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UMR CNRS #5627 INGENIERIE DES MATERIAUX POLYMERES. Institut National des Sciences Appliquées de Lyon 69621 Villeurbanne (France) http://www.insa-lyon.fr/Laboratories/LMM. Laboratoire des Matériaux Macromoléculaires Institut National des Sciences Appliquées Head: Prof. J.F. Gérard
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UMR CNRS #5627INGENIERIE DESMATERIAUX POLYMERES Institut National des Sciences Appliquées de Lyon 69621 Villeurbanne (France) http://www.insa-lyon.fr/Laboratories/LMM
Laboratoire des Matériaux Macromoléculaires Institut National des Sciences Appliquées Head: Prof. J.F. Gérard Laboratoire des Matériaux Polymères & Biomatériaux Université Claude Bernard Lyon I - ISTIL Head: Dr. G. Seytre UMR CNRS #5627 / IMP Ingénierie des Matériaux Polymères Head UMR: Prof. J.F. Gérard
Laboratory Macromolecular Materials STAFF (47 permanents) 22 Professors or Assistant professors 12 CNRS senior scientists 14 Engineers/Technicians & Administratives 62 PhD students 5 Post-Docs 25 DEA (Masters) UMR CNRS #5627Polymer Materials Engineering IMPHead: Prof. Gérard J.F. Laboratory Polymer Materials & Biomaterials
IMP - UMR CNRS #5627 Outcomes 1999-2002 302 Papers (referred) 93 Invited lectures 250 Lectures 204 Posters 24 Patents 48 PhDs (defended) 8 PhDs (shared with other research groups) International symposia organized Workshops or Conferences Polymer Blends May 2002, ‘Nanocomposites à charges lamellaires’ March 2003, Journées Transalpines des Polymères October 2003, Elaboration matériaux polymères nanoporeux January 2004, MODEST September 2004
IMP - UMR CNRS #5627Research Topics Fundamental research devoted to practical objectives (Materials Engineering) Polymer chemistry Frontiers with polymer (Chemical Engineering) Processing / Formulation physics Polymer chemistries Blends, Filled polymers and Composite materials Surface and interface chemistries Reactive and non-reactive processes Influence of the Process Parameters Properties
IMP - UMR CNRS #5627Research Topics • Synthesis of Polymers Having Controlled Architecture & Properties Syntheses and Chemical Modifications • Processing Engineering of Polymers, Blends, and Composite Materials • Surfaces & Interfaces Organization & Functionality • Architecture-Morphology / Mechanical, Electrical, and Transport Relationships of Polymers & Multimaterials • Natural & Bioartificial Polymer Materials
IMP - UMR CNRS #5627Applications - Examples • Composites / Nanocomposites MaterialsToughening, Gas barrier, Durability / Aging Intelligent Processing, Formulations, etc. • Surfaces, adhesives, coatings & multilayers Formulations, Processing requirements, powder coatings, UV coatings, adhesives, Designed surfaces Practical adhesion properties, Wettability, gas barrier • Polymers with Controlled Properties Mechanical Properties, Life Cycle (Aging, Recyclability,..) Electrical and dielectric properties (low K, etc) Transport / Barrier / Permeation, Diffusion, etc.
