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N dordre 2008-ISAL-0089

Anne 2008

Thse

Influence des charges sur lvolution des proprits mcaniques des EPDM chargs lors de leur vieillissement par irradiation
Prsente devant

LInstitut National des Sciences Appliques de Lyon

Pour obtenir

Le grade de Docteur
Ecole doctorale : Matriaux de Lyon Par Emilie PLANS Soutenue le 12 Novembre 2008 devant la Commission dExamen Jury MM.
Prsident du jury Rapporteurs BALANZAT Emmanuel (CIRIL Caen) VERDU Jacques (LIM ENSAM Paris) LAUPRETRE Franoise (LRP Thiais) Examinateurs VALLAT Marie-France (Universit de Mulhouse) FOURNIER Jrme (NEXANS Lyon) Directeurs de thse VIGIER Grard (INSA Lyon Villeurbanne) CHAZEAU Laurent (INSA Lyon Villeurbanne)

Remerciements

Ce travail de a pris part au Contrat Programme Recherche Composite & POLymer Ageing . Je remercie tous les partenaires acadmiques et industriels (EDF, CEA, Laborelec, Nexans, INRA) pour la confiance quils mont accorde dans la ralisation de ces travaux. Cette thse a fait lobjet dune collaboration plus spcifique entre la socit Nexans et le laboratoire MATEIS de lINSA de Lyon. Je tiens donc remercier plus particulirement Jrme Fournier et Thomas Stuhldreier pour mavoir accueillie au sein du centre de recherche de Nexans Lyon et particip mon encadrement. Je remercie galement Jean-Yves Cavaill puis Jol Courbon pour mavoir accueillie pendant ces trois annes au sein du laboratoire MATEIS. Pour finir, je tiens adresser dimmenses remerciements mes directeurs de thse : Laurent Chazeau et Grard Vigier qui ont su me donner le got de la recherche et avec qui jai pris beaucoup de plaisir travailler. Je souhaite associer Isabelle Stevenson ces remerciements. Je voudrais remercier Jacques Verdu et Franoise Lauprtre pour avoir accept de rapporter ce manuscrit, ainsi que Emmanuel Balanzat qui ma fait lhonneur de prsider mon jury de thse et Marie-France Vallat pour sa contribution en tant quinvite. Je noublie pas mes compagnons de la vie de tous les jours sans qui les pauses caf nauraient pas t si agrables : Agns, Catherine, David, Jenny, Laurent, Jean-Marc C et P, LouiseAnne, Marianna, Olivier, Sverine Un grand merci Jean-Marc mon co-bureau pour ses prcieux conseils. Enfin, parce quil ny a pas que la science dans la vie, je remercie mes amis, ma famille et en particulier mes parents.

Sommaire
Introduction.1

PARTIE 1 : Synthse bibliographique..6 1re PARTIE : Elastomres non chargs ..................................................................................... 1. Elastomres Elasticit caoutchoutique Consquences sur les proprits mcaniques 9 1.1. 1.1.1. 1.1.2. 1.1.3. 1.2. 1.2.1. 1.2.2. 1.2.3. 2.1. 2.2. 2.2.1. 2.2.2. 2.2.3. 2.2.4. 2.3. 2.3.1. 2.3.2. 3.1. 3.2. Gnralits ............................................................................................................... 9 Quest ce quun lastomre ? ............................................................................... 9 Thorie de llasticit caoutchoutique.................................................................. 9 Dfauts dans les lastomres .............................................................................. 11 Cas particulier des copolymres dthylne et de propylne ................................. 12 Synthse ............................................................................................................. 13 Rticulation par les peroxydes des EPDM ......................................................... 14 Cristallinit ......................................................................................................... 15 Interactions entre les radiations de hautes nergies et un polymre ...................... 17 Cintique des mcanismes de vieillissement ......................................................... 17 La loi dArrhenius .............................................................................................. 18 Schma mcanistique de base ............................................................................ 19 Quantification des produits doxydation ............................................................ 20 Modle de Verdu15-16-17-18 ............................................................................ 22 Influence des paramtres matriaux ....................................................................... 22 Nature chimique du polymre ............................................................................ 23 Cristallinit ......................................................................................................... 25 Pour les polythylnes ........................................................................................... 27 Pour les EPDM ...................................................................................................... 30

2. Vieillissement par irradiation des lastomres non chargs .......................................... 15

3. Consquences sur la microstructure et les proprits mcaniques ................................ 25

2me PARTIE : Elastomres chargs ..................................................................................... 30 1. Les charges .................................................................................................................... 30 1.1. 1.2. 1.2.1. 1.2.2. Gnralits ............................................................................................................. 31 Charges tudies .................................................................................................... 31 La silice nanoscopique ....................................................................................... 31 Les trihydroxydes daluminium ATH ............................................................. 31

2. Mise en ?uvre et microstructure des lastomres chargs Consquences sur les proprits mcaniques .......................................................................................................... 32 2.1. 2.1.1. 2.1.2. 2.1.3. 2.2. 2.2.1. 2.2.2. 2.2.3. 2.2.4. 3.1. 3.2. 3.2.1. 3.2.2. 3.2.3. 3.2.3.1. 3.2.3.2. 3.3. Microstructure des lastomres chargs ................................................................ 33 Les renforts ......................................................................................................... 33 La cristallinit ..................................................................................................... 33 Polymre li ........................................................................................................ 34 Proprits mcaniques des lastomres chargs .................................................... 34 Comportement dans le domaine linaire ............................................................ 35 Modlisation du renforcement ........................................................................... 37 Comportement mcanique non linaire .............................................................. 38 Comportement la rupture ................................................................................. 40 Diffusion de loxygne .......................................................................................... 41 Modification des interactions charges-matrice ...................................................... 41 Consquences de lirradiation sur la silice ......................................................... 41 Consquences de lIrradiation sur les ATH ....................................................... 42 Modification des interactions charge-matrice .................................................... 42 Dans le cas des polymres chargs silice ....................................................... 43 Dans le cas des polymres charges ATH ........................................................ 45

3. Vieillissement par irradiation des lastomres chargs ................................................. 41

Consquences sur la microstructure et les proprits mcaniques ........................ 46

4. Conclusions & Perspectives .......................................................................................... 48

PARTIE 2 : Matriaux Conditions de vieillissement Techniques exprimentales.56 1. Prsentation des matriaux ............................................................................................... 57 1.1. Les matriaux ............................................................................................................ 57 La matrice ........................................................................................................... 57 Les charges ......................................................................................................... 57 La silice nanoscopique .................................................................................... 57 Les trihydrates daluminium ATH ................................................................. 58 1.1.1. 1.1.2. 1.1.2.1. 1.1.2.2. 1.2. 1.3. 2. 2.1.

Les formulations ........................................................................................................ 59 Mise en ?uvre............................................................................................................. 60 Vieillissement radiochimique .................................................................................... 61 Description du dispositif .................................................................................... 61 Dosimtrie .......................................................................................................... 62 Droulement de la premire campagne dirradiation temprature ambiante .. 64 Droulement de la seconde campagne dirradiation 80C .............................. 65

Dispositif de vieillissement ............................................................................................... 61 2.1.1. 2.1.2. 2.1.3. 2.1.4.

2.2. 3. 3.1. 3.2.

Vieillissement thermique ........................................................................................... 65 Spectroscopie Infra-Rouge ........................................................................................ 65 Mesures de gonflement .............................................................................................. 67 Mesures de gonflement dans un solvant : le xylne ........................................... 67 Utilisation de la thorie de Kraus ....................................................................... 68 Mesures de gonflement mixte : xylne/ammoniaque ......................................... 69 Mesure de prise en eau ....................................................................................... 69

Mthodes danalyses ......................................................................................................... 65

3.2.1. 3.2.2. 3.2.3. 3.2.4. 3.3. 3.4. 3.5.

Thermoporosimtrie .................................................................................................. 70 Analyses thermiques diffrentielles (DSC) ............................................................... 71 Essais de traction ....................................................................................................... 73

3.6. Diffusion des X aux petits angles (SAXS) et aux grands angles (WAXS) Mesures in-situ en traction .................................................................................................................. 74 3.6.1. 3.6.2. 3.7. SAXS .................................................................................................................. 74 WAXS ................................................................................................................ 77

Observations microscopiques .................................................................................... 78

PARTIE 3 : Rsultats et discussions.80 Article 1: Evolution of EPDM networks aged by gamma-irradiation Consequences on mechanical properties.81 Abstract .................................................................................................................................... 83 1. 2. Introduction ....................................................................................................................... 83 Experimental ..................................................................................................................... 85 2.1. 2.2. 2.3. Materials .................................................................................................................... 85 Ageing conditions ...................................................................................................... 86 Instruments ................................................................................................................ 86 Swelling measurements ...................................................................................... 87 Tensile tests ........................................................................................................ 87 Thermoporosimetry ............................................................................................ 88

2.3.1. 2.3.2. 2.3.3. 3. 3.1. 3.2. 3.3. 3.4. 4. 5.

Results ............................................................................................................................... 88 Degradation kinetic.................................................................................................... 95 Large strain behavior ............................................................................................... 100 Network heterogeneity ............................................................................................ 102 Simulation ................................................................................................................ 108

Discussion ....................................................................................................................... 109 Conclusions ..................................................................................................................... 110

Acknowledgements ................................................................................................................ 111

Annexe 1: Complments article 1113

Article 2: Crystalline microstructure and mechanical properties of crosslinked EPDM aged under gamma irradiation.119 Abstract .................................................................................................................................. 121 1. 2. Introduction ..................................................................................................................... 121 Experimental ................................................................................................................... 123 2.1. 2.2. 2.3. Materials .................................................................................................................. 123 Irradiation conditions ............................................................................................... 123 Instruments .............................................................................................................. 123 Tensile tests ...................................................................................................... 123 Differential scanning calorimetry..................................................................... 124 SAXS measurements ........................................................................................ 125 In-situ SAXS measurements during stretching ............................................ 127

2.3.1. 2.3.2. 2.3.3. 2.3.3.1. 3. 3.1. 3.2. 3.3. 4.

Results & Discussions..................................................................................................... 127 Microstructure of unaged sample and undeformed sample ..................................... 127 Microstructure evolution during stretching of unaged samples .............................. 132 Consequences of gamma irradiation ........................................................................ 135

Conclusions ..................................................................................................................... 137

Acknowledgments .................................................................................................................. 138 References .............................................................................................................................. 139

Annexe 2: Essais de traction in-situ sous WAXS 25 C et 80 C pour les EPDM non chargs141

Article 3: Influence of fillers on mechanical properties of ATH filled EPDM during ageing by gamma-irradiation...146 Abstract .................................................................................................................................. 148 1. 2. Introduction ..................................................................................................................... 148 Experimental ................................................................................................................... 149 2.1. 2.2. 2.3. Materials .................................................................................................................. 149 Ageing conditions .................................................................................................... 150 Instruments .............................................................................................................. 151

2.3.1. 2.3.2. 2.3.2.1. 2.3.2.2. 2.3.3. 2.3.4. 2.3.5. 3. 3.1. 3.2. 3.3. 3.4.

IR spectroscopy ................................................................................................ 151 Swelling measurements .................................................................................... 151 Swelling in xylene ........................................................................................ 151 Ammonia fumes treatment + swelling in xylene .......................................... 152 Microscopy ....................................................................................................... 152 Tensile tests ...................................................................................................... 153 Differential scanning calorimetry..................................................................... 153

Results ............................................................................................................................. 154 Preliminary characterization of non irradiated materials ........................................ 154 Oxidation ................................................................................................................. 156 Degradation kinetic.................................................................................................. 156 Consequences on mechanical properties at 80C .................................................... 160 At small deformations ...................................................................................... 160 At large deformations ....................................................................................... 162

3.4.1. 3.4.2. 3.5. 3.6. 4.

Evaluation of the filler influence on the degradation kinetic .................................. 165 Consequences on mechanical properties at 25C .................................................... 169

Conclusions ..................................................................................................................... 173

Acknowledgment ................................................................................................................... 174 References .............................................................................................................................. 175

Article 4: Influence of fillers on mechanical properties of silica filled EPDM during ageing by gamma-irradiation......177 Abstract .................................................................................................................................. 179 1. 2. Introduction ..................................................................................................................... 179 Experimental ................................................................................................................... 181 2.1. 2.2. 2.3. Materials .................................................................................................................. 181 Ageing conditions .................................................................................................... 182 Instruments .............................................................................................................. 182 IR spectroscopy ................................................................................................ 182 Swelling meausrements .................................................................................... 183 Swelling in xylene ........................................................................................ 183 Water uptake ................................................................................................. 183 Tensile tests ...................................................................................................... 184 Differential scanning calorimetry analysis ....................................................... 184

2.3.1. 2.3.2. 2.3.2.1. 2.3.2.2. 2.3.3. 2.3.4. 3.

Results and discussion .................................................................................................... 186

3.1. 3.2. 3.3.

Preliminary characterization of studied materials ................................................... 186 Oxidation ................................................................................................................. 187 Degradation kinetic Consequences on mechanical properties at 80C ................ 187 For E-CR material ............................................................................................ 187 For E-SiU material ........................................................................................... 190 For E-SiT material ............................................................................................ 192

3.3.1. 3.3.2. 3.3.3. 3.4. 4.

