References of "Leclère, Philippe"
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See detailNanostructured polymer blends: from core/shell nanoobjects to continuous three-phase morphologies
Lei, Liangcai; Detrembleur, Christophe ULg; Jeusette, Mélanie et al

in Macromolecular Materials and Engineering (2011), 296(2), 122-130

A PS-b-PIP-b-PMMA copolymer has been melt-blended with homo-PMMA with a similar molecular weight as the PMMA block. For a 50:50 wt.-% mixture, the components form 3D bicontinuous lamellae. Upon annealing ... [more ▼]

A PS-b-PIP-b-PMMA copolymer has been melt-blended with homo-PMMA with a similar molecular weight as the PMMA block. For a 50:50 wt.-% mixture, the components form 3D bicontinuous lamellae. Upon annealing at 190 °C, a more regular network is observed, which consists of PMMA and 55 nm-thick bilayered lamellae of triblock copolymer, both being continuous. This co-continuity persists even when of the homo-PMMA is twice that of the PMMA block in the copolymer. For 30:70 and 20:80 wt.-% copolymer/homopolymer pair, the copolymer forms cylindrical and spherical phases, respectively. Blends have also been prepared by solvent casting. Large domains of copolymer interconnected by few lamellae are observed in the 50:50 blend that reorganize into a bicontinuous network upon annealing. [less ▲]

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See detailPolymer coating of steel by a combination of electrografting and atom-transfer radical polymerization
Claes, Michaël; Voccia, Samuel; Detrembleur, Christophe ULg et al

in Macromolecules (2003), 36(16), 5926-5933

Cathodic electrografting of poly(2-chloropropionate ethyl acrylate) (poly[cPEA]) onto steel followed by the styrene grafting-from by atom transfer radical polymerization (ATRP) is an efficient strategy to ... [more ▼]

Cathodic electrografting of poly(2-chloropropionate ethyl acrylate) (poly[cPEA]) onto steel followed by the styrene grafting-from by atom transfer radical polymerization (ATRP) is an efficient strategy to impart strong adhesion to polystyrene films onto the electrically conductive substrate. Electrografting of poly(cPEA) chains at an appropriate potential and persistence of the activated chloride in the grafted chains were confirmed by XPS. Polystyrene deposition by ATRP with a ruthenium-based catalyst was analyzed by scanning electron microscopy and Raman spectroscopy. Adhesion of the polystyrene layer to the substrate is so strong that it cannot be detached by standard Scotch brand tapes. Moreover, local thermal analysis showed a loss of mobility for the PS chains tethered at the surface. [less ▲]

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See detailControlled free radical polymerization of styrene initiated from alkoxyamine attached to polyacrylate chemisorbed onto conducting surfaces
Voccia, Samuël; Jérôme, Christine ULg; Detrembleur, Christophe ULg et al

in Chemistry of Materials (2003), 15(4), 923-927

A new inimer that associates an alkoxyamine, which is an initiator/mediator in nitroxide mediated radical polymerization (NMP), and a polymerizable acrylate has been synthesized and used in a two-step ... [more ▼]

A new inimer that associates an alkoxyamine, which is an initiator/mediator in nitroxide mediated radical polymerization (NMP), and a polymerizable acrylate has been synthesized and used in a two-step "grafting-from" method. The acrylate has been first electropolymerized under a cathodic potential, such that the polymer is chemisorbed on the cathode. NMP of styrene has then been initiated from the electrografted polyacrylate chains with formation of polystyrene with controlled molecular weight and narrow polydispersity. [less ▲]

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See detailMorphology and mechanical properties of poly(methylmethacrylate)-b-poly(alkylacrylate)-b-poly(methylmethacrylate)
Tong, J. D.; Leclère, Philippe; Doneux, C. et al

in Polymer (2001), 42(8), 3503-3514

A series of well-defined poly(methylmethacrylate) (PMMA)-b-poly(alkylacrylate)-b-PMMA triblock copolymers (MAM) has been synthesized by transalcoholysis of PMMA-b-poly(tert-butylacrylate)-b-PMMA ... [more ▼]

