bridging on the elasticity and stability of the hydrogels. The formation and properties of the obtained gels are also shown to depend on the copolymer concentration, block length, and composition. Addition of salt also allows us to tune the phase transition temperatures of these double thermoresponsive hydrogels. [less ▲]

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See detailGradient foaming of polycarbonate/carbon nanotube based nanocomposites with supercritical carbon dioxide and their EMI shielding performances
Monnereau, Laure; Urbanczyk, Laetitia; Thomassin, Jean-Michel ULg et al

in Polymer (2015), 59

Sorption and diffusion of supercritical carbon dioxide (scCO2) into polycarbonate (PC) nanocomposites loaded with 0, 1 and 2 wt% of multi-walled carbon nanotubes (MWNTs) have been investigated. After ... [more ▼]

Sorption and diffusion of supercritical carbon dioxide (scCO2) into polycarbonate (PC) nanocomposites loaded with 0, 1 and 2 wt% of multi-walled carbon nanotubes (MWNTs) have been investigated. After determination of the saturation equilibrium, the samples have been saturated with scCO2 to ensure a partial foaming with a density gradient from the surface to the center of the samples and the morphology of the porous materials has been analysed by SEM. The gradient materials were very advantageous for EMI shielding since the foamed structure at the surface had low dielectric constant and limited the reflection of the EM signal while the presence of highly conductive solid in the middle ensured a high absorption of the electromagnetic radiation. [less ▲]

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See detailIn situ investigation of scCO2 assisted impregnation of drug into polymer by high pressure FTIR micro-spectroscopy
Champeau, Mathilde ULg; Thomassin, Jean-Michel ULg; Jérôme, Christine ULg et al

in Analyst (2015), 140(3), 869-879

An original experimental set-up combining a FTIR microscope with a high pressure cell has been built in order to analyze in-situ the impregnation of solute into microscopic polymer samples, such as fibers ... [more ▼]

An original experimental set-up combining a FTIR microscope with a high pressure cell has been built in order to analyze in-situ the impregnation of solute into microscopic polymer samples, such as fibers or films, subjected to supercritical CO2. Thanks to this experimental set-up, key factors governing the impregnation process can be simultaneously followed such as the swelling of the polymeric matrix, the CO2 sorption, the kinetic of impregnation and the drug loading into the matrix. Moreover, the solute/polymer interactions and the speciation of the solute can be analyzed. We have monitored in situ the impregnation of aspirin and ketoprofen into PEO (Polyethylene Oxide) platelets at T=40°C and P=5; 10 and 15 MPa. The kinetic of impregnation of aspirin was quicker than the one of ketoprofen and the final drug loading was also higher in case of aspirin. Whereas the CO2 sorption and the PEO swelling remain constant when PEO is just subjected to CO2 under isobaric conditions, we noticed that both parameters can increase while the drug impregnates PEO. Coupling these results with DSC measurements, we underlined the plasticizing effect of the drug that also leads to decrease the crystallinity of PEO in situ thus favoring the sorption of CO2 molecules into the matrix and the swelling of the matrix. The plasticizing effect increases with the drug loading. Finally, the speciation of drug was investigated considering the shift of the carboxyl bands of the drugs. Both drugs were found to be mainly homogeneously dispersed into PEO. [less ▲]

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See detailNanocomposite foams of polypropylene and carbon nanotubes: preparation, characterization, and evaluation of their performance as EMI absorbers
Tran, Minh-Phuong; Thomassin, Jean-Michel ULg; Alexandre, Michaël et al

in Macromolecular Chemistry and Physics (2015), 216(12), 1302-1312

Highly expanded nanocomposite foams of polypropylene and carbon nanotubes (PP/CNT) are formed using supercritical carbon dioxide (scCO 2 ) technology. The foaming parameters (temperature, pressure) are ... [more ▼]

Highly expanded nanocomposite foams of polypropylene and carbon nanotubes (PP/CNT) are formed using supercritical carbon dioxide (scCO 2 ) technology. The foaming parameters (temperature, pressure) are investigated to establish their infl uence on the morphology of the resulting foams and their impact on the electrical con- ductivity. As promising electromagnetic-interference (EMI) absorbers, the EMI shielding performance of the foams is determined, and a preliminary relationship is established between foam morphology and the EMI shielding perfor- mance. The best candidates are highly expanded foams with a volume expansion of >25, containing 0.1 vol% CNTs; they are able to absorb more than 90% of the incident radiation between 25 and 40 GHz. [less ▲]