Consequences on mechanical properties at 25C .................................................... 195

Conclusions ..................................................................................................................... 198

Acknowledgments .................................................................................................................. 199 References .............................................................................................................................. 200

Annexe 3: Observations microscopiques de profils de fractures.........201

Article 5: Role of temperature during ageing by gamma irradiation of filled EPDM Consequences on mechanical properties.206 Abstract .................................................................................................................................. 209 1. Introduction ..................................................................................................................... 209 2.1. 2.2. 2.3. Materials .................................................................................................................. 211 Ageing conditions .................................................................................................... 211 Experiments ............................................................................................................. 212 IR spectroscopy ................................................................................................ 212 Swelling in xylene ............................................................................................ 212 Tensile tests ...................................................................................................... 213

2.3.1. 2.3.2. 2.3.3. 3. 3.1. 3.2.

Results and Discussion ................................................................................................... 214 Homogeneity of the degradation process ................................................................ 214 For unfilled EPDM .................................................................................................. 215 Thermal ageing at 80C.................................................................................... 215 Irradiation at 25C ............................................................................................ 217 Irradiation at 80C ............................................................................................ 218 Thermal ageing at 80C.................................................................................... 221 Irradiation at 25C ............................................................................................ 223 Irradiation at 80C ............................................................................................ 224 Thermal ageing at 80C.................................................................................... 225 Irradiation at 25C ............................................................................................ 227

3.2.1. 3.2.2. 3.2.3. 3.3. 3.3.1. 3.3.2. 3.3.3. 3.4. 3.4.1. 3.4.2.

Consequences of the different ageing conditions on the E-ATHU rubber .............. 221

Consequences of the different ageing conditions on the E-SiU rubber ................... 225

3.4.3. 4.

Irradiation at 80C ............................................................................................ 228

Conclusions ..................................................................................................................... 229

Acknowledgments .................................................................................................................. 229 References .............................................................................................................................. 230

Annexe 4 : Consquences du vieillissement par irradiation 80 C sur les proprits mcaniques temprature ambiante des chantillons non chargs...231

Conclusions et Perspectives..237

Introduction

Introduction

Introduction
Lindustrie nuclaire doit matriser, un degr ingal de fiabilit, les proprits des multiples matriaux quelle utilise dans des conditions dusage trs svres. La prvision du vieillissement des matriaux sous irradiation constitue une tape importante pour la sret des installations nuclaires. Parmi les matriaux utiliss, les polymres, bien que minoritaires par rapport aux mtaux, sont incontournables dans les cbles lectriques, joints et autres passages tanches, peinture et revtements. Ds lorigine des programmes nuclaires, la sensibilit des polymres aux rayonnements ionisants a conduit ltude du comportement long terme en temprature et sous irradiation de ces matriaux. Le vieillissement des polymres, en particulier le vieillissement sous irradiation a t le sujet de nombreux travaux au cours des dernires dcennies. Ils nont conduit pour linstant quau dveloppement de modles cintiques dont lefficacit est limite au cas particulier des polymres sans additifs et sans charges1-2-3. Or dans le cadre dapplications industrielles, afin de les renforcer les polymres sont gnralement mlangs avec des charges. Les charges reprsentent en gnral un pourcentage important de la formulation des polymres industriels et constituent la principale htrognit. Comprendre leur impact sur la nature et la cintique des mcanismes de vieillissement des polymres est un passage oblig. Le renforcement obtenu par la prsence de ces charges est fonction de plusieurs paramtres : les proprits de la phase polymre et des charges, la proportion de charges, la nature des charges et des diffrentes interactions prsentes dans le composite : charge-charge et charge-matrice. Ltude de leffet potentiel des charges sur le vieillissement et des relations entre le vieillissement de la matrice polymre et de linterface charge-matrice avec les proprits macroscopiques telles que les proprits mcaniques na t que trs peu aborde jusqu prsent4-5. Ces rares travaux ont nanmoins montr toute la complexit induite par la prsence de charges. Celles-ci peuvent par exemple modifier la diffusion de loxygne et dans ce cas les mcanismes de dgradation peuvent tre diffrents par rapport ceux observs pour la matrice non charge. En outre, il est bien connu que les paramtres essentiels intervenant dans la rponse mcanique des lastomres chargs, outre ltat de dispersion des charges, sont ltat de rticulation de la phase polymre et le renforcement produit par les charges ncessitant la prise en compte des interactions chargescharges et charge-matrice6-7. Dans le cas de charges microniques, le renforcement peut tre facilement prdit. Par contre pour les charges nanoscopiques, le renforcement est gnralement suprieur celui observ pour des charges microniques mme fraction volumique. En effet, du fait de leur taille, ces charges prsentent une surface dinterface leve et le rle des interactions charge-charge et charge-matrice est prpondrant. Cela a pour consquence de favoriser la formation au sein du composite dun rseau connexe de charges dont les proprits, dpendantes des deux types dinteraction, vont commander pour une trs grande part la rponse mcanique macroscopique du composite. Ainsi si seule la modification de la matrice est considre lors du vieillissement, tant donn le complexe couplage charge-matrice et le comportement mcanique du matriau composite rsultant, il est difficile dvaluer les consquences de lirradiation. En effet, le lien entre les proprits mcaniques du composite et celles de la matrice nonc prcdemment est difficile tablir. De plus, la modification chimique de la matrice sous irradiation peut aussi modifier les interactions charge-matrice. Enfin les charges, si elles ne sont pas inertes sous rayonnement gamma, peuvent induire leurs propres mcanismes de dgradation, qui peuvent modifier leur surface et leurs interactions avec la matrice, et mme induire dventuelles ractions avec la phase polymre. Dans le cas particulier des cbles, les polymres utiliss ont gnralement une forte proportion en thylne, par consquent ceux-ci sont souvent semi-cristallins. La prsence ventuelle de ces cristallites dans les polymres complexifie la comprhension des mcanismes de dgradation lors de leur vieillissement. Du fait de la faible permabilit
2

Introduction
loxygne des cristallites, la phase amorphe peut tre plus sensible la dgradation et les mcanismes de dgradation peuvent tre perturbs via une diffusion htrogne de loxygne. Ainsi les polymres semi-cristallins peuvent tre plus sensibles lirradiation lorsquils sont vieillis une temprature suprieure la temprature de fusion de leurs cristallites. De plus aprs un vieillissement par irradiation en temprature au dessus de cette temprature, un retour temprature ambiante peut permettre une organisation diffrente du matriau. Ce processus assist par les coupures de chanes permet une prservation des proprits mcaniques. Laddition de charges rend encore plus complexe le problme puisque les charges peuvent bien entendu perturber les processus de cristallisation. Ces diffrentes questions intressent tout particulirement le Contrat de ProgrammeRecherche COPOLA dans lequel sinscrivent ces travaux de thse. Celui-ci rassemblant divers partenaires acadmiques et industriels (CNRS, CEA, EDF, Nexans, Electrabel) a lobjectif ambitieux de mettre au point un modle de prdiction de dure de vie des matriaux soumis au vieillissement. Dans cette thse, linfluence du vieillissement sur le comportement des lastomres chargs a t tudie dans le cas de formulations utilises pour les cbles lectriques pour des applications nuclaires et basse-moyenne tension. Nos efforts ont donc port sur ltude dune seule matrice semi-cristalline (5-20%) dj bien tudie : il sagit de lEPDM (Ethylne-Propylne-Dine-Monomer) norbordne8-9 et les charges tudies ont t de deux types : La silice pour faire le lien avec les tudes rcentes4-5, elle est nanoscopique de faon augmenter les interactions charges-matrice et est traite ou non afin dtudier le rle de sa surface. Les trihydrates daluminium (ATH) qui sont une priorit industrielle ; ce sont des charges microniques, leur concentration est importante comme pour les formulations industrielles, cela signifie que comme les charges nanoscopiques les interactions charges-charges et charge-matrice ne sont pas ngligeables.

Lvolution de ces matriaux a t tudie dans le cadre du vieillissement par irradiation : il importe de connatre lvolution de ces matriaux lorsquils sont soumis des conditions de marche normale dune centrale nuclaire (0,2-0,3 Gy/h pendant environ 40ans soit une dose totale absorbe denviron 100kGy). Ainsi nous avons choisi comme type dirradiation : lirradiation gamma. Elle a t ralise en prsence doxygne de manire reproduire au mieux les conditions de vieillissement naturel. Une premire campagne a t ralise temprature ambiante, puis pour tudier leffet de la temprature, une autre campagne a t effectue 80C. En effet, les tempratures dutilisation dans les centrales nuclaires peuvent tre suprieures 25C. Le prsent manuscrit sarticule autour de la dmarche suivante. La premire partie a pour but de faire un point bibliographique, dune part, sur les connaissances acquises sur le vieillissement dlastomres EPDM non chargs ou des matriaux qui sont proches (polythylne) en terme de mcanismes de dgradation, de modles cintiques et de consquences sur les proprits mcaniques ; et dautre part sur les tudes antrieures menes sur le vieillissement par irradiation dlastomres chargs. La seconde partie est consacre la prsentation des matriaux tudis : leur origine et leur mise en uvre et rappelle les conditions de vieillissement ainsi que les techniques exprimentales utilises pour la caractrisation de ces matriaux lors de leur vieillissement.
3

Introduction
Enfin les rsultats obtenus sont prsents et discuts dans la troisime partie. Cette dernire est crite sous la forme de cinq articles en anglais*. Le premier est consacr aux consquences du vieillissement par irradiation temprature ambiante sur les proprits mcaniques ltat amorphe dEPDM non chargs. Les rsultats exprimentaux sont compars un modle prenant en compte les coupures de chanes dans un rseau lastomre. Le deuxime article concerne les mmes matriaux tudis cette fois-ci temprature ambiante. Lventuelle volution de la morphologie cristalline au cours de lirradiation ainsi que les consquences sur les proprits mcaniques ltat semi-cristallin sont exposes. Ensuite les troisimes et quatrimes articles illustrent respectivement le rle des charges silice et ATH sur lvolution des proprits mcaniques lors du vieillissement par irradiation temprature ambiante. Enfin le cinquime article se consacre leffet de la temprature dirradiation pour les trois types de matriaux (non charg, charg silice ou ATH). Des conclusions et des perspectives globales de ces travaux de thse sont proposes en fin de manuscrit. Afin dapprofondir certains articles, trois annexes ont t insres dans la thse. La premire concerne les essais de traction in-situ sous WAXS (diffusion des X aux grands angles) 25C et 80C pour les matriaux non chargs. Ces expriences ont permis dtudier linfluence du degr de rticulation ainsi que celle du vieillissement par irradiation sur lorientation de la phase amorphe lors dun essai de traction temprature ambiante. La deuxime rend compte des observations de facis de rupture dlastomres chargs avant et aprs irradiation. La dernire propose dtudier les consquences de lirradiation 80C sur les proprits mcaniques temprature ambiante de lEPDM non charg par lintermdiaire dune caractrisation de lvolution de sa morphologie cristalline.

Article Non chargs X X X X X

Matriaux Chargs ATH Chargs silice

Conditions de vieillissement Irr 25C* X X X X X Irr 80C* VTh 80C**

Temprature de caractrisation 25C 80C X X X X X X X

1 2 3 4 5

X X X X

(*Irr = Irradiation, **VTh = vieillissement thermique)

Ce choix a des consquences sur lorganisation de cette partie, mme si nous nous sommes efforcs de les articuler comme lauraient t cinq sous-parties rdiges en franais. Afin dallger la lecture du manuscrit, les redites sont en italique.
4

Introduction
Rfrences
1

KHELIDJ N., C.X., AUDOUIN L., VERDU J., MONCHY-LEROY C., PRUNIER V., Oxidation of Polyethylene under Irradiation at Low Temperature and Low Dose Rate. Part II. Low Temperature Thermal Oxidation. Polymer Degradation and Stability, 2006 91:1598-1605 2 KHELIDJ N., C.X., AUDOUIN L., VERDU J., MONCHY-LEROY C., PRUNIER V., Oxidation of Polyethylene under Irradiation at Low Temperature and Low Dose Rate. Part I. The case of "pure" Radiochemical Initiation. Polymer Degradation and Stability, 2006 91-1593-1597 3 KHELIDJ N., C.X., AUDOUIN L., VERDU J., A Simplified Approach for the Lifetime Prediction of PE in Nuclear Environments. Nuclear Instruments and Methods in Physics Research B, 2005. 236: p. 88-94. 4 STEVENSON I., et al., Influence of SiO2 Fillers on the Irradiation Ageing of Silicone Rubbers. Polymer, 2001. 42: p. 9287 - 9292. 5 PATEL M., et al., Gamma Radiation Induced Effects on Silica and on Silica-Polymer Interfacial Interactions in Filled polysiloxane Rubber. Polymer Degradation and Stability, 2006. 91: p. 406-413. 6 CHAZEAU L., et al., Relationships Between Microstructural Aspects and Mechanical Properties in Polymer Based Nanocomposites. Handbook of "organic-inorganic hybrid materials and nanocomposites, Pt2" Dr. H.S. Nalwa ed., American Scientific Publishers, 2004. 7 RAMIER J., et al., Grafting of Silica during the Processing of Silica-Filled SBR : Comparison between Length and Content of the Silane. Journal of Applied Polymer Science: Part B: Polymer Physics, 2006. 44: p. 143-152. 8 CELETTE N., et al., Relaxation Behaviour of Radiochemically Aged EPDM Elastomers. Nuclear Instruments and Methods in Physics Research B, 2001. 185: p. 305 - 310. 9 RIVATON A., CAMBON S., and GARDETTE J.L., Radiochemical Ageing of EPDM Elastomers. 3. Mechanism of Radiooxidation. Nuclear Instruments and Methods in Physics Research B, 2005. 227: p. 357 - 368.

