UMR CNRS #5627UMR CNRS #5627INGENIERIE DESINGENIERIE DES

MATERIAUX MATERIAUX POLYMERESPOLYMERES

Institut National

des Sciences Appliquées de Lyon

69621 Villeurbanne (France)http://www.insa-lyon.fr/Laboratories/LMM

UMR CNRS #5627 / IMP UMR CNRS #5627 / IMP

Ingénierie des Matériaux PolymèresIngénierie des Matériaux Polymères

Laboratoire des Matériaux Macromoléculaires

Institut National des Sciences AppliquéesHead: Prof. J.F. Gérard

Laboratoire des Matériaux Polymères & Biomatériaux

Université Claude Bernard Lyon I - ISTILHead: Dr. G. Seytre

Head UMR: Prof. J.F. Gérard

UMR CNRS #5627UMR CNRS #5627Polymer Materials Engineering IMPPolymer Materials Engineering IMPHead: Prof. Gérard J.F.Head: Prof. Gérard J.F.

STAFF (47 permanents)

22 Professors or Assistant professors12 CNRS senior scientists14 Engineers/Technicians & Administratives

62 PhD students5 Post-Docs25 DEA (Masters)

Laboratory Macromolecular MaterialsLaboratory Polymer Materials &

Biomaterials

Outcomes 1999-2002

302 Papers (referred)93 Invited lectures250 Lectures204 Posters24 Patents48 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 #5627IMP - UMR CNRS #5627

IMP - UMR CNRS #5627IMP - UMR CNRS #5627Research TopicsResearch Topics

Reactive and non-reactive processesInfluence of the ProcessParameters

Polymer chemistriesBlends, Filled polymers andComposite materialsSurface and interface chemistries

Properties

Fundamental research devoted to practical objectives (Materials Engineering) Polymer chemistry Frontiers with polymer (Chemical Engineering) Processing / Formulation physics

IMP - UMR CNRS #5627IMP - UMR CNRS #5627Research TopicsResearch Topics

1. Synthesis of Polymers Having Controlled Architecture & Properties Syntheses and Chemical Modifications

2. Processing Engineering of Polymers, Blends, and Composite Materials

3. Surfaces & Interfaces Organization & Functionality

4. Architecture-Morphology / Mechanical, Electrical, and Transport Relationships of Polymers & Multimaterials

5. Natural & Bioartificial Polymer Materials

IMP - UMR CNRS #5627IMP - UMR CNRS #5627Applications - ExamplesApplications - Examples

Composites / Nanocomposites MaterialsToughening, Gas barrier, Durability / Aging

Intelligent Processing, Formulations, etc.

Surfaces, adhesives, coatings & multilayersFormulations, Processing requirements, powder

coatings, UV coatings, adhesives, Designed surfacesPractical adhesion properties, Wettability, gas barrier

Polymers with Controlled PropertiesMechanical 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

IMPIMPUMR #5627UMR #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, gels)

- 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

Research Topic#1

Synthesis of Polymers Having Controlled Architecture & Properties Syntheses and Chemical Modifications

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PEI

10% 20% 30% 45% 60%

3 m

PPE(A.Bonnet et al, Macromolecules 1999)

PHASEINVERSIO

N

EPOXYMATRIX

TP MATRIX

POLYETHERIMIDE

POLYPHENYLENE ETHER

PURE EPOX

Y

PURE THERMO

PLASTIC

High Tg thermoplastic-thermoset blendsToughening (KIc)

Processing aids

Research Topic#1

Synthesis of Polymers Having Controlled Architecture & Properties Syntheses and Chemical Modifications

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TPU « self crosslinkable »from

‘soft’ hydrolysis

diol,diamine

networkwith designed

properties humidity

Directcrosslinking

complete and fast

C=ONH

C=ONH

C=ONH

NCO

N-C-O N-C-O N-C-O

O O O

NCO

NCO

aminoalkoxysilane

hydroxyalkylacrylate

crosslinkable TPU from

photopolymerization

2

4

3

1

Chemical modifications of thermoplastic polyurethanes TPU done in the molten state - reactive extrusion -

LMM/IMP INSA Lyon - UMR CNRS #5627LMM/IMP INSA Lyon - UMR CNRS #5627Scientific TopicsScientific Topics