Research Topic#1 Synthesis of Polymers Having Controlled Architecture & Properties Syntheses and Chemical Modifications IMP UMR #5627 1.- Reaction mechanisms and kinetics * Conventional polymerization routes (condensation, free radical, hydrol. condens.) * Interfacial route: in-situ crosslinking of particles, microencapsulation * Controlled radical polymerization: end-linking crosslinking, grafting from, … * Structural changes during polymerization – chemiorheology – 2.- Formulations of reactive systems * Chemical modification of oligomers (PUA, silicon alkoxide-term., HBP, TPU) * Chemistries et organization at different scale lengths - dispersion of pre-formed heterogeneities (HPB, grafted nanosilica, mgels) - organized polymer nanolayers (CRP grafting from) * Amphiphilic networks TPU/PDMS 3.- Phase separation thermodynamics and kinetics in reactive systems * High Tg thermoplastic/thermoset formulations (PEI, PES, PPE, PVC, PET, sPS) * Nanostructured thermosets from block copolymers, POSS, HBP * Porous networks from phase separation process
PEI 10% 20% 30% 45% 60% 3 mm Research Topic#1 Synthesis of Polymers Having Controlled Architecture & Properties Syntheses and Chemical Modifications IMP UMR #5627 Toughening (KIc) High Tg thermoplastic-thermoset blends Processing aids POLYETHERIMIDE TP MATRIX PURE EPOXY EPOXY MATRIX PHASE INVERSION PURE THERMO PLASTIC PPE POLYPHENYLENE ETHER (A.Bonnet et al, Macromolecules 1999)
TPU « self crosslinkable » from ‘soft’ hydrolysis 3 aminoalkoxysilane 2 network with designed properties diol, diamine humidity Direct crosslinking complete and fast 1 hydroxyalkylacrylate 4 crosslinkable TPU from photopolymerization Research Topic#1 Synthesis of Polymers Having Controlled Architecture & Properties Syntheses and Chemical Modifications IMP UMR #5627 Chemical modifications of thermoplastic polyurethanes TPU done in the molten state - reactive extrusion -
LMM/IMP INSA Lyon - UMR CNRS #5627Scientific Topics Chemistries Under Study • EPOXIES • epoxy-amine, anhydride, homopolymerisation, • cationic , anionic types • encapsulation of amines, functionalization of hyperbranched pol. • water-borne and solvent-based formulations, linear epoxies • photopolymerization of cycloaliphatic epoxies • epoxy-thermoplastic blends (toughening, processing-aids) • PPE, PES, PEI, PS, sPS, PVC, … • POLYURETHANES, POLYUREAS • alcohol-isocyanate, amine-isocyanate, • blocked and encapsulated isocyanates, functionalization of hyperbranched pol. • segmented and crosslinked PU /PUR • dispersed TPU, reactive extrusion of TPU for crosslinking • CYANATE-ESTERS • POLYESTERS (PET)
LMM/IMP INSA Lyon - UMR CNRS #5627Scientific Topics Chemistries Under Study (continued) • FREE RADICAL POLYMERIZATION • unsaturated polyesters, acrylates • BENZOXAZINES • ACRYLATE CHEMISTRY FOR COATINGs • epoxy- and polyurethane-acrylate based formulations • for thermal or UV curings • SOL-GEL CHEMISTRY FROM SILICON - ALKOXIDES • hybrid organic – inorganic materials based on PU and • (meta) acrylates • synthesis and introduction of polyhedralsilsesquioxanes POSS • CHEMISTRIES AT THE INTERFACES • reactive extrusion of immiscible polymers and filled polymers • generation of tailored interphases from specific interactions • establish at the interface (metal – epoxy/amine) • grafting on various types of surface (silica and silicates, …)
Research Topic#2 Processing Engineering of Polymers, Blends, & Composite Materials IMP UMR #5627 1.- Chemistry and processing – Reactive processing * Reactive extrusion - Polymerization copolymer synthesis on-line crosslinking of a dispersed phase (TPV, epoxy-amine) - Chemical modifications - Control and stabilization of morphologies in blends and nanocomposites * Reactive molding - Resin Transfer Molding RTM - Reaction Injection Molding RIM 2.- Physics associated to processing * Pressure-Volume-Temperature behaviour * Pressure and shear effects on crystallization processes * Generation of designed morphologies in thermoplastic-based blends Deformation of the dispersed phase
Research Topic#2 Processing Engineering of Polymers, Blends, & Composite Materials IMP UMR #5627 Reactive extrusion Dryer Feeders (V, w) Pumps NIR & MIR spectroscopies Polymerization in bulk and in the dispersed phase Homopolymerization of e-caprolactone Reactive epoxy-amine dispersed phase in PS Thermoset/thermoplastic blends Spectro UV Chemical modification in extruder Anhydride-alcohol reaction (copolymers) Alcoholis of PET TPU modification m-wave channel Computer-controlled extruder (P,T, rot., …) Instrumention of twin-screw extruder Reactive solvants – Foams Other investigated routes Exchange reactions ester – alkoxysilane (TPV) Compatibilization blends nanofillers (nanoclays) Non-compatibilized and in-situ compatibilized PP/PE blends