A series of well-defined poly(methylmethacrylate) (PMMA)-b-poly(alkylacrylate)-b-PMMA triblock copolymers (MAM) has been synthesized by transalcoholysis of PMMA-b-poly(tert-butylacrylate)-b-PMMA precursors by alkyl alcohols. The molecular weight (MW) of the outer PMMA blocks is in the 10,000-50,000 range, compared to 50,000-200,000 for the inner poly(alkylacrylate) block. Phase separation, as studied in direct space by atomic force microscopy, is observed for all the investigated triblock copolymers, except for the PMMA-b-poly(ethylacrylate)-b-PMMA and the PMMA-b-poly(n-propylacrylate)-b-PMMA triblocks of 10,000-50,000-10,000 MW. The ultimate tensile strength measured for the MAM triblocks is strongly dependent on the MW between chain entanglements for the central block. The tensile behavior is however affected by the partial miscibility of the outer and inner blocks when the PMMA MW is low. When this situation prevails, it makes the melt processing possible at temperatures lower than 200°C. [less ▲]

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See detailPhase-separated microstructures in "all-acrylic" thermoplastic elastomers
Leclère, Philippe; Rasmont, A.; Brédas, Jean-Luc et al

in Macromolecular Symposia (2001), 167

Atomic Force Microscopy (AFM) is used to study the phase separation process occurring in block copolymers in the solid state. Measuring simultaneously the amplitude and the phase of the oscillating ... [more ▼]

Atomic Force Microscopy (AFM) is used to study the phase separation process occurring in block copolymers in the solid state. Measuring simultaneously the amplitude and the phase of the oscillating cantilever in tapping-mode operation provides the surface topography along with the cartography of microdomains with different mechanical properties. This in turn allows to characterize the organization of the various components at the surface in terms of well-defined morphologies (e.g., spheres, cylinders, or lamellae). Here this approach is applied to a series of symmetric triblock copolymers made of a central elastomeric segment (polyalkylacrylate) surrounded by two thermoplastic sequences (polymethylmethacrylate). The occurrence of microphase separation in these materials and the resulting microscopic morphology are essential factors for determining their potential applications as a new class of thermoplastic elastomers. This paper describes how the surface morphology can be controlled by the molecular structure of the copolymers (volume ratio between the sequences, molecular weight, length of the alkyl side group) and by the experimental conditions used for the preparation of the films. The molecular structure of the chains is fully determined by the synthesis of the copolymers via living anionic polymerization while the parameters that can be modified when preparing the samples are the nature of the solvent and the thermal annealing of the films. Finally, we report on a systematic comparison between images and approach-retract curve data. We show that this experimental comparison allows the origin of the contrast that produces the image to be straightforwardly evaluated. The method provides an unambiguous quantitative measurement of the contribution of the local mechanical response to the image. We show that most of the contrast in the height and phase images is due to variations in local mechanical properties and not in topography. [less ▲]

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See detailMicrophase separation at the surface of block copolymers, as studied with atomic force microscopy
Rasmont, A.; Leclère, Philippe; Doneux, C. et al

in Colloids and Surfaces B : Biointerfaces (2000), 19(4), 381-395

Atomic force microscopy (AFM) is used to study the phase separation process occurring in block copolymers in the solid state. The simultaneous measurement of the amplitude and the phase of the oscillating ... [more ▼]

Atomic force microscopy (AFM) is used to study the phase separation process occurring in block copolymers in the solid state. The simultaneous measurement of the amplitude and the phase of the oscillating cantilever in the tapping mode operation provides the surface topography along with the cartography of the microdomains of different mechanical properties. This technique thus allows to characterize the size and shape of those microdomains and their organization at the surface (e.g. cubic lattice spheres, hexagonal lattice of cylinders, or lamellae). In this study, a series of symmetric triblock copolymers made of a inner elastomeric sequence (poly(butadiene) or poly(alkylacrylate)) and two outer thermoplastic sequences (poly(methylmethacrylate)) is analyzed by AFM in the tapping mode. The microphase separation and their morphology are essential factors for the potential of these materials as a new class of thermoplastic elastomers. Special attention is paid to the control of the surface morphology, as observed by AFM, by the molecular structure of the copolymers (volume ratio of the sequences, molecular weight, length of the alkyl side group) and the experimental conditions used for the sample preparation. The molecular structure of the chains is completely controlled by the synthesis, which relies on the sequential living anionic polymerization of the comonomers. The copolymers are analyzed as solvent-cast films, whose characteristics depend on the solvent used and the annealing conditions. The surface arrangement of the phase-separated elastomeric and thermoplastic microdomains observed on the AFM phase images is discussed on the basis of quantitative information provided by the statistical analysis by Fourier transform and grain size distribution calculations. [less ▲]