PARTIE 1

Synthse Bibliographique

PARTIE 1
Synthse bibliographique

PARTIE 1

Synthse Bibliographique

1re PARTIE : Elastomres non chargs .................................................................................................. 9 1. Elastomres Elasticit caoutchoutique Consquences sur les proprits mcaniques .. 9 1.1. 1.1.1. 1.1.2. 1.1.3. 1.2. 1.2.1. 1.2.2. 1.2.3. 2. Gnralits ........................................................................................................................... 9 Quest ce quun lastomre ? .......................................................................................... 9 Thorie de llasticit caoutchoutique .......................................................................... 11 Dfauts dans les lastomres......................................................................................... 11 Cas particulier des copolymres dthylne et de propylne............................................. 12 Synthse ......................................................................................................................... 12 Rticulation par les peroxydes des EPDM .................................................................... 13 Cristallinit .................................................................................................................... 14

Vieillissement par irradiation des lastomres non chargs ................................................ 15 2.1. 2.2. 2.2.1. 2.2.2. 2.2.3. 2.2.4. 2.3. 2.3.1. 2.3.2. Interactions entre les radiations de hautes nergies et un polymre .................................. 15 Cintique des mcanismes de vieillissement ..................................................................... 17 La loi dArrhenius ......................................................................................................... 17 Schma mcanistique de base ....................................................................................... 18 Quantification des produits doxydation ....................................................................... 19 Modle de Verdu15-16-17-18 ............................................................................................... 20 Influence des paramtres matriaux .................................................................................. 22 Nature chimique du polymre ....................................................................................... 22 Cristallinit .................................................................................................................... 23

3.

Consquences sur la microstructure et les proprits mcaniques ..................................... 25 3.1. 3.2. Pour les polythylnes ....................................................................................................... 25 Pour les EPDM .................................................................................................................. 27

2me PARTIE : Elastomres chargs ..................................................................................................... 30 1. Les charges ............................................................................................................................... 30 1.1. 1.2. 1.2.1. 1.2.2. Gnralits ......................................................................................................................... 30 Charges tudies ................................................................................................................ 31 La silice nanoscopique .................................................................................................. 31 Les trihydroxydes daluminium ATH.......................................................................... 32

2. Mise en uvre et microstructure des lastomres chargs Consquences sur les proprits mcaniques .................................................................................................................... 33 2.1. 2.1.1. 2.1.2. Microstructure des lastomres chargs ............................................................................ 33 Les renforts .................................................................................................................... 33 La cristallinit ............................................................................................................... 33
7

PARTIE 1
2.1.3. 2.2. 2.2.1. 2.2.2. 2.2.3. 2.2.3.1. 3.

Synthse Bibliographique

Polymre li ................................................................................................................... 34 Proprits mcaniques des lastomres chargs ................................................................ 34 Comportement dans le domaine linaire ....................................................................... 34 Modlisation du renforcement ....................................................................................... 35 Comportement mcanique non linaire......................................................................... 37 Comportement la rupture ....................................................................................... 38

Vieillissement par irradiation des lastomres chargs ....................................................... 40 3.1. 3.2. 3.2.1. 3.2.2. 3.2.3. 3.2.3.1. 3.2.3.2. 3.3. Diffusion de loxygne ...................................................................................................... 41 Modification des interactions charges-matrice .................................................................. 41 Consquences de lirradiation sur la silice ................................................................... 41 Consquences de lIrradiation sur les ATH .................................................................. 42 Modification des interactions charge-matrice .............................................................. 42 Dans le cas des polymres chargs silice .................................................................. 43 Dans le cas des polymres charges ATH................................................................... 45

Consquences sur la microstructure et les proprits mcaniques .................................... 46

4.

Conclusions & Perspectives .................................................................................................... 48

PARTIE 1

Synthse Bibliographique

Cette partie a pour but de faire un point bibliographique des connaissances acquises dans le domaine du vieillissement des lastomres. Dans un premier temps, un bref rappel des proprits caractristiques des lastomres non chargs sera prsent, un point sera galement fait sur le cas particulier des terpolymres thylne propylne dine monomre (EPDM), puis des rsultats antrieurs concernant les cintiques de vieillissement de ces lastomres non chargs ou de polymres de nature proche ainsi que les consquences de ces mcanismes de dgradation sur les proprits mcaniques seront exposes. La seconde partie traitera des lastomres chargs. Tout dabord seront prsentes les charges tudies dans cette thse ainsi que les proprits mcaniques des lastomres chargs en gnral ; cette partie sera ensuite complte par ltat de lart concernant leur vieillissement par irradiation. Comme il existe peu dtudes traitant du vieillissement par irradiation des EPDM chargs ATH ou silice, il a t choisi de montrer comment les charges dune part pouvaient modifier les mcanismes de dgradation et dautre part, comment les proprits mcaniques de ces matriaux voluaient au cours du vieillissement.

1re PARTIE : Elastomres non chargs 1. Elastomres Elasticit caoutchoutique Consquences sur les proprits mcaniques
1.1. Gnralits 1.1.1. Quest ce quun lastomre ? Un polymre est constitu de longues chanes formes par la rptition dun motif unitaire le monomre , qui peut tre toujours le mme (homopolymre) ou de nature variable (copolymre). Ces chanes sont replies et enchevtrs ltat amorphe. Les enchevtrements agissent comme des points de rticulation physique quand le matriau est soumis une contrainte pendant un temps court ; mais si la dformation est lente, le matriau non pont se dsenchevtre. Les lastomres sont un type particulier de matriau polymre qui possde limpressionnante facult de pouvoir supporter de trs grandes dformations. Il se caractrise aussi par la quasi-recouvrance de ses proprits initiales quand la sollicitation cesse. Le plus souvent, il nacquiert ses proprits quaprs une opration dite de rticulation qui consiste crer des liaisons chimiques fortes entre les chanes macromolcules constituant le matriau. En gnral ladditif permettant lors dun traitement thermique la rticulation est le soufre mais peut tre aussi le peroxyde. Lintrt du peroxyde est double. Il permet tout dabord de rticuler les lastomres compltement saturs (copolymres thylne-propylne, polythylne chlor, polysiloxanes) mais galement, compte tenu du fait quil conduit la formation de liaison carbone carbone particulirement solides, de rticuler les lastomres diniques lorsque lon veut confrer aux vulcanisats une bonne rsistance la chaleur. La plus classique met en jeu des peroxydes organiques. La rticulation par irradiation peut tre aussi utilise. Elle est particulirement utilise dans le cas du polythylne, mme industriellement. Aujourdhui pour les lastomres, la rticulation
9

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Synthse Bibliographique

par irradiation est prsente comme une alternative par rapport aux mthodes chimiques classiques. Cette mthode possde un certain nombre davantages : labsence de traitement thermique, dajouts dadditifs chimiques, un procd rapide, une facilit et une uniformit du traitementPar exemple la rticulation par irradiation des silicones, sans ajouts dadditifs chimiques prsente un rel intrt pour les applications mdicales. Aprs rticulation, les chanes polymres forment un filet trois dimensions plus communment appel rseau polymre. Les nuds de rticulation bloquent la diffusion des chanes. Cela confre au rseau un caractre solide de grandes chelles spatiales (~ 0,1 m). Cest la raison pour laquelle ce type de matriau ne coule pas et conserve sa forme. Localement, les chanes gardent la possibilit de se reconfigurer, ce qui donne au matriau les caractristiques dun liquide cette chelle. Cette dualit liquide-solide confre au rseau polymre des proprits lastiques de type caoutchoutique, leur permettant de subir de faon rversible de grandes dformations. Les polymres strospcifiques, donc rguliers, peuvent cristalliser au dessus dune certaine temprature. Et pour certains polymres, ils cristallisent spontanment au-del dune certaine extension alors quils sont au dessus de leur temprature de fusion normale. Durant la dformation, les chanes sorientent partir de leur tat alatoire en pelote dans le sens de ltirement. Lordre cre diminue lentropie de conformation impliquant laugmentation de la temprature interne de cristallisation. Une phase cristalline par opposition la phase amorphe apparat et se dveloppe ainsi avec la dformation. Les deux phnomnes sont particulirement intressants car ils confrent au matriau des proprits exceptionnelles.

Figure 1 : a) Courbe de spectromtrie mcanique pour un lastomre classique : module lastique en fonction de la temprature. En pointills : courbe dun lastomre rticul, en trait plein : courbe dun lastomre cru (non rticul) ; b) Courbe contrainte-dformation dun lastomre classique Sur la figure 1 a), la courbe montre le comportement typique dun lastomre lors dune sollicitation dynamique frquence constante en fonction de la temprature : A basse temprature, llastomre est ltat vitreux. Le module mesur est de lordre de quelques GPa. Cette rigidit est due au grand nombre dinteractions de type Wan der Waals (intrachanes). Lnergie mise en jeu dans les interactions entre les segments est suprieure celle de lagitation thermique. Quand la temprature augmente, une diminution brutale du module lastique est observe appele relaxation (T) associe la transition vitreuse de llastomre. La
10

PARTIE 1

Synthse Bibliographique

valeur de T dpend de la mobilit intrinsque des chanes influence par lencombrement strique des segments, de leur polarit, et trs lgrement de la rticulation. Pour les plus fortes tempratures, correspondant ltat caoutchoutique, la valeur du module est le plus souvent comprise entre 0.1 et 1 MPa. Lagitation thermique devient prdominante sur les interactions entre les chanes. Le module de llastomre est directement li lenchevtrement des chanes (liaisons physiques) et la rticulation (liaisons chimiques). En outre le matriau est peu visqueux. Les lastomres sont utiliss ltat caoutchoutique. Pour de trs faibles sollicitations comme le montre la figure 1 b), le comportement de llastomre est linaire et le module est indpendant de la dformation (ou de la contrainte) applique. Pour de plus grandes dformations, un comportement non linaire est observ qui se traduit par un fort durcissement du matriau. 1.1.2. Thorie de llasticit caoutchoutique Les proprits remarquables des lastomres ont t thorises dans les annes 40 indpendamment par W. Kuhn et H.M. James et E. Guth1 : llastomre est constitu de chanes fondues lies par des nuds de rticulation. Chaque chane constitue un ressort entropique : la traction tend orienter dans la mme direction, par contre lagitation thermique tend lui confrer une orientation alatoire, ce qui donne lieu une force alatoire2. Une approche thermodynamique de ce processus permet de modliser la force de rappel de la chane tire. La modlisation des proprits de llastomre passe alors par la dfinition de la structure de rseau quelle constitue. Le premier modle a t dvelopp par James et Guth (1943) et consiste placer les chanes sur les cts dun rseau cubique. En utilisant lapproximation gaussienne pour le calcul de la force entropique exerce par la chane, lexpression de la contrainte nominale n en fonction de lallongement est la suivante :
n

N c kbT

1
2

o Nc est le nombre de chanes actives, kB la constante de Boltzmann et T la temprature. Ce modle peut tre raffin au niveau de la description du rseau. Un modle huit chanes a t dvelopp par Arruda et Boyce3, a lavantage de donner des expressions analytiques et de permettre de mieux rendre compte des observations dans des situations de contraintes complexes (type de dformation traction flexion compression) et des comportements aux grandes dformations, puisquil utilise une statistique Langevin pour la description de la chane seule. Sa grande maniabilit explique quil est actuellement trs utilis. 1.1.3. Dfauts dans les lastomres Il nest pas rare que ces rseaux lastomres comportent un certain nombre de dfauts ayant des consquences plus ou moins importantes sur les proprits mcaniques. Htrognit du rseau lastomre : Daprs Groebler et al.4, lhtrognit de la rticulation permet damliorer les proprits mcaniques par une meilleure dissipation dnergie. Les rseaux bimodaux forms de chaines longues et de chaines courtes sont un exemple de rseau htrogne. Dans plusieurs tudes
11

PARTIE 1

Synthse Bibliographique

traitant des proprits mcaniques de ces matriaux, Mark et al.5-6 ont montr que la rsistance passe par un maximum, lorsque la proportion de chanes courtes augmente. Cependant, une proportion trop leve de chanes courtes conduit un comportement fragile : la dformation est limite par lextensibilit maximum des chanes courtes. Les chanes libres et pendantes : La prsence de fraction soluble dans un lastomre a pour consquence de diminuer le module lastique. En ce qui concerne les chanes pendantes, il est relativement difficile de dterminer leur influence, la part du problme tant dobtenir des informations sur leur proportion, leur tailleSeules quelques informations sur les rseaux PDMS sont disponibles7. Andrady et al.7 ont tudi linfluence des chanes pendantes sur les proprits mcaniques dun rseau lastomre PDMS. Ils ont montr une diminution modre du durcissement et du module aux petites dformations avec une augmentation de la proportion de chanes pendantes, mais le rle de ces dernires reste tout de mme incompris. Kluppel8 a galement suggr que les chanes pendantes peuvent rduire la contrainte la rupture, car elles ne contribuent pas au module et ont essentiellement un effet dilution . Il a aussi adopt le point de vue que les proprits la rupture sont avant tout rgies par la proportion denchevtrements pigs. 1.2. Cas particulier des copolymres dthylne et de propylne Les premiers copolymres dthylne-propylne possdant des proprits lastiques ont t dvelopps dans les annes 50. Compte tenu de leur facilit de fabrication, du faible cot des monomres utiliss, on aurait pu penser que ces nouveaux lastomres prendraient trs rapidement une place prpondrante. Or, aujourdhui, ils ne reprsentent quune place ngligeable de la consommation mondiale des lastomres. En effet, tout dabord, les premiers copolymres ne pouvaient tre rticuls que par des peroxydes du fait de leur complte saturation et cest un mode de rticulation peu pris par les transformateurs. Lapparition des terpolymres rticulables par les moyens classiques na pas pour autant lev les difficults qui peu peu se sont rvles quant limpossibilit dutiliser ce type dlastomres pour la fabrication des pneumatiques9. En contrepartie, ils peuvent absorber une grande quantit de charges et de plastifiants (ce qui permet une diminution importante du prix de revient) et ils ont, en outre, de remarquables proprits de rsistance au vieillissement. Pour ces deux raisons, ils ont trouv de nombreux dbouchs dans dautres secteurs. Par exemple, ils sont particulirement utiliss dans lindustrie du cble. 1.2.1. Synthse Les EPDM sont synthtiss par un procd de polymrisation en solution en une tape, dans un hydrocarbure aliphatique (hexane), par raction entre lthylne, le propylne et le dine en prsence dun catalyseur de type Ziegler-Natta. Les EPDM peuvent tre galement obtenus par polymrisation en suspension, en prsence dun catalyseur de type Ziegler-Natta. Les diffrents types commerciaux dEPDM se diffrencient par : Le rapport entre units de type propylne et units de type thylne (pourcentage dthylne compris entre 40 et 75%). La nature du dine : ENB : 5-thylne 2-norbornne HD : 1,4-hexadine
12