Research Topic#2 Processing Engineering of Polymers, Blends, & Composite Materials IMP UMR #5627 Reaction Injection Molding RIM Design of reactive systems In-situ analysis of reaction FT-IR (NIR) Microdielectrometry Resin Transfer Molding RTM Intelligent processing (in-situ analysis: mdielectrometry, US, NIR) Modeling mold filling (chemiorheology, permeability) Combined processes (in-situ dissolution of TP films or fibers) RTN Polynetset GROWTH Soltex
Research Topic#2 Processing Engineering of Polymers, Blends, & Composite Materials IMP UMR #5627 Design of morphologies from processing conditions High shape factor dispersed phase Effect of pressure and shear rate on crystallization processes PVT apparatus Device for high shear rate testing in the molten state PE/PET blend Injection molding process SCOOP (Shrinkage Crystallinity Orientation of Polymers) FISH (Fiber-filled polymer Injection & Shrinkage) Solvay / Moldflow / legrand
Research Topic#3 Surfaces & Interfaces Organization and Functionality IMP UMR #5627 1.- Development of new methods for analysis and processing of surfaces * Controlled Radical Polymerization applied to surfaces (grafting from) * AFM developments: chemical mapping, surface forces, etc. * Modeling of interfaces in blends and composites (microcomposites) * Molecular modeling of bulk and surface properties 2.- Study of structure/organization of surfaces and interfaces in macromolecular systems * PRC for grafting ultra-thin PS layers * Effect of interactions at the interface with an inorganic surface (nanofillers) * Interactions/reactions at polymer-polymer interfaces * Interfacial adhesion in polymer-based materials 3.- Design, modification, and functionalization of surfaces and interfaces * Methodology for intercalation/exfoliation of lamellar nanofillers and nanoparticles in TPs and TSs * Synthesis of gradient interphases – Chemistries of interfaces * Design of interactive/reactive surfaces using chemical and/or physical methods
Research Topic#3 Surfaces & Interfaces Organization and Functionality IMP UMR #5627 Development of tools and methodologies for studying surfaces and interfaces Theoretical Modeling wettability of polymer surfaces Analysis of interactions between PDMS and silica Experimental ADCB method for fracture energy of polymer-polymer interfaces Microcomposites
Research Topic#3 Surfaces & Interfaces Organization and Functionality IMP UMR #5627 Nanocomposites - Management of nanoparticles dispersion state in polymers from tailoring the interactions at the interface PDMS - silica Polypropylene PP – montmorillonite MMT Effect of the nature of the quaternary ammonium chains on intercalation/exfoliation Effect of grafting level of silica
Research Topic#4 Architecture-Morphology / Mechanical, Electrical, and Transport Relationships of Polymers & Multimaterials IMP UMR #5627 1.- Mechanical and viscoelastic properties of polymer and multimaterials * Molecular architecture-morphology / mechanical behavior relationships * Feedback to synthesis, formulation, and processing conditions * Adhesion of polymer layers on substrates 2.- Electrical and optical properties of polymers * Study of diffusion and relaxation mechanisms * Electrical response – physicochemical events relationships * Electroactive polymers * Interfacial adhesion in polymer-based materials 3.- Transport of small molecules in dense macromolecular materials * Transport mechanisms and modeling: solubility vs. diffusion * Architecture-morphology / transport properties relationships * Effects of additional parameters: humid environment, etc.
( f = 1 kHz , T = 161 ° C) Polarized light Polarized light 13 3,0E-08 2,5E-08 12 Permittivity E E 11 2,0E-08 Ionic conductivity (ohm.cm)-1 AC AC 1,5E-08 10 : PEN spacer (25 µm) 9 1,0E-08 : PVDF sample (30 µm) 5,0E-09 8 : Aluminium lead : ITO glass 7 0 500 1000 1500 2000 2500 time (sec.) 1694 s. 200 s. 714 s. 944 s. 520 s. 1274 s. Research Topic#4 Architecture-Morphology / Mechanical, Electrical, and Transport Relationships of Polymers & Multimaterials IMP UMR #5627 Use of combined methods for studying crystallization of thermoplastics Dielectric spectroscopy DEA Optical microscopy PVDF crystallization