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See detailMorphology and rheology of poly(methyl methacrylate)-block-poly(isooctyl acrylate)-block-poly(mehtyl methacrylate) triblock copolymers, and potential as thermoplastic elastomers
Tong, Jiang-Dong; Leclère, Philippe; Rasmont, A. et al

in Macromolecular Chemistry and Physics (2000), 201(12), 1250-1258

The phase morphology and rheological properties of a series of poly(methyl methacrylate)-block-poly(isooctyl acrylate)-block-poly(methyl methacrylate) triblock copolymers (MIM) have been studied. These ... [more ▼]

The phase morphology and rheological properties of a series of poly(methyl methacrylate)-block-poly(isooctyl acrylate)-block-poly(methyl methacrylate) triblock copolymers (MIM) have been studied. These copolymers have well-defined molecular structures, with a molecular weight (MW) of poly(methyl methacrylate) (PMMA) in the range of 3 500-50 000 and MW of poly(isooctyl acrylate) (PIOA) ranging from 100 000 to 140 000. Atomic force microscopy with phase detection imaging has shown a two-phase morphology for all the MIM copolymers. The typical spherical, cylindrical, and lamellar phase morphologies have been observed depending on the copolymer composition. MIM consisting of very short PMMA end blocks (MW 3 500-5 000) behave as thermoplastic elastomers (TPEs), with however an upper-service temperature higher than the traditional polystyrene-block-polyisoprene-block-polystyrene TPEs (Kraton D1107). A higher processing temperature is also noted, consistent with the higher viscosity of PMMA compared to PS. [less ▲]

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See detailSynthesis and bulk properties of poly(methyl methacrylate)-b-poly(isooctyl acrylate(isooctyl acrylate)-b-poly(methyl methacrylate)
Tong, J. D.; Leclère, Philippe; Doneux, C. et al

in Polymer (2000), 41(12), 4617-4624

A series of well-defined poly(methylmethacrylate) (PMMA)-b-poly(isooctylacrylate) (PIOA)-b-PMMA triblock copolymers (MIM) has been synthesized by transalcoholysis of PMMA-b-poly(tert-butylacrylate) (PtBA ... [more ▼]

A series of well-defined poly(methylmethacrylate) (PMMA)-b-poly(isooctylacrylate) (PIOA)-b-PMMA triblock copolymers (MIM) has been synthesized by transalcoholysis of PMMA-b-poly(tert-butylacrylate) (PtBA)-b-PMMA precursors (MTM) by isooctyl alcohol. Phase separation is observed for all the investigated triblock copolymers, thus containing PMMA outer blocks in the 3500-50,000 molecular weight (MW) range and PIOA inner block with MW in the 100,000-300,000 range. The ultimate tensile properties of these MIM triblock copolymers are poor even when PMMA blocks of 50,000 MW are associated with an inner PIOA block of 300,000 MW. A reasonable explanation should be found in the molecular weight between chain entanglements (Me), which has been estimated at 60,000 for PIOA, much higher than Me for the traditional polydiene central blocks in the well-known thermoplastic elastomers of the triblock type. The tensile behavior of MIM copolymers has been successfully accounted for by a simple elastomer model free from chain entanglements, supporting the view that the lack of entanglements in the central block is very detrimental to the mechanical properties of the investigated fully (meth)acrylate triblock copolymers. [less ▲]

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See detailSynthesis, morphology, and mechanical properties of poly(methyl methacrylate)-b-poly(n-butyl acrylate)-b-poly (methyl methacrylate) triblocks. Ligated anionic polymerization vs atom transfer radical polymerization
Tong, Jiang-Dong; Moineau, Georges; Leclère, Philippe et al

in Macromolecules (2000), 33(2), 470-479

Poly(methyl methacrylate)-b-poly(n-butyl acrylate)-b-poly(methyl methacrylate) triblock copolymers have been prepared by ligated anionic polymerization (LAP; 8K-50K-8K) and atom transfer radical ... [more ▼]

Poly(methyl methacrylate)-b-poly(n-butyl acrylate)-b-poly(methyl methacrylate) triblock copolymers have been prepared by ligated anionic polymerization (LAP; 8K-50K-8K) and atom transfer radical polymerization (ATRP; 9K-51K-9K). Size exclusion chromatography, nuclear magnetic resonance, and differential scanning calorimetry have confirmed that the molecular structure of the two triblock copolymers is essentially identical. However, important differences are found in dynamic mechanical properties, viscoelastic properties, and stress−strain behavior. Indeed, the ATRP copolymer has low storage modulus, high complex viscosity, high order−disorder transition temperature, and poor ultimate tensile strength and elongation at break, compared to those of the LAP analogue. Marked differences also observed by tapping mode atomic force microscopy in the microscopic morphology of thin films of these copolymers. All these observations can be explained by the slow initiation of MMA by the poly(n-butyl acrylate) macroinitiator used in ATRP in contrast to what happens when MMA is added to living poly(tert-butyl acrylate) anions. As a result, the polydispersity of the short poly(methyl methacrylate) (PMMA) outer blocks is much broader in the ATRP copolymer, although the polydispersity index of the triblock is only 1.15. This heterogeneous structure of the ATRP triblock is also supported by the comparison of homo-PMMAs prepared by LAP and ATRP. [less ▲]