PARTIE 1
DCPD : dicyclopentadine
CH2 CH CH2 CH DCPD ENB CH3 CH CH HD CH3

Synthse Bibliographique

Figure 2 : Les diffrents dines Ces monomres diniques possdent une double liaison suffisamment ractive pour copolymriser avec les units thylne et propylne tandis que lautre insaturation, prsente sur la chane latrale, ne participe pas aux ractions de polymrisation. Le taux de dine (de 0,5 10%) La masse molaire et la distribution en masse 1.2.2. Rticulation par les peroxydes des EPDM Les EPDM peuvent tre rticuls par les peroxydes organiques selon le mcanisme radicalaire suivant :

(1) RO (2) (3) R 2 P

OR O

R O P

Dcomposition du peroxyde Arrachage de l'hydrogne Rticulation

+
R C CH3

P P

+
OR

ROH

P P

(4) P (5)

Pas de rticulation CH2 CH3 CH2

H C H Scission

CH2

CH2

CH2

(6) 2

CH2

C CH3

CH2

CH2

CH2

CH CH3

CH2

CH2

CH2 CH3

CH

CH2

Figure 3 : Rticulation au peroxyde des EPDM10 La raction de rticulation est base sur la dcomposition des peroxydes qui conduisent la formation de radicaux peroxyles (1), ils peuvent ragir avec les chanes polymres par arrachage dun hydrogne labile pour produire un macroradical (2). La combinaison de deux macroradicaux cre un nud de rticulation (3). Cependant les ractions (4), (5) et (6) sont en comptition avec la raction de rticulation (3). Larrachage dhydrognes a lieu sur les
13

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Synthse Bibliographique

hydrognes les plus labiles : allylique > tertiaire > secondaire > primaire. La ractivit des radicaux produits suit lordre inverse. En absence de dine, larrachage dhydrogne a lieu sur les squences thylne et propylne. La rticulation des EPM ou EPDM est possible mais est de faible efficacit cause des ractions de scissions ayant sur lieu sur les radicaux tertiaires provenant de larrachage dhydrogne sur les squences polypropylnes. Le rsultat de la comptition entre les phnomnes de rticulation et de scissions de chanes est fortement dpendant des proportions dthylne et de propylne. Plus la proportion en propylne sera importante, plus les scissions de chanes seront favorises lors de la phase de rticulation. En prsence du dine, les radicaux peuvent ragir de deux faons diffrentes sur la double liaison : par arrachage dhydrogne ou par addition sur la double liaison. La seconde voie est favorise lorsque la double liaison est terminale. En effet, les radicaux produits par raction daddition sont relativement ractifs, et ils peuvent ragir facilement sur une autre double liaison terminale. Ainsi un nud de rticulation est cr sans pour autant dtruire un radical. Laddition dun radical sur une double liaison interne est plus difficile, car les radicaux allyliques sont stabiliss par rsonance. Finalement, la formation de radicaux partir des units insatures est dtermine par leur position (interne-terminale), le nombre dhydrognes allyliques, leur accessibilit et la stabilit relative des radicaux allyliques qui peuvent tre cres. La rticulation au peroxyde dans le cas de lEPDM-ENB est trs efficace par rapport lEPDM-HD. En effet comme lENB possde une double liaison ainsi que 5 hydrognes allyliques : il sagit donc dune structure trisubstitue, le mcanisme de rticulation par addition est particulirement favorable. 1.2.3. Cristallinit De fait, contrairement de nombreux lastomres synthtiques (styrne butadine rubber, acrylonitrile butadine styrne), les EPDM peuvent tre semi-cristallins. Dans le cas dune proportion majoritaire dthylne, les cristallites sont composes de segments thylniques. Comme dans le polythylne ces cristallites peuvent tre assimiles des nano-renforts lamellaires pour plusieurs raisons : Leur forme : la phase cristalline est constitue de lamelles dominantes et laxe des chanes est orient selon la direction de priodicit des lamelles. Leur facteur de forme : dans les sphrolites de polythylne, les lamelles cristallines peuvent crotre jusqu plusieurs dizaine de microns pour des paisseurs de lamelles amorphes souvent voisines de 15-20 nm. Les lamelles cristallines prsentent donc des facteurs de forme levs compris entre 100 et 1000. Leurs proprits lastiques : les proprits lastiques des cristallites, bien que difficiles dterminer avec prcision, sont anisotropes. En outre, selon la direction perpendiculaire laxe des chanes le module des cristallites est faible tant donn que seules les forces de Van Der Waals. En contrepartie, selon laxe des chanes, les liaisons covalentes assurent aux cristallites une lasticit comparable celles des mtaux dans le cas darrangement parfait des chanes cristallines dans les lamelles. Ainsi dans les polymres semi-cristallins, lalternance priodique des lamelles cristallines et des couches amorphes peut tre compare la structure dun nanocomposite forts taux de renforts organiques dans lequel les lamelles cristallines seraient assimiles des renforts lamellaires rigides haut facteur de forme. La phase amorphe serait assimile la phase continue (matrice).

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PARTIE 1

Synthse Bibliographique

En ce qui concerne les copolymres EPDM base dthylne, plus la part dthylne est basse, plus est faible le taux de cristallinit ainsi que la temprature de fusion. Les copolymres ayant une part en thylne infrieure 60% massique sont essentiellement amorphes. La gamme de temprature de cristallisation de ces matriaux est gnralement trs large et bien infrieure la temprature de fusion du polythylne. En fait, Lorsque que le taux dthylne diminue, les volutions de temprature de fusion et de taux de cristallinit observes sont provoques par une diminution de la taille des cristallites, paramtre intrinsquement li la longueur des segments thylnes capables de cristalliser : la morphologie cristalline correspondante se trouve altre.

2. Vieillissement par irradiation des lastomres non chargs


2.1. Interactions entre les radiations de hautes nergies et un polymre Le terme de radiation de haute nergie dsigne tout type de radiation corpusculaire ou de radiation lectromagntique possdant respectivement lnergie cintique ou le quantum dnergie nettement suprieur lnergie de dissociation dune liaison. Dans le cas dune radiation ionisante, celle-ci a une nergie suprieure au potentiel dionisation. Les diffrents types de rayonnement ionisants sont habituellement groups en deux grandes catgories : Les rayonnements de nature lectromagntique. Les rayons X, UV, et sont les plus couramment tudis. Des radionuclides (noyau 60Co et 137Cs) mettent des photons avec des dbits de dose faibles (infrieurs 6kGy/h) et il faut des temps dexposition longs pour obtenir des doses fortes. Les rayonnements non photoniques (neutrons, protons, lectrons, ions). Un flux continu ou puls de ces rayonnements peut tre gnr industriellement et acclr par des champs lectromagntiques (sauf dans le cas des neutrons). Il est ainsi possible dobtenir des nergies allant jusqu plusieurs dizaines de MeV. Rappel : Lnergie absorbe par la matire est appele dose. Lunit de la dose est le Gray (Gy) qui correspond un joule dnergie absorbe par kg de matire irradie. Lnergie absorbe par unit de temps est le dbit de dose. Lunit du dbit de dose est le Gy/s ou le kGy/h. Une autre grandeur souvent utilise est le rendement radiochimique G dune raction, qui est dfini comme le nombre despces chimiques formes pour 100 eV absorbes. Dans le cadre de cette tude, nous nous limiterons aux effets produits sous un rayonnement . Les rayonnements sont des radiations lectromagntiques de haute nergie mises par des noyaux atomiques. Les sources classiques de rayonnement gamma sont les noyaux radioactifs longue dure de vie tels que le 60Co et le 137Cs. Leffectif dune population datomes radioactifs diminue exponentiellement avec le temps : cest la loi de dcroissance radioactive. Dans ltude, ce sont des noyaux 60Co qui ont t utiliss. Le 60Co a une dure de demi-vie de 5.26 ans ; il met des photons gamma de 1.17 MeV et de 1.33 MeV. Les rayonnements gamma ne possdent pas de charge lectrique. Ils interagissent avec la matire suivant trois processus (effet photolectrique, effet Compton, cration de paires lectron-positron). Mais dans le cas de rayonnement gnrs par le 60Co, le phnomne
15

PARTIE 1

Synthse Bibliographique

principal qui participe aux interactions entre les photons et le matriau polymre est leffet Compton. Pour cet effet, le photon gamma possde une nergie plus que suffisante pour arracher un lectron d'orbitale; l'nergie restante est rmise sous forme d'un nouveau photon gamma de moindre nergie et dont la direction d'mission est diffrente de la direction incidente du photon gamma d'origine. L'efficacit de la diffusion Compton diminue avec l'augmentation de l'nergie des photons; on pense que c'est le principal mcanisme d'absorption des rayons gamma dans la gamme d'nergie entre 100 keV et 10 MeV, qui est celle qui inclut la plus grande part de radiations gamma provenant d'une explosion nuclaire. La diffusion Compton est relativement indpendante du numro atomique de la matire absorbant les photons gamma. Lorsque le rayonnement interagit avec les lectrons des orbitales molculaires ou atomiques, des lectrons secondaires seront jects. Ces lectrons possdent une nergie suffisante pour provoquer des ionisations supplmentaires ou des excitations lectroniques des molcules environnantes. Dans le cas de lirradiation dun polymre, les principales ractions radicalaires qui interviennent au cours du vieillissement sont les suivantes : Les ractions de dcomposition radicalaire qui constituent lacte damorage : R-X R + X Les ractions de recombinaison radicalaire, parmi lesquelles on peut citer les ractions de rticulation : R + X RX Les ractions de dismutation au cours desquelles deux radicaux se recombinent pour former deux molcules stables, lune tant plus insature que lautre : R + P A + B Les ractions de propagation parmi lesquelles on peut citer le transfert dhydrogne : Propagation : RX + Y R + XY Transfert dhydrogne : R + XH RH + X Les ractions daddition des radicaux sur les molcules insatures pour former un nouveau radical : R + C=C R-C-C Lnergie des radiations de haute nergie est nettement suprieure toute nergie de liaison. La probabilit dinteraction photon-liaison dpend peu de la nature de cette dernire, sauf si elle appartient une structure rsonante dans laquelle lnergie absorbe se rpartit rapidement sur un grand nombre de liaisons. Les actes damorage sont donc distribus de faon statistique dans le matriau. Les radicaux forms au cours de ltape damorage sont trs ractifs. Les mcanismes qui entrent en jeu dpendent des conditions dirradiation: Dans certains cas le milieu est priv doxygne. Ce cas est rencontr lorsque le matriau est vieilli sous vide ou dans un environnement satur en gaz inerte ou pour des chantillons de trs faibles paisseurs mais irradi avec des forts dbits de dose. Dans ces conditions, loxygne dissous dans la structure est vite consomm et sa cintique de diffusion ne permet pas de le renouveler. Les radicaux forms donnent soit de nouvelles rticulations soit des coupures de chanes. Il y a gnralement comptition entre les deux phnomnes mais la vitesse des mcanismes dpend du
16