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See detailNanocomposites based on MWCNT and polystyrene, styrene-acrylonitrile copolymer, or polymethylmethacrylate, obtained by miniemulsion polymerization
Donescu, Dan; Corobea, Mihai Cosmin; Petcu, Cristian et al

in Journal of Applied Polymer Science (2014), 131(23), 411481-10

Free radical miniemulsion polymerization of styrene (St), St/acrylonitrile 3 : 1 mixture or methylmethacrylate in the presence of multiwalled carbon nanotubes (MWCNT) was proven as a convenient way to ... [more ▼]

Free radical miniemulsion polymerization of styrene (St), St/acrylonitrile 3 : 1 mixture or methylmethacrylate in the presence of multiwalled carbon nanotubes (MWCNT) was proven as a convenient way to obtain homogenous hybrids with perspectives in associated applications like foams specialties materials. Miniemulsion polymerization was viable up to 2% wt. MWCNT to monomer, without agglomerations. The grafting on MWCNT during the polymerization occurs without the need for supplementary functionalization and the polymer grafted nanotubes showed stable dispersions in the polymer solvent. Monomer polarity affected the grafting ability during the polymerization process. The nanocomposites obtained after purification and drying were used in foaming process. MWCNT presence in the related nanocomposites decreased the pore sizes in foam-like materials (for all three different matrices). At 1 wt % MWCNT content, low density (< 0.3 g/cm3), low pore size (< 10 μm) and high cell density (>109 cell/cm3) were achieved. [less ▲]

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See detailDouble thermoresponsive di- and triblock copolymers based on N-vinylcaprolactam and N-vinylpyrrolidone: synthesis and comparative study of solution behaviour
Kermagoret, Anthony ULg; Mathieu, Kevin ULg; Thomassin, Jean-Michel ULg et al

in Polymer Chemistry (2014), 5(22), 6534-6544

Poly(N-vinylcaprolactam) (PNVCL) and poly(N-vinylpyrrolidone) (PNVP) are water soluble polymers of interest especially in the biomedical field. Moreover, PNVCL is characterized by a lower critical ... [more ▼]

Poly(N-vinylcaprolactam) (PNVCL) and poly(N-vinylpyrrolidone) (PNVP) are water soluble polymers of interest especially in the biomedical field. Moreover, PNVCL is characterized by a lower critical solution temperature close to 36 °C in water, which makes it useful for the design of thermoresponsive systems. In this context, we used the cobalt-mediated radical polymerization (CMRP) and reaction coupling (CMRC) for synthesizing a series of well-defined NVCL and NVP-based copolymers, including statistical copolymers as well as double thermoresponsive diblocks and triblocks. Dynamic light scattering and turbidimetry analyses highlighted the crucial impact of the copolymer composition and architecture on the cloud point temperature (TCP) of each segment and also their influence on the multistep assembly behaviour of block copolymers. Addition of NaCl enabled us to adjust the inter-TCP range of the di- and triblock in which selective precipitation of one block and self-assembly of the copolymer were favoured. Overall, data presented here provide a basis for the synthesis of a broad range of NVCL/NVP based copolymer architectures with a tunable thermal response in water. [less ▲]

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See detailRecyclable shape-memory materials based on photo or thermo-reversible crosslinking
Defize, Thomas ULg; Riva, Raphaël ULg; Wauters, Céline et al

Poster (2014, November 11)

Shape memory polymers (SMPs) are remarkable materials able to switch from a stressed deformed state (temporary shape) to their initial relaxed state (permanent shape) by the application of a stimulus ... [more ▼]