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See detailDirect observation of microdomain morphology in "all-acrylic" thermoplastic elastomers synthesized via living radical polymerization
Leclère, Philippe; Moineau, Georges; Minet, Michaël et al

in Langmuir (1999), 15(11), 3915-3919

We investigate the microscopic morphology of thin films of symmetric triblock copolymers synthesized via a two-step “living” radical polymerization of n-butylacrylate and methyl methacrylate. These ... [more ▼]

We investigate the microscopic morphology of thin films of symmetric triblock copolymers synthesized via a two-step “living” radical polymerization of n-butylacrylate and methyl methacrylate. These copolymers with low poly(methyl methacrylate) contents constitute a new class of potential thermoplastic elastomers with higher service temperature and oxidation resistance compared to conventional polydiene−polystyrene-based thermoplastic elastomers. The straightforward synthetic pathway allows for strict control of molecular weight, molecular-weight distribution, and composition. The presence in the copolymer of immiscible segments covalently bound to each other leads to phase separation on the nanometer scale. Regular organization of the phase-separated nanodomains is observed in real space by scanning force microscopy. The data point to a strong contrast in the local mechanical properties, corresponding to the microphase morphology. Cylinders of the minority phase are found to orient perpendicular to the surface, because of the surface energy difference between the constituents. Lamellae are also arranged perpendicular to the surface, in contrast to what is usually observed in block copolymers. This particular orientation is thought to result from the symmetric character of these triblock systems, with the outer blocks more polar than the central sequence. [less ▲]

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See detailCarbon black-filled polymer blends : a scanning probe microscopy characterization
Leclère, Philippe; Lazzaroni, Roberto; Gubbels, Frédéric et al

in Materials Research Society Symposium Proceedings (1997), 457

Conducting polymer composites, that consist of a conducting filler randomly distributed throughout an insulating polymer or polymer blend, attract interest in several application fields such as sensors or ... [more ▼]

Conducting polymer composites, that consist of a conducting filler randomly distributed throughout an insulating polymer or polymer blend, attract interest in several application fields such as sensors or electromagnetic radiation shielding. The macroscopic electrical resistivity of the filled polyblend strongly depends on the localization of the filler. Here, we investigate the morphology of Carbon Black (CB)-filled polymer blends in order to determine the parameters governing the selective localization of CB in one phase of the blend components or at the interface between the components. The dispersion of the CB particles in the polymer blend is observed by means of Lateral Force Microscopy (LFM) as a function of the blend composition and the load in CB. The selective localization of CB at the interface enables the reduction of the percolation threshold down to 0.5 wt%; as a result, the mechanical properties of the polymer blend can be fully retained. Different techniques can be used to locate the CB at the interface; we compare their efficiency experimentally. [less ▲]

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See detailMicrodomain morphology analysis of block copolymers by atomic force microscopy with phase detection imaging
Leclère, Philippe; Lazzaroni, Roberto; Brédas, Jean-Luc et al

in Langmuir (1996), 12(18), 4317-4320

We use atomic force microscopy (AFM) with phase detection imaging (PDI) in order to study the surface microdomain morphology of thick (i.e., ca. 2 mm) films of triblock copolymers. We present here the ... [more ▼]

We use atomic force microscopy (AFM) with phase detection imaging (PDI) in order to study the surface microdomain morphology of thick (i.e., ca. 2 mm) films of triblock copolymers. We present here the results obtained on a poly(methyl methacrylate)-block-polybutadiene-block-poly(methyl methacrylate) (PMMA-b-PBD-b-PMMA) copolymer prepared by using a 1,3-diisopropenylbenzene (DIB)-based difunctional anionic initiator. Our data illustrate the interest of PDI for the elucidation of surface phase separation in block copolymers. We show that the surface of thick films studied by this new technique exhibits a two-phase structure corresponding to the two types of components. [less ▲]

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