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Synthse Bibliographique

type de polymre et un des deux effets est prdominant. En labsence doxygne, on observe la formation dinsaturations. Dans le cas de lEPDM, Rivaton et al.11-12 ont montr que sa dgradation sous irradiation lectronique sous atmosphre inerte (argon) engendrait des mcanismes de rticulation, la formation dinsaturations (transvinylne, vinyle, vinylidne, et dinique) et a pour consquence la production de dihydrogne. Lirradiation en prsence doxygne conduit gnralement plus de scissions de chanes que sous gaz neutre. La rticulation fait intervenir des couplages de radicaux, et dans un milieu riche en oxygne, ces molcules ragissent rapidement avec les radicaux et empchent les recombinaisons donc la rticulation du polymre. Lirradiation tant li la diffusion de loxygne, les problmes dhtrognits de dgradation peuvent intervenir quand les chantillons sont pais. La temprature laquelle est ralise la campagne dirradiation peut galement avoir des incidences. Des tudes rcentes13 se sont intresses cette question. Un couplage entre temprature et irradiation a t mise en vidence et a t attribue : Laugmentation du coefficient de diffusion de loxygne provoque par laugmentation de la temprature. Il sagit dun paramtre pertinent lorsque les matriaux vieillis sont massifs, dans ce cas, une meilleure diffusion de loxygne permet une homognisation du profil doxydation. Lactivation par la temprature des ractions de dgradation. Un mcanisme additionnel : la dcomposition des hydroperoxydes (unimolculaire et/ou bimolculaire). Au-del dune temprature, ces composs ne sont plus stables thermiquement et leur dcomposition entraine lamorage de nouvelles chanes. 2.2. Cintique des mcanismes de vieillissement Les processus de vieillissement dun polymre expos en temprature ou des irradiations sont varis et trs complexes. Malgr les nombreux travaux raliss sur le sujet, il nexiste aujourdhui aucun modle pouvant prvoir la fin de vie dun matriau. La simple loi dArrhenius est gnralement utilise pour rendre compte de leffet de la temprature sur la cintique de vieillissement des polymres. 2.2.1. La loi dArrhenius Il existe plusieurs modes de vieillissement des polymres (thermique, irradiation). Chacun deux est un phnomne complexe, dcomposable en un nombre plus ou moins important de processus lmentaires : ractions chimiques, mouvements molculaires, relaxations mcaniques La plupart de ces processus sont thermo-activs et leur cintique obit une loi dArrhenius :
0

exp

E RT

O est le temps caractristique du processus la temprature T, 0 et E des paramtres propres au processus et au matriau, et R la constante des gaz parfaits. Lquation dArrhenius est sans aucun doute la relation dquivalence temps-temprature la plus couramment utilise dans le domaine du vieillissement des polymres. Le principe de cette approche est de prdire lvolution dune proprit P par extrapolation des rsultats obtenus haute temprature. Mais ce point de vue renferme plusieurs hypothses :
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La cintique dvolution de la proprit est simplement lie la cintique de dgradation du matriau. La vitesse doxydation obit la loi dArrhenius, c'est--dire que la dgradation est assimile un processus lmentaire. Les mcanismes chimiques mis en jeu ne varient pas avec la temprature ou le dbit de dose. Plusieurs arguments plaident contre lutilisation de cette loi : La prsence de transitions propres aux matriaux : transition vitreuse, fusion La coexistence de divers processus thermochimiques avec des paramtres dactivation diffrents, i.e. prdominants dans des intervalles de tempratures diffrents Lespce tudie est implique dans diffrentes ractions dnergies dactivation thermique diffrentes La coexistence de modes damorage radicalaire par dcomposition dhydroperoxydes et par irradiation 2.2.2. Schma mcanistique de base Des modles plus complexes prenant en compte les mcanismes de dgradation chimique ont t galement dvelopps. Le tout premier a t tabli par les chercheurs du RAPRA dans les annes 1940 pour les polymres hydrocarbons saturs non stabiliss14. Amorage Polymre (PH) P Propagation P + O2 POO Propagation POO + RH POOH + P Terminaison P + P Produits Terminaison P + POO Produits Terminaison POO + POO Produits + O2 Ces diffrentes ractions entranent trois types de modifications structurales dans les polymres : Des coupures de chanes Des rticulations Des modifications des groupements latraux (produits doxydation greffs sur les chanes polymres) Ces diffrents processus peuvent par ailleurs saccompagner de gaz (dihydrogne, mthane, dioxyde de carbone) La connaissance des produits doxydation peut se rvler tre trs intressante. En effet, leurs natures, leurs formations et leurs concentrations sont typiques du matriau vieilli. Cette approche prsente lavantage de donner des indices sur les mcanismes de formation des produits doxydation lors de leur vieillissement, mais celle-ci ne donne pas dinformations directes sur les mcanismes de scissions de chanes, ou de rticulations quimpliquent ces ractions.
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2.2.3. Quantification des produits doxydation La dtermination des produits doxydation met en uvre en gnral les mthodes de caractrisation suivantes : RPE (rsonance paramagntique lectronique), RMN (rsonance magntique nuclaire) et spectroscopie Infra-Rouge. Lessentiel des travaux de Rivaton et al.11-12 concerne ltude du comportement dun EPDM et dun EPR (Ethylne Propylne Rubber) sous leffet de lirradiation de haute nergie en prsence doxygne pour en dterminer les mcanismes de dgradation radio-oxydative (les irradiations ont t effectues temprature ambiante sur des films de 100 200m dpaisseur). Ils ont propos un mcanisme de dgradation de lEPDM sous irradiation gamma en prsence doxygne (figure 4). Linteraction des radiations de haute nergie avec le matriau est non slective : les effets les plus significatifs produits par les radiations de hautes nergies sur le matriau rsultent des interactions au hasard avec les lectrons orbitalaires. La radiolyse des polyolfines (PH) permet la scission des liaisons les plus fortes C-H, alors que les liaisons CC sont moins affectes. Quand lexposition des polyolfines des radiations de haute nergie est effectue sous atmosphre oxygne, beaucoup de radicaux alkyles P rsultant des effets directs des radiations (scissions des liaisons C-H et C-C, raction (1)) peuvent se combiner avec loxygne (Raction (2)) dissout dans le polymre. Les radicaux peroxydes (PO2) quant eux peuvent ragir de deux faons : La premire est labsorption des atomes dhydrogne sur la chane polymre qui permet que les premiers produits doxydation forms soient les hydroperoxydes (raction (3)). Ceci propage le processus doxydation de chanes car la formation des macro-radicaux alkyles (P) relance des ractions doxydation des chanes ; La seconde est la recombinaison des radicaux peroxyles, qui conduit la terminaison des chanes doxydation du polymre (raction 4) donnant comme produits finaux des ctones et des alcools. Les ractions (3) et (4) sont en comptition. La raction (3) requiert une nergie dactivation suffisante. Cette raction a plus facilement lieu lorsque la temprature est augmente. La raction (4) peut avoir lieu temprature modre pour de faibles concentrations de PO2.

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Figure 4 : Mcanisme de vieillissement par irradiation gamma de lEPDM sous atmosphre oxygne11-12 En associant la technique de titration chimique et la spectrophotomtrie IR, les rendements de formation en espces ctone, acide carboxylique, alcool et hydroperoxyde ont t dtermins. Les rsultats obtenus pour lEPR et lEPDM montrent que le second se dgrade plus rapidement que le premier11-12.

2.2.4. Modle de Verdu15-16-17-18 A partir de la quantification des produits doxydation, des schmas mcanistiques ont pu tre mis en place. Certains sont trs simplistes (tel que celui prsent prcdemment) car trs loigns de lexprience ou si pour dautres le schma est utilis dans son intgralit, les hypothses laccompagnant sont souvent trs rductrices. En guise dexemple, nous allons prsenter le modle de radio-oxydation du polythylne tabli par Verdu et al.15-16-17-18 qui nous apparat lun des plus aboutis pour ce polymre. Il utilise les donnes exprimentales de Decker et ses collaborateurs publies dans les annes 197019-20. Ces donnes ont t obtenues pour des chantillons irradis par rayonnement gamma 45C sous air, les paisseurs des chantillons taient de lordre de 50 m, de telle sorte quaucun phnomne ne soit contrl par la diffusion de loxygne. Ces donnes ont pos plusieurs questions : Le rendement en radicaux peut tre obtenu partir de trois modes de calculs diffrents et ceux-ci donnent trois rsultats diffrents. Concernant les groupes carbonyle, quel mcanisme par combinaison bimolculaire conduit la formation despces carbonyle. Pourquoi le processus de dismutation de Russel na-t-il pas t envisag ?
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Le phnomne de scission de chanes doit tre pris en compte puisquil sagit du phnomne prdominant conduisant la dgradation du matriau. Or ce phnomne nest pas inclus dans le schma mcanistique de base. Ainsi Verdu et Kelidj15 proposent un nouveau modle pour la radio-oxydation du polythylne pour rpondre ces incohrences. Afin de pouvoir rsoudre numriquement ces schmas cintiques (systmes dquations diffrentielles linaires), un certain nombre de ractions ont t supprimes, permettant de dterminer un critre de fin de vie. Dans ce modle, ils ont galement fait lhypothse de lunicit du site actif, qui reste incontournable, pour la rsolution mathmatique du problme. Dans le cas du polythylne ce site est :
H CH2 C

A noter que pour lEPDM, il parat indispensable de considrer la contribution des deux sites ractifs, lun li au monomre thylne et lautre au monomre propylne. Dans le cas du polypropylne, lhypothse de lunicit du site actif peut en outre tre remise en cause ; en effet le site ractif majoritaire est le carbone tertiaire mais il nest pas exclu que le site du carbone secondaire puisse ragir Dans ce cas, la prise en compte de ces aspects ncessiterait des moyens de calcul bien plus performants puisque le nombre de ractions augmente quasi exponentiellement avec le nombre de sites ractifs. Aux trs forts dbits de doses (I > 0.5 Gy/s), la dcomposition des hydroperoxydes est considre comme ngligeable. La source principale de radicaux est la radiolyse du polymre c'est--dire les coupures des liaisons latrales C-H sur les chanes macromolculaires. Plus tt, un certain nombre dincohrences dans le modle de Decker, Mayo et Richardson19-20 avaient t mises en vidence et une manire possible de rpondre toutes ces interrogations est de considrer quune fraction des combinaisons bimolculaires des radicaux peroxyles PO2 nest pas terminante et que certaines paires de radicaux PO diffusent hors de la cage. Les radicaux PO peuvent donner des groupements carbonyles selon le mcanisme de scission ou encore arracher des hydrognes. En utilisant les mmes ractions damorage et de propagation du schma mcanistique de base, Kelidj et al15 proposent de considrer les ractions de terminaison suivantes : PO2 + PO2 [PO OP]cage + O2 [PO OP]cage POOP [PO OP]cage P=O + P-OH [PO OP]cage 2P + 2 1 s + 2 1 P=O + 2(1- 1) P-OH La dernire raction inclut un mcanisme de scission de chanes. 1 est le rendement de formation des carbonyles au cours du processus de raction non terminante et s le rendement en scission de chanes. Les rsultats ont t obtenus partir des donnes de Decker et al20 sur deux polythylnes de cristallinit diffrentes (50% et 75%) des deux dbits de dose diffrents (0.108 Gy.s-1 soit 389 Gy.h-1 et 0.292 Gy.s-1 soit 1.05 kGy.h-1).
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Les rsultats montrent un petit effet du dbit dose : son augmentation semble augmenter le rendement de scissions de chanes. Quel que soit le dbit de dose, ils montrent galement que le taux de cristallinit des matriaux joue un rle sur ce rendement : ce paramtre est dautant plus faible que le matriau est plus cristallin. Ainsi nous pouvons conclure que les scissions de chanes ont lieu majoritairement dans la phase amorphe et que la dgradation de la phase cristalline est postrieure celle de la phase amorphe. Mais cela laisse penser que la temprature laquelle sont ralises les irradiations peut avoir des incidences normes : quelle va tre ltendue de la dgradation du matriau si celui-ci est irradi au dessus de la temprature de fusion de ses cristallites ? 2.3. Influence des paramtres matriaux Diffrents paramtres matriaux peuvent influencer les mcanismes de dgradation 2.3.1. Nature chimique du polymre Il est intressant de comparer les rsultats de Decker et al.19-20 obtenus pour des copolymres thylne-propylne. Les chantillons ont t soumis lirradiation gamma pendant 70 heures 45C des dbits de 6 et 17.5 Gy/min. Ici nous exposerons seulement les rsultats pour le dbit 17.5Gy/min soit 1.05 kGy/h.

Figure 5 : Evolution des rendements radiochimiques de produits doxydation et consommation doxygne en fonction de la fraction molaire dthylne19-20 La figure 5 ci-dessus montre une forte diminution des rendements radiochimiques en POOH et en consommation doxygne avec la fraction molaire dthylne, en fait les plus grosses variations sont observes lors du passage du copolymre EP avec une fraction molaire dthylne de 0.37 au polypropylne. Cela suggre que le propylne est beaucoup plus
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sensible aux coupures de chanes que lthylne. Nanmoins il faut noter que la cristallinit est directement li la variation de proportion dthylne, ce point sera discut plus loin.

Figure 6 : Evolution du rendement de consommation doxygne avec I-0.5 (I est le dbit de dose)21 : Irradiations aux lectrons dEPDM-HD PO2 = 15mbar, valeurs de Dly21 ; : Irradiations aux lectrons dEPDM-HD PO2 = 15mbar, valeurs de Corbin22 ; : Irradiation Gamma dun copolymre Ethylne-Propylne avec une fraction molaire dthylne de 0.86 PO2 = 870 mbar, valeurs de Decker et al20 ; : Irradiation Gamma du PP PO2 = 870 mbar, valeurs de Decker et al19 ; : Irradiation Gamma dEPDM-ENB sous flux doxygne, valeurs de Cambon13-14 ; : Irradiation Gamma dEPR sous flux doxygne, valeurs de Cambon13-14 Par ailleurs, la figure 6 prsente lvolution du rendement de la consommation doxygne avec I-0.5 pour diffrents matriaux tudis dans plusieurs publications. Les deux matriaux EPDM de Corbin et Cambon (qui ne diffrent que par la nature et la teneur du dine ainsi que la teneur en thylne), donnent des rsultats en bon accord (si la droite de Decker et Mayo des rsultats de Corbin est extrapole). On peut noter par contre que Dly et Corbin 2122 bien quils aient utilis le mme matriau, les diffrences entre les valeurs obtenues sont en partie dues au fait que Corbin a utilis une mthode indirecte qui ne peut pas en prendre en compte tous les produits doxydation. La valeur du rendement de lEPR de Cambon est infrieure celle de lEPDM, en effet lunit dinique est connue pour augmenter la consommation en oxygne.