Research Topic#5 Native & Bioartificial Materials IMP UMR #5627 1.- Basic analysis of kinetics and thermodynamics of extraction mechanisms of polymers from biomass 2.- Kinetics and thermodynamics of chemical modification reactions of chitine and chitosane for processing biomimetic structures 3.- Study of interactions in solution and in the solid state 4.- Design of complex physical shapes from solutions * Physical hydrogels from chitosane * Nanoparticle formation * Bio-encapsulation 5.- Physico-chemical interactions from physical hydrogels 6.- Metallic ions and dyes sorption on chitosane and cellulose 7.- Interface with life sciences
Research Topic#5 Native & Bioartificial Materials IMP UMR #5627 Objectives Use of native structures existing partially which can be induce various non-conventional biological responses, i.e. polysaccharides : glycosaminoglycanes (GAG), chitine, chitosane • N-acetylglucosamine extracellular matrix (GAG, glycoconjuguated) as simple and sulfate forms - b bond, (14) biological media, - Influence of DA management of the biological response
IMP - UMR CNRS #5627European Research Training Networks • POLYNETSET Thermoset-Based Polymer Blends LMM-IMP INSA Lyon Lyon (France) Coordinator Institute Polymerforschung Dresden (Germany) Politecnico Milano Milano (Italy) Université Catholique de Louvain Louvain (Belgium) Imperial College London (Great Britain) Basque County University San Sebastian (Spain) Siegen University Siegen (Germany) • NBB-HYBRIDS Hybrid Organic-Inorganic Materials LMM-IMP INSA Lyon Lyon (France) Coordinator Institute Polymerforschung Dresden (Germany) UPMC Université Paris VI Paris (France) Trento University Trento (Italy) Institute Macromolecular Sci. Prague (Czech Republic) Franhaufer Inst. Silicatforschung Wursburg (Germany)
IMP - UMR CNRS #5627European Programme 6th PCRD • Network of Excellence NANOFUN-POLY Nanostructured and Multifunctional Polymer-Based Materials and Nanocomposites INSTM (Italian Univ.) Perugia (Italy) Coordinator IMP INSA Lyon Lyon (France) Vice-Coordinator Consortium of 28 partners • STREP‘NANOFIRE’ Nanocomposites for Fire Retardancy Materials Politecnico Torino Alessandria (Italy) coordinator LMM-IMP INSA Lyon Lyon (France) Partner
IMP - UMR CNRS #5627Scientific Collaborations • PICS Program CRMM /Technical University Lodz Lodz (Poland) Coal InstituteGliwicze (Poland) • Australia Monash University Melbourne Queensland University Brisbane Queensland University of Technology Brisbane Wollongong University Wollongong • Weizmann InstituteRehovot (Israël) • INTEMAMar-del-Plata (Argent.) • W. & M. CollegeWilliamsburg (USA) • Ecole Polytechnique de LausanneLausanne (Switzerland) • Politecnico TorinoTorino (Italy) • Réseau Transalpin des Polymères CH – Vaud /Genève / Valais I - Lombardie / Ligurie / Vallée F – Région Rhône-Alpes d’Aoste
IMP - UMR CNRS #5627Scientific Collaborations • Fédération des Polyméristes Lyonnais NMR facilities Center, etc. • Programmes (GDR, ACI...) CPR " Reactive Extrusion" ACI Nanomaterials " Clay-Based Nanocomposites" ACI Adhesion " Metal / Polymer Interfaces" PREDIT Transportation " RTM Process" Ministry of Industry " RTM Preforms " RECORD 2000 " Recycling of Polymer Blends " RNMP " PROSPET ", " NENATEX " PACO " POLYSTOCK " Hydrogen storage • Rhône-Alpes County Emergence " Nanocomposites Varnishes and Adhesives " Materials ‘Non-permeable/Breathing PU’ Materials " Nanocomposites based on lamellar nanofillers"" Materials " Reactive TS/TD formulations for new cables " • French Research groups ISITEM Nantes, ENSAM Paris, ESPCI Paris, Univ. Lille, Clermont-Ferrand Univ., etc.
IMP - UMR CNRS #5627Connections with Industry About 87% of research activities are associated with industrial contracts • Chemical Companies Ato-Fina, Solvay, Rhodia, Rhodia Silicones, Dow Chem., Exxon Vantico, Tergal, Wacker Chem. • Polymer Users Companies Compounding/ Formulation Multibase Dow Corning, Gemoplast, SAMI Acome, Merilithe, Chauzu, Allrim Automotive/Aeronautics Renault, Inoplast, EADS – Airbus, CTTM Coatings/Paints Celliose, Becker Ind., Arcelor Packaging Pechiney/Cébal, Nestlé, Pernod-Ricard, Vitembal, Tetrapak Electricity / Electronics Nexans, EDF, Porcher, RCE, Trixell-Thalès Civil Engineering St. Gobain, Soprema, Lafarge, Gerflor, Spit Others IFP, CEA, Rossignol, IFTH Kodak , Air Liquide
IMP - UMR CNRS #5627Connections with industrial partners Types of collaboration • PhD Doctorates CIFRE, BDI-CNRS, DGA, R-A County, EC 5th PCRDT • Post-doctorates R-A County, EC 5th PCRDT • ‘End of Study’ / Master Projects which can be connected with a following 5/6 month-long training period in industry • ‘Transfer Engineer’ INSA Initial Research and Development Studies for SME companies (duration: few months ) Technology and Literature Survey and Watching Experiments / Data Analysis