Chemistries Under Study

•EPOXIESepoxy-amine, anhydride, homopolymerisation, cationic , anionic types encapsulation of amines, functionalization of hyperbranched

pol.water-borne and solvent-based formulations, linear epoxiesphotopolymerization of cycloaliphatic epoxiesepoxy-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 /PURdispersed TPU, reactive extrusion of TPU for crosslinking

•CYANATE-ESTERS

•POLYESTERS (PET)

LMM/IMP INSA Lyon - UMR CNRS #5627LMM/IMP INSA Lyon - UMR CNRS #5627Scientific TopicsScientific Topics

Chemistries Under Study (continued)

•FREE RADICAL POLYMERIZATIONunsaturated polyesters, acrylates

•BENZOXAZINES

•ACRYLATE CHEMISTRY FOR COATINGsepoxy- and polyurethane-acrylate based formulations for thermal or UV curings

•SOL-GEL CHEMISTRY FROM SILICON - ALKOXIDEShybrid organic – inorganic materials based on PU and (meta) acrylatessynthesis and introduction of polyhedralsilsesquioxanes POSS

•CHEMISTRIES AT THE INTERFACESreactive extrusion of immiscible polymers and filled polymersgeneration 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 IMPIMP

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1.- Chemistry and processing – Reactive processing

* Reactive extrusion - Polymerization

copolymer synthesison-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 IMPIMP

UMR #5627UMR #5627

Reactive extrusion NIR & MIR

spectroscopies

Spectro UV

Computer-controlled extruder (P,T, rot., …)

DryerFeeders (V, w)

Pumps

wavechannel

Polymerization in bulk and in the dispersed phase Homopolymerization of -caprolactone Reactive epoxy-amine dispersed phase in PS Thermoset/thermoplastic blends

Chemical modification in extruder Anhydride-alcohol reaction (copolymers) Alcoholis of PET TPU modification

Reactive solvants – Foams

Other investigated routes Exchange reactions ester – alkoxysilane (TPV) Compatibilization blends nanofillers (nanoclays)

Non-compatibilized and in-situ compatibilized PP/PE blends

Instrumention of twin-screw extruder

Research Topic#2

Processing Engineering of Polymers, Blends, & Composite Materials IMPIMP

UMR #5627UMR #5627

Resin Transfer Molding RTM

Curing

Thermoplastic filmStacking of

prepreg layers

Glass fibers

Matrix

Diffusion of thermoplastic

Reaction Injection Molding RIM

Design of reactive systemsIn-situ analysis of reaction

FT-IR (NIR)Microdielectrometry

Intelligent processing (in-situ analysis: dielectrometry, US, NIR)Modeling mold filling (chemiorheology, permeability)Combined processes (in-situ dissolution of TP films or fibers)RTN PolynetsetGROWTH Soltex

Research Topic#2

Processing Engineering of Polymers, Blends, & Composite Materials IMPIMP

UMR #5627UMR #5627

Design of morphologies from processing conditions

High shape factor dispersed phase Effect of pressure and shear rate on crystallization processes

PE/PET blendDevice for high shear ratetesting in the molten state

PVT apparatus

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 FunctionalityIMPIMP

UMR #5627UMR #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 FunctionalityIMPIMP

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ADCB method for fracture energy ofpolymer-polymer interfaces

Microcomposites

Modeling wettability of polymer surfacesAnalysis of interactions between PDMS and silica

Development of tools and methodologies for studying surfaces and interfaces

Theoretical

Experimental

Research Topic#3

Surfaces & Interfaces Organization and FunctionalityIMPIMP

UMR #5627UMR #5627

Nanocomposites - Management of nanoparticles dispersion state in polymers from tailoring the interactions at the interface

PDMS - silica Polypropylene PP – montmorillonite MMT

Effect of grafting level of silica Effect of the nature of the quaternary ammonium chains on intercalation/exfoliation

Research Topic#4

Architecture-Morphology / Mechanical, Electrical, and Transport Relationships of Polymers & Multimaterials

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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.