2.3.2. Cristallinit Les rsultats de Decker et Mayo19-20 sont reports sur la figure 7 pour illustrer leffet de la cristallinit sur loxydation des polythylnes et copolymres thylne-propylne. Les rendements en espces carbonyle et peroxyde restent quasiment stable, avec le taux de cristallinit, au contraire des rendements en consommation doxygne et en hydroperoxydes qui diminue, avec un taux de cristallinit croissant. Ainsi loxydation a lieu en majeure partie dans la phase amorphe. En effet, loxydation est largement limite dans les cristallites, donc plus le matriau sera cristallin, plus il sera rsistant la cristallisation. Nanmoins, la prsence de cristallites dans le matriau peut induire une htrognit doxydation, puisque la diffusion de loxygne dans lpaisseur du matriau sera perturbe par la prsence dune
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phase plus permable loxygne. Dans le cas des EPDM il est difficile de sparer leffet de la cristallinit de celui de la proportion en propylne puisque les deux sont lis.

Figure 7 : Evolution des rendements radiochimiques de produits doxydation et consommation doxygne en fonction du taux de cristallinit pour des matriaux PE et des copolymres EP19-20

Outre son influence sur les cintiques de ractions chimiques, la temprature dirradiation a galement des consquences sur la microstructure cristalline du matriau. Si la temprature dirradiation est en dessous de la temprature de fusion des cristallites, le matriau est semicristallin ; au dessus de la temprature de fusion, le matriau est totalement amorphe, donc la dgradation est gnralement plus importante. Ainsi ltude de lirradiation dun EPDM temprature ambiante et 80C dAssink et al.23 a mis en vidence des diffrences entre les deux vieillissements, attribues par les auteurs au fait que 80C est au dessus de la temprature de fusion dune partie des cristallites. A noter que la mobilit du polymre peut galement tre modifie au passage de la transition vitreuse. Sous cette temprature, tous les processus diffusionnels sont quasiment gels , alors quils sont favoriss par la mobilit cooprative ltat caoutchoutique. Cest ainsi que des polymres comportant des groupements hydrocarbons rputs facilement oxydables, comme les polyimides, sont considrs comme thermostables ltat vitreux14. Il en est de mme pour bon nombre dpoxy24-25.

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3. Consquences sur la microstructure et les proprits mcaniques


3.1. Pour les polythylnes Leffet des radiations de haute nergie sur le polythylne a largement tudi dans le pass26-27-28-29-30 . Cela peut se traduire par une volution de la cristallinit du matriau. Par exemple, une tude de Bateja27 a rapport que ce degr augmentait avec une dose dirradiation croissante dans le cas dun vieillissement sous air et pour des doses relativement raisonnables. Cette augmentation est gnralement explique par des scissions de chanes se droulant dans la phase amorphe qui peuvent cristalliser. Ce processus est plus communment nomm chimie-cristallisation. Plusieurs auteurs31-32-33 ont expliqu la prservation des proprits mcaniques temprature ambiante par ce processus. Il a t particulirement mis en vidence dans le cas dun recuit aprs le vieillissement : la phase de recuit peut renouveller les proprits mcaniques. Dans le cas de vieillissement thermique des tempratures en dessous de la temprature de fusion des cristallites, le retour temprature ambiante permet une rorganisation du matriau. De plus, Aslanian et al.28 a montr que les rgions cristallines pouvaient tre aussi attaques par lirradiation. Cela cre des dfauts qui peuvent induire un dcalage du pic de fusion vers les basses tempratures. Simultanment des nuds de rticulation peuvent tre forms dans la phase cristalline. Gnralement on tudie les consquences du vieillissement par irradiation temprature ambiante sur les proprits mcaniques des polythylnes cette mme temprature, i.e. quand ce polymre est ltat semi-cristallin. La dgradation se manifeste par des coupures de chanes comme dans le cas dun vieillissement thermique. La nature semi-cristalline du matriau limite les consquences de cette dgradation sur lvolution du module lastique. Par contre la dgradation conduit au passage rapide dun comportement ductile un comportement fragile. A titre dexemple, le mcanisme de dgradation thermique induisant la fragilisation du polythylne a t rcemment tudi par Fayolle et al.34. Ltude a t mene sur un polythylne haut densit avec une masse molaire moyenne en masse de 110 kg mol -1 pendant une thermo-oxydation 80C et 90C. Sa cristallinit voisine de 42% ltat non vieilli, augmente lgrement pendant le vieillissement jusqu 50%. La figure ci-dessous (gauche) montre lvolution de lallongement la rupture et de la concentration en carbonyles pendant le vieillissement 80C. La fragilisation, correspondant la diminution catastrophique de llongation la rupture se produit quand la concentration en carbonyles est proche de 0.1 mol kg-1. De plus si on dfinit le temps dinduction partir de la croissance en produits doxydation (ici environ 13 jours), il apparat que le temps de fragilisation est plus lev que le temps dinduction.

Figure 8 gauche : Evolution de lallongement la rupture et de la concentration en carbonyles pendant un vieillissement 80C ; Figure 8 droite : Comportement aux grandes
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dformations du polythylne tudi non vieilli (courbe) et enveloppe de rupture (points) : contrainte la rupture en fonction de lallongement la rupture pour diffrents temps de vieillissement 80C35 Les essais de traction raliss temprature ambiante correspondants sont prsents dans la figure 8 droite. Lenveloppe de rupture (volution de la contrainte la rupture en fonction de lallongement la rupture pendant la thermo-oxydation 80C) suit globalement la courbe de traction de lchantillon non vieilli, ce qui suggre en effet que la fragilisation est due essentiellement aux coupures de chanes.

Figure 9 : Evolution de lallongement la rupture en fonction de la masse molaire moyenne en masse obtenue partir de plusieurs tudes35-36-37-38-39-40 Lallongement la rupture en fonction de la masse molaire moyenne en masse Mw a t trac pour diffrentes tudes dans la figure 9. Dans tous les cas, lapparition de la fragilisation se trouve environ 100 kg mol-1. Deux types de comportement peuvent tre observs. Dans le cas de Fayolle et al.35 et dans le cas dun vieillissement naturel tudi par Mendes et al. 35, la transition ductile-fragile est vraiment rapide. Sa largeur est denviron 10% autour de la valeur de masse molaire moyenne en masse critique. Dans le cas dun vieillissement thermique tudi par Horgh et Klemchuk36-37 comme dans le cas dun vieillissement radiochimique tudi par Suarez et al.38-39, la transition est plus progressive et stale de 10 100 kg mol-1. Ceci peut tre expliqu dans le cas de la radio-oxydation par le fait quun phnomne de rticulation a lieu en mme temps, ce qui a pour consquences de modifier les valeurs de masses molaires et de dcaler la transition ductile-fragile. La diffrence de comportement entre ltude de Fayolle et al. et Klemchuk et Horgh a t attribu, la nature du polymre tudi : dans le cas de Fayolle et al. le polythylne a un index de polydispersit voisin de deux, alors que dans lautre tude, le polymre est trs polydisperse (Mw/Mn = 18). Comme le font remarquer les auteurs, lapparition de cette fragilisation entre 50 et 100 kg mol-1 est en parfait accord avec les donnes disponibles pour les polythylnes vierges et cette masse molaire critique Mc est relativement loigne de la masse molaire entre enchevtrements Me voisine de 1.7 kg mol-1. Ceci est caractristique des polymres semi-cristallins et la masse molaire de fragilisation parat tre contrle par dautres facteurs que la densit denchevtrements : la fragilisation a lieu bien avant que le rseau denchevtrements prsent dans la phase ait atteint une dgradation significative.
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Une possible explication de ce comportement, base sur le travail de Kennedy et al.40, est que le domaine de ductibilit pour un polymre est limit par des conditions particulires sur la masse molaire moyenne en nombre Mw et sur lpaisseur de la lamelle amorphe la. Dans les conditions de vieillissement tudies par Fayolle et al., le matriau est essentiellement soumis un phnomne de scissions de chanes : ainsi Mw diminue ; mais dans le mme temps une augmentation de sa cristallinit est observe, rsultant dun phnomne de chimiecristallisation : ainsi la diminue galement. Ces deux processus ne peuvent conduire qu une fragilisation. Les auteurs ont considr deux options : soit le matriau vieilli est quivalent un chantillon vierge avec une distribution de masses molaires diffrente soit des critres spcifiques doivent tre tablis pour la dtermination de la transition ductile-fragile (molcules liens). Le premier modle est intressant car il est bas sur des hypothses simples mais na pas pu tre valid car les mesures de paramtres morphologiques tels que la ont t peu souvent ralises dans la littrature. La deuxime approche sous-tend une modification spcifique de la microstructure induite par lirradiation : cela peut avoir pour origine des molcules liens plus ractives mme si il est difficile dexpliquer cette diffrence de ractivit. Une autre origine41 possible est quun petit nombre de coupures de chanes est ncessaire pour dtruire les liens interlamellaires qui sont essentiellement composs denchevtrements. Pour linstant, aucun des deux modles nest privilgi.

3.2. Pour les EPDM Pour le polythylne, les rgions cristallines reprsentent la phase majoritaire et gnralement la temprature dirradiation est bien infrieure la temprature de fusion, mais ce nest pas le cas de lEPDM. Tout dabord, comme il sagit dun copolymre, le taux de cristallinit directement li la proportion dthylne est gnralement faible (~ 5-20%), donc la dgradation est plus importante (cf. paragraphe 2.3.2). Dautre part la temprature de fusion des cristallites est faible et stale sur un large domaine de temprature : ainsi le vieillissement par irradiation temprature ambiante de ces matriaux peut avoir des consquences sur la microstructure cristalline du matriau.

EPDM (), EPDM rticul (), EPDM rticul stabilis () Figure 10 : Evolution de la temprature de fusion Tm en fonction de la dose dirradiation pour les 3 formulation42-43

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Figure 11 : Evolution du module de conservation E 25C (en haut) 90C (en bas) en fonction de la dose dirradiation pour les 3 formulations EPDM (), EPDM rticul (), EPDM rticul stabilis (avec un antio-oxydant) ()42-43 Celette et al.42-43 a tudi lvolution de la phase cristalline durant le vieillissement pour trois formulations base dEPDM. Ltude a t complique puisque le taux de cristallinit est particulirement faible : environ 6%. Il ny avait pas de variation significative du taux de cristallinit, mais avec des valeurs aussi faibles de cristallinit, il est difficile dobtenir des rsultats trs prcis. Ils ont nanmoins not une augmentation de la temprature de fusion de 0 200 kGy puis cette temprature se stabilise pour des doses suprieures : ils en ont dduit que la taille des cristallites augmente, nanmoins la faible augmentation de temprature releve implique un trs faible paississement des lamelles cristallines (calculable par la relation Gibbs-Thomson). Les mmes auteurs se sont intresss aux consquences du vieillissement sur les proprits mcaniques. Ltude du module lastique 90C a permis dterminer la cintique de dgradation des matriaux (cf. Figure 11). Le phnomne majoritaire de scissions de chanes conduit une diminution continue du module lastique dans le cas de lEPDM rticul et de lEPDM rticul stabilis. En revanche la rticulation observe en dbut dirradiation de lEPDM non rticul conduit une augmentation de son module. Les consquences des rticulations et des scissions de chanes, particulirement visibles 90C, sont compltement masques par la prsence des cristallites. Au cours du vieillissement, un certain nombre de leurs proprits sont modifies. La fonction premire dun cble est lisolation lectrique ; donc il paratrait judicieux de prendre comme critre de fin de vie un critre dilectrique. Mais en pratique, il a t dmontr que la proprit
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la plus sensible est lallongement la rupture. Le critre de fin de vie est donc le temps au bout duquel lallongement la rupture atteint 50% de la valeur initiale (du polymre non vieilli).

Figure 12 : Essais de traction pour des matriaux EPDM et EPDM rticuls non irradis et irradis 400 kGy temprature ambiante et 80C42-43 A 80C (temprature de caractrisation), pour lEPDM rticul, lallongement la rupture et la contrainte la rupture diminuent avec la dose dirradiation (cf. Figure 12). La diminution du module lastique confirme la prdominance du phnomne de coupure de chanes lors de lirradiation, par contre pour un lastomre classique, lorsque la densit de rticulation est diminue, lallongement la rupture est plutt augment, ce qui est en complte contradiction avec lvolution observe sur la figure. Pour lEPDM non rticul, les comptitions de scissions et de rticulations des chanes rendent difficile lanalyse des proprits mcaniques aux grandes dformations. A 25C (temprature de caractrisation), comme dans le cas du polythylne, les consquences du vieillissement se manifestent par une diminution de lallongement la rupture et une augmentation la rupture. Cependant les auteurs nont pas interprt ces rsultats. En conclusion, les consquences de coupures de chaines sur la microstructure des lastomres sont mal connues et il est par consquent difficile de comprendre lvolution des proprits mcaniques que soit au dessus de la temprature de fusion des cristallites ou temprature ambiante. Laddition de charges rend le problme encore plus complexe.