Shape memory polymers (SMPs) are remarkable materials able to switch from a stressed deformed state (temporary shape) to their initial relaxed state (permanent shape) by the application of a stimulus, such as heat or light. Typically, the shape memory property is generally observed for chemically or physically cross-linked polymers that exhibit an elastomeric behavior above a phase transition, e.g. glass or melting transition. Cross-linked semi-crystalline poly(ε-caprolactone) (PCL) is already widely studied for the development of SMPs. However, the tensile strength of standard PCL-based SMPs remains quite low, limiting their use in some applications. A convenient way to enhance the strength of SMPs relies on the introduction of nanofillers, such as silica nanoparticles, leading to an enhancement of mechanical strength. Moreover, silica nanoparticles can be advantageously used as multifunctional crosslinking nodes, with the purpose to increase the cross-linking density of the material. As most of SMPs are irreversibly cross-linked material, their reprocessing is impossible preventing any recycling. Thereby, reversible reactions, allowing the formation/cleavage of the network, raise tremendous interest in macromolecular engineering. Recently, a reversibly cross-linked 4-arm star-shaped PCL-based SMP was prepared using the Diels-Alder (DA) reaction between furan and maleimide moieties, well-known to create reversible bonds. This shape memory material demonstrated to be implementable, and so recyclable, and was characterized by excellent fixity and recovery before and after recycling experiments. However, the relatively low retro-DA temperature of the furan- maleimide adducts led to an inelastic deformation during shape memory tensile cycles. In order to get rid of this drawback, two alternative approaches were investigated. Firstly, the substitution of the DA reaction by a photo-reversible reaction, typically the photo- induced (2+2) cycloaddition of coumarins, was proposed to crosslink the PCL matrix. The second approach is based on the use of surface functionalized silica nanoparticles as crosslinking nodes with the purpose to increase the crosslinking density of the material. The network formation and cleavage were studied by solid-state NMR and rheology.4 The resulting shape memory materials were characterized by excellent one-way and two-way shape memory properties as demonstrated by dynamical mechanical analysis. [less ▲]

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See detailA facile and fast electrochemical route to produce functional few-layer graphene sheets for lithium battery anode application
Ouhib, Farid ULg; Aqil, Abdelhafid ULg; Thomassin, Jean-Michel ULg et al

in Journal of Materials Chemistry A (2014), 2(37), 15298-15302

A simple approach for the production of polymer functionalized graphene nanosheets is reported. The resulting polyacrylonitrile chemisorbed on graphene sheets is made of 1 to 2 layers, with a large ... [more ▼]

A simple approach for the production of polymer functionalized graphene nanosheets is reported. The resulting polyacrylonitrile chemisorbed on graphene sheets is made of 1 to 2 layers, with a large majority of graphene single-layers. This novel functionalized graphene exhibits good cycling stability as an anode in Li-ion batteries without a conductive additive or binder. [less ▲]

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See detailElaboration of degradable PCL-based shape memory materials
Defize, Thomas ULg; Thomassin, Jean-Michel ULg; Alexandre, Michaël et al

Poster (2014, September 02)

Shape memory polymers (SMPs) are smart materials presenting the remarkable property to switch from a temporary shape (stressed) to a permanent shape (relaxed) upon exposure to a stimulus, such as heat or ... [more ▼]

Shape memory polymers (SMPs) are smart materials presenting the remarkable property to switch from a temporary shape (stressed) to a permanent shape (relaxed) upon exposure to a stimulus, such as heat or light. SMPs raised a lot of interest, especially for biomedical applications, for the elaboration of suture wires and stents. In the last few years, biodegradable aliphatic polyesters, typically poly(ɛ-caprolactone) (PCL) and poly(lactide) (PLA) were widely studied for the synthesis of SMPs. This communication aims at reporting a new concept for the synthesis of PCL-based SMPs. In order to meet the increasingly stringent requirements of biomedical applications, a metal-free process is proposed occurring at relatively low temperature, which can be compatible with the presence of a drug during implementation. [less ▲]

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See detailSupercritical CO2, impregnation to prepare drug-loaded implants: inpregantion of anti-inflammatory drugs into sutures
Champeau, Mathilde; Tassaing, Thierry; Thomassin, Jean-Michel ULg et al

Conference (2014, July 10)

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See detailIn situ FTIR micro-spectroscopy to investigate polymeric fibers under supercritical carbon dioxide: CO2 sorption and swelling measurements
Champeau, Mathilde; Thomassin, Jean-Michel ULg; Jérôme, Christine ULg et al

in Journal of Supercritical Fluids (2014), 90

An original experimental set-up combining a FTIR (Fourier Transformed InfraRed) microscope with a high pressure cell has been built in order to analyze in situ and simultaneously the CO2 sorption and the ... [more ▼]