Research Topic#4

Architecture-Morphology / Mechanical, Electrical, and Transport Relationships of Polymers & Multimaterials

IMPIMPUMR #5627UMR #5627

Use of combined methods for studying crystallization of thermoplastics

(f = 1 kHz, T = 161 °C)

200 s. 944 s.714 s.520 s. 1694 s.1274 s.

: PEN spacer (25 µm)

: PVDF sample (30 µm): Aluminium lead

: ITO glass

EEACAC

Polarized lightPolarized light

7

8

9

10

11

12

13

0 500 1000 1500 2000 2500time (sec.)

Perm

itti

vity

5,0E-09

1,0E-08

1,5E-08

2,0E-08

2,5E-08

3,0E-08

Ion

ic c

on

du

cti

vity

(oh

m.c

m)-

1

Dielectric spectroscopy DEADielectric spectroscopy DEAOptical microscopy Optical microscopy

PVDF crystallization

Research Topic#5

Native & Bioartificial MaterialsIMPIMPUMR #5627UMR #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 MaterialsIMPIMPUMR #5627UMR #5627

Use of native structures existing partially which can be induce various non-conventional biological responses, i.e.

- N-acetylglucosamine extracellular matrix (GAG, glycoconjuguated) as simple and sulfate forms

- Influence of DA management of the biological response

- bond14) biological media,

polysaccharides : glycosaminoglycanes (GAG), chitine, chitosane

Objectives

IMP - UMR CNRS #5627IMP - UMR CNRS #5627European Research Training NetworksEuropean Research Training Networks

POLYNETSET Thermoset-Based Polymer Blends

LMM-IMP INSA Lyon Lyon (France) CoordinatorInstitute 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 MaterialsLMM-IMP INSA Lyon Lyon (France) CoordinatorInstitute 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 #5627IMP - UMR CNRS #5627European Programme 6th PCRDEuropean Programme 6th PCRD

Network of Excellence

NANOFUN-POLYNanostructured and Multifunctional Polymer-

Based Materials and NanocompositesINSTM (Italian Univ.) Perugia (Italy)

CoordinatorIMP INSA Lyon Lyon (France) Vice-

CoordinatorConsortium 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 #5627IMP - UMR CNRS #5627Scientific CollaborationsScientific Collaborations

PICS Program CRMM /Technical University Lodz Lodz (Poland) Coal Institute Gliwicze (Poland)

AustraliaMonash University MelbourneQueensland University BrisbaneQueensland University of Technology BrisbaneWollongong University Wollongong

Weizmann Institute Rehovot (Israël) INTEMA Mar-del-Plata (Argent.) W. & M. College Williamsburg (USA) Ecole Polytechnique de Lausanne Lausanne (Switzerland) Politecnico Torino Torino (Italy)

Réseau Transalpin des PolymèresCH – Vaud /Genève / Valais I - Lombardie / Ligurie / Vallée F – Région Rhône-Alpes

d’Aoste

IMP - UMR CNRS #5627IMP - UMR CNRS #5627Scientific CollaborationsScientific 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 #5627IMP - UMR CNRS #5627Connections with IndustryConnections with Industry

Chemical Companies Ato-Fina, Solvay, Rhodia, Rhodia Silicones, Dow Chem., Exxon

Vantico, Tergal, Wacker Chem.

Polymer Users Companies

Compounding/ Formulation Multibase Dow Corning, Gemoplast, SAMIAcome, Merilithe, Chauzu, Allrim

Automotive/Aeronautics Renault, Inoplast, EADS – Airbus, CTTM

Coatings/Paints Celliose, Becker Ind., ArcelorPackaging 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, IFTHKodak , Air Liquide

About 87% of research activities are associated with industrial contracts

IMP - UMR CNRS #5627IMP - UMR CNRS #5627Connections with industrial partnersConnections with industrial partners

PhD Doctorates CIFRE, BDI-CNRS, DGA, R-A County, EC 5th PCRDT

Post-doctoratesR-A County, EC 5th PCRDT

‘End of Study’ / Master Projects which can be connected with a following 5/6 month-

long training periodin industry

‘Transfer Engineer’ INSAInitial Research and Development Studiesfor SME companies (duration: few months )Technology and Literature Survey and WatchingExperiments / Data Analysis

Types of collaboration