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2me PARTIE : Elastomres chargs 1. Les charges


1.1. Gnralits Les lastomres sont en gnral utiliss en mlange avec des charges minrales. Cette addition a pour objectif de renforcer les lastomres. Par renforcer, il est suggr accrotre le module, diminuer les pertes par hystrse, augmenter les caractristiques la rupture, la rsistance la fatigue ou encore diminuer lusure. De plus, sur un plan conomique, on cherche toujours diminuer le prix de revient dune pice condition den conserver ou si possible den amliorer les proprits. Selon les applications et le renforcement souhait, diffrents types de charge peuvent tre utiliss : Trs peu renforantes : craie naturelle, talc Semi-renforantes : kaolins, silicoaluminates, carbonates de calcium Renforantes : noir de carbone, silice Les paramtres qui permettent de caractriser les charges : La surface spcifique : Cest la surface dveloppe de la charge par unit de masse. Plus la taille de la particule est petite, plus la surface spcifique est grande. Elle est de 10 40m2/g pour les kaolins, de quelques m2/g 150m2/g pour les noirs de carbone et elle peut atteindre 400m2/g pour certaines silices. De manire gnral, plus la surface spcifique est grande, plus le renforcement potentiel est important. La structure : Elle se dfinit selon les diffrentes chelles de taille. La structure primaire de la plupart des charges nanomtriques dcoule du regroupement lors de la synthse de particules lmentaires sous forme dagrgat indivisible. Une attraction plus faible existe aussi entre les agrgats conduisant la formation dune structure secondaire sous forme dagglomrats. La structure secondaire est destructible sous leffet dune action mcanique comme par exemple lors du malaxage ou au cours de sollicitations. Lactivit chimique de la surface : Elle permet de contrler la compatibilit (dispersion et formations dinteractions) entre la charge et la matrice. Lnergie de surface dtermine les interactions charge-charge et polymre-charge. Les noirs de carbone sincorporent trs facilement dans les lastomres hydrocarbons du fait de leurs natures chimiques proches, comme la silice dans les silicones. Dans le cas de la silice, son incorporation au sein dlastomres hydrocarbons ncessite gnralement lutilisation dun traitement de surface afin damliorer leur compatibilit Ces trois paramtres caractristiques des charges vont tre dterminants lors de lincorporation et la dispersion de la charge au sein de la matrice. Ainsi, dans le cas de charges avec une grande surface spcifique et une structure leve, une bonne dispersion ncessite un trs fort cisaillement du mlange lors de la mise en uvre.

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1.2. Charges tudies 1.2.1. La silice nanoscopique

Synthse Bibliographique

Lune des silices les plus utilises est la silice de prcipitation obtenue en milieu liquide par hydrolyse dun silicate alcalin soluble. Laddition dacide conduit la formation dacide silicique, Si(OH)4, qui va conduire la naissance de particules collodales de trs petites tailles (sol). Le sol se transforme en gel ou en prcipit lors dune raction dpendant du pH. Dans le cas dune silice de prcipitation44, la plus petite entit que lon peut disperser est appele agrgat dans lequel les particules lmentaires de 5 30 nm sont relies par condensation des silanols de surface (cf. figure 13). La taille des particules indestructibles (agrgats) dtermine la surface spcifique qui varie de 25 400 m2/g. Les agrgats de silice se rassemblent en agglomrats de quelques microns. Les liaisons au sein de ces agglomrats sont des liaisons physiques hydrogne. Laptitude des agglomrats se diviser influence la dispersibilit de la silice.

Figure 13 : Taille des diffrentes structures Une autre proprit importante de la silice est son activit chimique. Les groupements chimiques en surface sont constitus essentiellement de groupes hydroxyle OH (silanols). Les silanols sont associs la prsence deau (de 4 7 %) qui est absorbe la surface par llastomre. La prsence dhydroxyles apparat sous plusieurs configurations : silanol simple Si-OH ou gmin =Si(OH)2 (cf. figure 14). Ces silanols peuvent sassocier par lintermdiaire de liaisons hydrogne entre eux ou avec leau de surface. On distinguera ainsi les silanols isols (voisins trop loigns), vicinaux, et internes dans ce cas non accessibles certaines molcules adsorbables. En gnral, le nombre de silanols45 est compris entre 4 et 8 OH/nm2.

Figure 14 : Diffrents types de silanols

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1.2.2. Les trihydroxydes daluminium ATH

Synthse Bibliographique

Les trihydroxydes daluminium (ATH), qui sont plus connus sous le nom de trihydrates daluminium, sont des charges anti-feu qui sont souvent utilises dans les polymres ou composites. Cette charge est trs populaire du fait de son faible cot, ses proprits antiflamme, sa fume non toxique. Les particules ATH ont une taille voisine de 1 m, et doivent tre disperses de faon uniforme dans la matrice, pour jouer leur rle anti-feu. Il est souvent ncessaire dajouter 50% en masse ou plus de charges pour obtenir une bonne rsistance au feu. Cependant, ces hauts taux de charges ont pour consquences de dgrader les proprits mcaniques du composite en particulier les proprits ultimes. Pour minimiser cet effet, les taux dATH sont diminus par lajout combin dautres agents anti-flamme comme les organo-halognes. Les hydroxydes daluminium, de formule chimique Al(OH)3, existent sous trois formes cristallises. La diffrence entre ces trois polymorphes consiste simplement en des empilements dans un ordre diffrent des feuillets. Ces derniers sont constitus par deux plans de groupements hydroxyles OH- en rseau quasiment compact enserrant un plan datomes daluminium qui remplissent les cavits octadriques aux deux tiers (cf. Figure 15). La dsignation minralogique des ces trois hydroxydes est la suivante : la gibbsite, la bayerite, et la nordstrandite. Les cristaux de bayerite ont la forme de plaquettes hexagonales plus ou moins paisses et reprsentent la forme cristalline la plus courante prsente dans les ATH.

Figure 15 : Reprsentation de la structure de la bayerite La dgradation thermique de ces charges montre deux rgions46 : De la temprature ambiante environ 220C, qui correspond au dpart de leau libre Ensuite un large pic exothermique vers 300C, correspondant la dshydratation de la charge i.e. cest dire la transformation des hydroxyles en eau. Cette raction est endothermique et absorbe environ 1 kJ de chaleur par gramme dATH. Ce dpart deau dans la flamme empche la combustion et restreint lexcs doxygne la surface du polymre. Latout de lATH est que cette raction produit des gaz non toxiques et non corrosifs.

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2. Mise en uvre et microstructure des Consquences sur les proprits mcaniques
2.1. Microstructure des lastomres chargs
a

Synthse Bibliographique

lastomres chargs

La mise en uvre des lastomres chargs est une tape dterminante car elle conditionne la dispersion non seulement des charges renforantes mais aussi des diffrents ingrdients de la formulation ainsi que la microstructure finale. Elle implique lutilisation de malaxeurs et de mlangeurs cylindres qui produisent un trs fort cisaillement. 2.1.1. Les renforts Le niveau dagglomration des charges au sein de llastomre dpend du processus de mise en ouvre, de la nature et de la quantit de charges. Quand le taux de charges augmente, un rseau continu de celles-ci peut stablir au-dessus dun certain seuil, seuil de percolation. Au niveau des proprits mcaniques, on attend une diffrence entre un rseau de charges lies uniquement par des liaisons directes (charge-charge) et un rseau constitu de liaisons chargematrice-charge pour lequel la transmission des contraintes se fait par lintermdiaire dune phase polymre ventuellement modifie47. Le seuil de percolation peut tre mis en vidence par : Des mesures mcaniques : une augmentation trs important du module est observe partir de 20 % en volume de billes dures Des mesures lectriques lorsque les particules sont conductrices (cas des noirs de carbone) Des observations microscopiques Selon certains auteurs, la complexit de la structure de la charge, de mme que celle du rseau form dagglomrats charges, suggre quune partie de llastomre peut tre compltement isole de la matrice par les charges. Ce polymre est dit occlus ; il ne subirait plus leffet dune sollicitation mcanique et ne participerait donc pas la macro-dformation48. 2.1.2. La cristallinit Dans le cas particulier des polymres semi-cristallins, les charges peuvent modifier la structure cristalline ne serait ce que par un effet strique. En outre, les cintiques de cristallisation peuvent tre perturbes selon la nature des interactions entre les charges et la matrice. Ainsi lors de la cristallisation froid du caoutchouc naturel lintroduction de charges (silice ou noir de carbone) a un effet sur la taille des cristallites et leur ventuel traitement a un impact sur les cintiques de cristallisation49. Les lamelles cristallines peuvent tre assimiles des renforts lamellaires dans les cas des polymres semi-cristallins (cf. 1re Partie), et associes des charges, peuvent confrer aux matriaux correspondants des proprits grandement amliores. En effet Maselleni-Varlot et al.50 ont ainsi montr pour des nanocomposites PE/argile dans certaines conditions de mise en uvre la formation dun rseau mixte charge-lamelle cristalline tridimensionnel expliquant les proprits mcaniques.

Note : Lusage est dexprimer la teneur en charge en pce : partie pour 100 g dlastomre (ou phr : parts per hundred parts of resin).
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2.1.3. Polymre li

Synthse Bibliographique

Ds la mise en uvre, les charges peuvent tre en interaction physique suffisamment forte pour quun bon solvant ne puisse que partiellement dissoudre le matriau non rticul (cru). La quantit de polymre ne pouvant tre ainsi spare des charges sappelle le polymre li. Il est souvent propos que ce polymre ltat caoutchoutique a une mobilit plus faible que celle de la matrice permettant ainsi dexpliquer les proprits particulires des lastomres chargs en particulier des niveaux trs levs de renforcement que leur procure les charges nanoscopiques51-52. Ainsi une telle hypothse a t faite dans le cas des PDMS chargs tudis par des mesures de spectroscopie dilectrique53. Leffet des charges sur la dynamique des chanes a t tudi et a montr une relaxation supplmentaire plus lente par rapport celle observe pour la transition vitreuse de la matrice seule. Elle est attribue par les auteurs la relaxation des chanes polymres se situant linterface polymre-charge dont la mobilit est rduite du fait de linteraction avec la charge. Cette interface a directement un effet sur la transition vitreuse de ces matriaux. Lensemble des caractristiques discutes ici telles que rseau de charges , polymre occlus et polymre li sont la base de linterprtation du comportement viscolastique des lastomres chargs. 2.2. Proprits mcaniques des lastomres chargs 2.2.1. Comportement dans le domaine linaire Le comportement caractristique dlastomres chargs type SBR charg silice(avec diffrents taux de charges) en fonction de la temprature est prsent dans le domaine linaire (dans ce cas, le module est indpendant de la contrainte applique) (cf. figure 16). Il est mesur ici par spectromtrie mcanique 1Hz.
3,00E+008

2,50E+008

2,00E+008

E' 0C (N/m )

1,50E+008

1,00E+008

5,00E+007

0,00E+000 0 20 40 60 80

Fraction massique de silice (phr)

Figure 16 gauche : Evolution du module lastique E en fonction de la temprature, pour diffrentes fractions massiques de silice54 (0, 5, 20, 40, 60, 80 phr) Figure 16 droite : Evolution du module lastique E 0C en fonction de la fraction massique de charges Comme pour la matrice, llastomre charg prsente une relaxation principale, qui se traduit par une chute de module lastique, lorsque la temprature augmente. Lvolution du module lastique prsente trois domaines : Au niveau du plateau vitreux, llastomre charg prsente un module plus important que celui de la matrice, du la prsence de charges plus rigides que la matrice.
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-

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Certains auteurs ont trouv que la valeur de la temprature de la relaxation T est influence par la prsence de charges et laugmentation de sa fraction volumique. Dans le cas de son augmentation elle est explique par la couche de polymre li prcdemment voque. A noter que cette temprature de relaxation est galement sensible au degr de rticulation de la matrice. A ltat caoutchoutique, laugmentation du module lastique avec la fraction volumique de la charge est beaucoup plus importante que dans le domaine vitreux. 2.2.2. Modlisation du renforcement

Les paramtres influenant le module lastique dun polymre charg sont (i) les proprits lastiques de chacune des deux phases, (ii) la fraction volumique de charges, (iii) leur morphologie (i.e. forme, facteur de forme, distribution des charges dans la phase polymre) et (iv) les diffrentes interactions : charge-charge, charge-matrice. De nombreux modles ont t proposs dans la littrature pour comprendre les diffrentes relations entre ces paramtres et permettant de prdire avec plus ou moins de succs le module lastique de ces composites. Une premire estimation du renforcement peut tre ralise sans faire dhypothse sur la gomtrie et la dispersion des charges. Faisant lhypothse dun tat uniforme de dformation, ou dun tat uniforme de la contrainte, deux bornes peuvent tre dfinies pour le module du composite Ec : Borne infrieure : Ec Borne suprieure : Ec

Em
Em E f

Ef

3 (dformations uniformes)

4 (contraintes uniformes) Em p E f p Avec la fraction volumique, E le module lastique et les indices m et f reprsentant respectivement la phase polymre et les charges.