An original experimental set-up combining a FTIR (Fourier Transformed InfraRed) microscope with a high pressure cell has been built in order to analyze in situ and simultaneously the CO2 sorption and the polymer swelling of microscopic polymer samples, such as fibers, subjected to supercritical carbon dioxide. Thanks to this experimental set-up, we have determined as a function of the CO2 pressure (from 2 to 15 MPa) the CO2 sorption and the polymer swelling at T = 40 °C of four polymer samples, namely PEO (polyethylene oxide), PLLA (poly-l-lactide acid), PET (polyethylene terephtalate) and PP (polypropylene). The quantity of CO2 sorbed in all the studied polymers increases with pressure. PEO and PLLA display a significant level of CO2 sorption (20 and 25% respectively, at P = 15 MPa). However, we observe that a lower quantity of CO2 can be sorbed into PP and PET (7 and 8% respectively, at P = 15 MPa). Comparing their thermodynamic behaviors and their intrinsic properties, we emphasize that a high CO2 sorption can be reach if on one hand, the polymer is able to form specific interaction with CO2 in order to thermodynamically favor the presence of CO2 molecules inside the polymer and on the other, displays high chains mobility in the amorphous region. PLLA and PEO fulfilled these two requirements whereas only one property is fulfilled by PET (specific interaction with CO2) and PP (high chains mobility). Finally, we have found that for a given CO2 sorption, the resulting swelling of the polymer depends mainly on its crystallinity. [less ▲]

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See detailComprehensive study of chemically cross-linked PCLs presenting one-way and two-way shape memory properties
Defize, Thomas ULg; Riva, Raphaël ULg; Thomassin, Jean-Michel ULg et al

Poster (2014, May 26)

Poly(ε-caprolactone) (PCL), a semi-crystalline polymer, is one of the most widely studied polymers for the development of shape memory materials when chemically cross-linked. PCL presents several ... [more ▼]

Poly(ε-caprolactone) (PCL), a semi-crystalline polymer, is one of the most widely studied polymers for the development of shape memory materials when chemically cross-linked. PCL presents several advantages such as a melting transition temperature close to human body temperature, a high biocompatibility and is (bio)degradable. So, this polymer is highly relevant for both biomedical devices such as stents or resorbable suture wires and also for degradable packaging. However, after cross-linking, the material can not be reprocessed, preventing any reuse/recycling of the material. One of the purposes of this work is to find a solution to this major drawback, which would then allow, for example, to reshape packaging films after use or to recycle trimmings remaining after fabrication. Amongst current trends in the design of new polymer and composite materials, the use of organic reactions that are able to create and reversibly disrupt chemical bonds upon an external stimulus (temperature, irradiation,…) is currently gaining more and more attention as it can lead to applications in various areas such as remendable materials, drug delivery systems, stimulus-degrading materials or recyclable materials. Amongst all the reversible links described in the literature, thermally (4+2) reversible cycloadditions present interesting features such as the creation of robust bonds and well defined reversibility conditions. As an example, the application of furan/maleimide adducts as covalent link, which cycloreversion is largely favored in the range of temperature (90-120°C), is widely reported. Typically, PCL-based shape memory materials have been prepared by mixing a stoichiometric amount of diene-bearing and maleimide-bearing PCLs in a twin-screw mini-extruder at a temperature at which DA cycloaddition is largely disfavored, followed by the curing of the blend above the melting temperature to improve the kinetic of DA adduct formation. The shape memory properties of the materials have been studied by cyclic tensile thermomechanical analysis. As cross-linked PCLs are knowned to exhibit one-way and two-way shape memory properties, a comprehensive study of the shape memory of these materials has been carried out. Unfortunately, creep from shape memory cycle to cycle was observed in DMA for the furan/maleimide sample, certainly due to the reversibility of the adduct. In order to limit this creep effect, the substitution of the furan/maleimide adduct by a more stable adduct is required. The anthracene/maleimide system was tested because this adduct is more stable under stress than the furan/maleimide one. This contribution aims at reporting a complete study of one-way and two-way shape memory properties of the PCL cross-linked by anthracene/maleimide adduct. The shape memory properties of this material have been assessed by DMA and DSC experiments. [less ▲]

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See detailUse of supercritical carbon dioxide to prepare drug-laoded polymer implants: impregnation of anti-inflammatory drugs into sutures
Champeau, Mathilde; Tassaing, Thierry; Thomassin, Jean-Michel ULg et al

Conference (2014, May 19)

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See detailSupercritical CO2 and polycarbonate based nanocomposites: A critical issue for foaming
Monnereau, Laure; Urbanczyk, Laetitia; Thomassin, Jean-Michel ULg et al

in Polymer (2014), 55(10), 2422-2431

Supercritical carbon dioxide readily induced foaming of various polymers. In that context, supercritical CO2 was applied to carbon nanotubes based polycarbonate nanocomposites to ensure their foaming ... [more ▼]

Supercritical carbon dioxide readily induced foaming of various polymers. In that context, supercritical CO2 was applied to carbon nanotubes based polycarbonate nanocomposites to ensure their foaming. Surprisingly, efficient foaming only occurs when low pressure is applied while at high pressure, no expansion of the samples was observed. This is related to the ability of supercritical carbon dioxide to induce crystallization of amorphous polycarbonate. Moreover, this behaviour is amplified by the presence of carbon nanotubes that act as nucleating agents for crystals birth. The thermal behaviour of the composites was analysed by DSC and DMA and was related to the foaming observations. The uniformity of the cellular structure was analysed by scanning electron microscopy (SEM). By saturating the polycarbonate nanocomposites reinforced with 1 wt% of MWNTs at 100 bar and 100 °C during 16 h, microcellular foams were generated, with a density of 0.62, a cell size ranging from 0.6 to 4 μm, and a cellular density of 4.1 × 1011 cells cm−3. The high ability of these polymeric foams to absorb electromagnetic radiation was demonstrated at low MWNT content as the result of the high affinity of the polycarbonate matrix for MWNTs, and therefore to the good MWNTs dispersion. [less ▲]

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See detailPoly(methyl methacrylate)/graphene oxide nanocomposites by a precipitation polymerization process and their dielectric and rheological characterization
Thomassin, Jean-Michel ULg; Trifkovic, Milana; Alkarmo, Walid et al

in Macromolecules (2014), 47(6), 2149-2155

We report a method for achieving controlled dispersion of graphene oxide (GO) in poly(methyl methacrylate) (PMMA) via the precipitation polymerization process in a water/ methanol mixture. GO acts as a ... [more ▼]

We report a method for achieving controlled dispersion of graphene oxide (GO) in poly(methyl methacrylate) (PMMA) via the precipitation polymerization process in a water/ methanol mixture. GO acts as a surfactant and adsorbs on the interface between polymerized PMMA particles and solvent mixture. Scanning electron and transmission electron microscopy confirmed that the precipitate consists of polymer particles (<1 μm) surrounded by the GO sheets. Compression molding of the precipitate yields a polymer nanocomposite with the GO organized into a regularly spaced 3D network which percolates at 0.2 wt % GO. Simple thermal reduction of the GO sheets dispersed in PMMA at relatively low temperature (210 °C) achieved electrical conductivity higher than 10−2 S/m at 0.4 wt % of GO. Parallel dielectric and rheological characterization demonstrated that the thermal reduction is a quite fast process without significant degradation of the polymer. The study should open up new opportunities in the design of GO-based polymer nanocomposites. [less ▲]

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See detailUse of supercritical carbon dioxide to prepare drug-loaded polymeric sutures
Champeau, Mathilde; Tassaing, Thierry; Jérôme, Christine ULg et al

Conference (2014, March 19)

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See detailRheological characterization of double thermo-responsive block copolymer hydrogels
Thomassin, Jean-Michel ULg; Mathieu, Kevin ULg; Kermagoret, Anthony ULg et al

Poster (2013, November 20)

The ability of double thermoresponsive block copolymers to form hydrogels has been thoroughly studied by rheology. These copolymers having two discrete LCSTs were synthesized following a one-pot strategy ... [more ▼]

The ability of double thermoresponsive block copolymers to form hydrogels has been thoroughly studied by rheology. These copolymers having two discrete LCSTs were synthesized following a one-pot strategy based on the sequential cobalt mediated radical polymeryzation of N-vinylcaprolactam (NVCL) followed by the copolymerization of N-vinylpyrrolidone (NVP) with the residual NVCL.Moreover, the very efficient cobalt mediated radical coupling of the growing chains was advantageously used to design triblock copolymers with similar morphological characteristics than the diblock copolymers (same external block length, copolymer ratio…) allowing direct comparison between their respective gels to be established. Different parameters have been compared such as the block length and the copolymer concentration. Temperature ramps were first performed to distinguish the different states, i.e., solubilized copolymers (below the two LCSTs), micelles (between the two LCSTs) and precipitated polymers (above the two LCSTs). [less ▲]

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