En pratique, des quations plus complexes sont utilises. Un cas simple concerne les charges sphriques avec une faible fraction volumiques (cas dilu). Le calcul analytique des champs de contraintes et dformations dune inclusion sphrique, reprsentant la charge, dans une matrice homogne conduit lexpression suivante : 15 1 m 1 E f / Em f Ec Em 1 5 7 5 m 2 4 5 m E f / Em Avec la fraction volumique, E le module lastique, le coefficient de Poisson et les indices m et f reprsentent respectivement la phase polymre et les charges. Dans le cas dune inclusion parfaitement rigide dans un matriau incompressible (ce qui correspond grossirement au cas dun lastomre charg), cette relation conduit la relation simplifie :

Ec

Em 1 2.5

Cette relation est quivalente lquation dEinstein pour la viscosit de sphres dilues dans un fluide incompressible (m = 0.5). En fait cette quation du 1er ordre est loin de reprsenter la ralit puisquelle ne tient pas compte, en particulier, des phnomnes dinteraction entre les particules de charges, et nest ainsi valable que pour les milieux trs dilus. La description
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des plus hauts taux de charges est plus complexe et pour cela Guth et Gold55 ont modifi cette quation en introduisant un 2nd terme du second ordre :

Ec

Em 1 2.5

14.1

2 f

Lquation (3) permet de prdire le comportement en dessous de la transition vitreuse et pour des taux relativement faibles. Le modle autocohrent 2+1 phases56-57 est une alternative pour des taux de charges suprieurs. Ce modle consiste considrer la charge comme une inclusion sphrique enveloppe dans une couche de matrice introduite dans un milieu quivalent homogne (MEH) avec les proprits mcaniques du composite. La dformation du milieu homognis soumis une contrainte uniforme est la moyenne volumique des dformations de chaque phase. Le module de cisaillement est alors obtenu en faisant le rapport entre la contrainte applique et la dformation du milieu homognise. Selon certains auteurs, dans le domaine vitreux, ce modle reste valable jusqu des fractions volumiques de charges de 40% quelle que soit leur taille (nanoscopique ou micronique) 67-58. Nanmoins dans le plateau caoutchoutique, il peine dcrire le comportement des nanocomposites59. Cest galement le cas de lquation (5). Cela suggre que des effets qui sont ngligeables ltat vitreux, peuvent avoir un rle important ltat caoutchoutique, les interactions charge-charge et/ou charge-matrice60. Chabert59 et al. utilisent alors un modle 3+1 phases pour introduire la phase de polymre aux proprits modifies la surface de la charge (interphase). Une telle dmarche ne prend pas en compte lagglomration des charges qui peut se produire des taux de charge infrieurs au seuil de percolation. Dans ce cas, Shaterzadeh61 tente den rendre compte en utilisant le modle 2+1 phases en deux tapes. La deuxime tape permet dintroduire des htrognits de concentrations de charges. Kluppel quant lui62utilise pour la description de la matrice un modle de reptation, dans lequel il ajoute pour prendre en compte les charges, un facteur damplification de dformation qui dpend de la structure fractale du rseau de charge. Maier et Goritzt63 ont une approche plus phnomnologique : ils considrent les charges comme des nuds de rticulation multifonctionnels qui sajoutent ceux de la matrice.

Une autre voie consiste reprendre lquation dEinstein, de prendre en compte la fraction dempilement maximum et lagglomration des particules. Broodnyan64 propose une expression simple (quivalente la formule Einstein pour de faibles fractions volumiques) en:

Ec

Em exp

2.5

0.407 1
f max

1.508 f

Avec f la fraction volumique de charge, ou est le facteur de forme, 1 < < 15, et max la fraction maximale dempilement, qui dpend de la gomtrie des agrgats et des agglomrats. A noter que et max sont des paramtres ajustables. En outre, Medalia65 prend en compte la contribution supplmentaire de la matrice occluse. Celle-ci conduit considrer un taux de charges effectif plus lev. Alberola et al.66 prennent en compte cette matrice occluse en utilisant un modle autocohrent 3+1 phases, dans lequel

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la matrice occluse est entoure par une coquille de renfort elle-mme entoure dune coquille de matrice. Pour conclure, le module lastique des lastomres chargs dpend une temprature donne de phnomnes interdpendants : - Le taux et type (taille, nature) des charges, qui vont influencer la dispersion. - Le traitement des charges, qui va modifier les interactions charges-matrice et chargescharges. 2.2.3. Comportement mcanique non linaire Dans le domaine de dformations infrieures 100%, llastomre sans charge montre un comportement linaire i.e. un module dynamique (mesur par spectromtrie mcanique) qui ne varie pas avec la dformation. Lintroduction de charges conduit une non-linarit du comportement, i .e. une forte diminution de ce module avec le taux de dformation. Aux faibles dformations, un plateau (module initial G0) correspondant au module dans le plateau caoutchoutique discut prcdemment. La valeur du module dcrot avec la dformation jusqu la valeur G o elle se stabilise. Ce phnomne est connu sous le nom deffet Payne. Cet effet est influenc par le taux de charges, la dispersion, la surface spcifique et sa structure. Il en existe de nombreuses interprtations de leffet Payne67-8-9-68 mais il est gnralement interprt par des processus de dsagglomration ou rupture du rseau de charges ou par des mcanismes mis en jeu linterface charge-matrice, i.e. les hypothses prcdemment voques pour expliquer le renforcement. En outre le comportement mcanique des lastomres chargs est modifi aprs lapplication dune premire extension. Cette extension entrane une perte de rigidit pour les dformations suivantes et une dformation rmanente (cf. figure 17). Ce phnomne appel effet Mullins est recouvrable partiellement sur des temps trs longs (plusieurs jours) ou en quelques heures des tempratures plus leve.

Figure 17 : Reprsentation de leffet Mullins Mullins69-70 assimile le renforcement dans cette gamme de dformation (<1) une modification de llasticit par une amplification de la contrainte et de la dformation. Lors de
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la sollicitation, les zones pauvres en charges sont principalement dformes ce qui augmente localement la contrainte. Exprimentalement, il a t montr une rupture du rseau secondaire71 et une rorganisation du rseau de charges72 durant la dformation. En considrant que la matrice subit localement de fortes dformations, leffet Mullins peut tre interprt comment un phnomne faisant intervenir essentiellement les chanes macromolculaires73-74 : du fait de la distribution de taille des chanes interparticulaires, chaque dformation, un certain nombre de chanes atteignent leur limite dextensibilit. Les chanes casses lors de la 1re dformation ne participent donc plus aux dformations suivantes expliquant ladoucissement de la contrainte observ entre les deux montes en dformation. En considrant les phnomnes linterface charges-matrice, un mcanisme impliquant le glissement des segments de chanes adsorbes sur la surface de la charge sous leffet de la dformation est propos par Dannenberg75 ou Boonstra76. Ce glissement permet au rseau daccommoder la dformation applique et prvient ainsi de la rupture : durant le processus, la contrainte est redistribue sur les chanes voisines, mais cette redistribution de contrainte entrane un alignement supplmentaire des molcules et une rsistance supplmentaire. Daprs Ambacher et al.77, linterprtation de leffet Mullins est mixte : elle implique le rseau de charges form dinteractions charges-charges et charges-matrice et sa dformation sous leffet de la contrainte applique. Quand la contrainte associe la dformation dpasse un certain seuil, la structure des agglomrats est irrversiblement brise et dforme. Ce phnomne serait responsable de la dformation rmanente aprs la dcharge. Pour les dformations suivantes, les mcanismes en jeu sont les mmes que ceux mis par Boonstra. 2.2.4. Comportement la rupture Lajout de charges induit une augmentation du module, cependant leur effet sur les proprits la rupture doit tre considr avec prcaution. Utilisant un simple modle, Nielsen78 a prdit le comportement contrainte-dformation en fonction de la concentration volumique de charges dans plusieurs cas : (a) adhsion parfaite entre polymre et charge, (b) aucune adhsion entre elles (cf. Figure 18).

Figure 18: Modle pour les polymres chargs (a) Adhsion parfaite, (b) aucune adhsion Supposant une adhsion parfaite (Figure 18 (a)), Nielsen value la dformation de la phase polymre du composite par rapport celle du matriau charg par la relation suivante :
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m c

Synthse Bibliographique

1 1

13 f

Avec m, c les dformations de la phase polymre et du composite, et f la fraction volumique de charges. Si on suppose que la rupture de la phase polymre est la mme que celle de la matrice non charge, llongation la rupture des systmes chargs est la suivante :
B

nc

13 f

10

Leffet des charges dans ce cas est de diminuer lallongement la rupture du composite, celui-ci est relativement ngligeable faibles fractions volumiques. Dans la majorit des cas, lajout de charges microniques conduit cette volution79-80, mme si il existe des exceptions concernant les charges microniques. Par exemple, Lavengood et al. 81 ont observ une augmentation des longations la rupture dans les poly(phenylene oxyde) chargs billes de verre. Lexplication propose est base sur lapparition de fissures dans la matrice. Ainsi le rle de la matrice ne semble pas si ngligeable. Une augmentation de lallongement la rupture est par contre observe dans le cas de lincorporation de charges nanoscopiques, indiquant que les caractristiques des charges (taille, surface spcifique, fraction volumique, traitement) sont des paramtres gouvernant la rupture.

Figure 19: Courbe contrainte-dformation des SBR non charg et charg silice non traite (25%vol, T=298K)

Cet effet est illustr par la courbe de traction dun SBR non charg et charg silice nanoscopique temprature ambiante (cf. Figure 19)82. Laugmentation de la contrainte peut tre explique par les effets damplification de dformation, qui sont connus dans ces matriaux complexes. Cependant, ceci ne suffit pas expliquer laugmentation de lallongement la rupture. Lenveloppe totale de rupture de ce type de matriau doit tre considre. Cette dernire est obtenue en traant le logarithme de la contrainte corrige de llasticit entropique par le facteur (Tref/T avec Tref une temprature de rfrence arbitraire) en fonction de la dformation la rupture. Les tests raliss diffrentes tempratures et vitesse de dformations conduisent une courbe unique comme le montre la figure 2083. Contrainte et dformation la rupture se dplacent sur la courbe lorsque la vitesse de dformation et/ou la temprature varient. A temprature leve et vitesse faible, les proprits
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la rupture se dgradent (contrainte et dformation la rupture sont faibles). Pour de faibles tempratures et une grande vitesse, la contrainte la rupture est amliore et la dformation la rupture passe par un maximum. Les proprits la rupture sont donc optimales dans une rgion intermdiaire. En prsence de charges, temprature donne, la contrainte la rupture augmente avec la fraction de charges. La dformation la rupture est globalement moins importante, mais lon observe une amlioration de cette dformation avec la temprature. Cette variation de proprits avec la temprature est telle que lon peut observer dans une certaine gamme de temprature une dformation la rupture plus importante avec des charges que sans charge.

Figure 20: Enveloppes de rupture pour une matrice SBR charge avec diffrent taux de noir de carbone (les courbes en train plein correspond au modle Bueche)83 Lapra84 a montr quen fonction de la temprature, la matrice SBR non charge avait un seuil de dformation optimum avant rupture pour 273K alors que dans le cas dune mme matrice charge avec de la silice (traite ou non), le maximum est proche de lambiante. Halpin et Bueche83 nexcluent pas limmobilisation du polymre au voisinage de la charge dans leur interprtation de ce dcalage vers les hautes tempratures des proprits ultimes.

3. Vieillissement par irradiation des lastomres chargs


Comme pour le polymre non charg, la phase polymre du composite va tre soumise trois types de modifications structurales lors de son vieillissement par irradiation : Des coupures de chanes Des rticulations Formation de produits doxydation greffs sur les chanes polymres Mais du fait de la prsence de charges, lirradiation de tels matriaux composites peut avoir des consquences diffrents niveaux : Les charges peuvent modifier la diffusion de loxygne et dans ce cas les mcanismes de dgradation peuvent tre diffrents par rapport ceux observs pour la matrice non charge. Si seule la modification de la matrice est considre, tant donn le complexe couplage charge-matrice et le comportement mcanique du matriau composite
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rsultant, il est difficile dvaluer les consquences de lirradiation. En effet, comme on la vu prcdemment le lien entre charges et matrice est difficile tablir. De plus, la modification chimique de la matrice sous irradiation peut aussi modifier les interactions charge-matrice. Les charges, si elles ne sont pas inertes sous rayonnement gamma, peuvent induire leurs propres mcanismes de dgradation, qui peuvent modifier leur surface et leurs interactions avec la matrice, et mme induire dventuelles ractions avec la phase polymre. Dans le cas dun polymre charg semi-cristallin, lirradiation peut avoir un effet sur le rseau mixte cristallites-charges. 3.1. Diffusion de loxygne Comme les charges ont gnralement une faible permabilit au gaz, la diffusion de loxygne peut tre modifie et par consquent induire une htrognit du profil doxydation. En gnral, les proprits de permation au gaz dans le cas de matrice renforce par des charges sphriques peuvent tre prdites par lquation de Maxwell85 :
Pf P0 1 1
f f

11

Avec Pf et P0 les coefficients de permabilit du polymre chargs et de la matrice, f la fraction volumique de charges. Naturellement ces valeurs de permabilit peuvent varier selon le facteur de forme des charges tudies. Ainsi pour une fraction volumique de charges de 18%, la permabilit du matriau sera rduite de 25% et une pour une fraction volumique de 35%, celle-ci sera diminue de 45%. Nanmoins, pour le matriau non charg, si le vieillissement a lieu dans une atmosphre sature doxygne, la diffusion restera relativement homogne. Il sera donc ncessaire de dterminer les profils doxydation des matriaux chargs vieillis, pour dterminer si la prsence de charge a rellement un effet sur la diffusion de loxygne dans lpaisseur. 3.2. Modification des interactions charges-matrice 3.2.1. Consquences de lirradiation sur la silice Patel et al.30 par des exprimentations en ESR (Electron Spin Resonnance) ont montr la prsence despces paramagntiques piges dans la charge dans un PDMS charg silice. Les dfauts lectroniques dtects par cette mthode sont les sites O-. Les dfauts gnralement crs sont les centres E (il sagit de dfauts paramagntiques possdant un lectron non appari), ils sont souvent interprts comme un lectron non appari localis sur un atome de silicium li trois atomes doxygne86 :

Un autre dfaut paramagntique NBOHC (Non Bridging Oxygen Hole Center) est form par laction de la radiation dans la masse de silice. Celui-ci reste pig faible dose, mais des
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doses plus leves a tendance se recombiner ou diffuser la surface de la charge. Ainsi ces espces peuvent facilement migrer dans la silice. Les espces excdentaires (qui ne peuvent pas tre piges) peuvent se recombiner ou diffuser confrant une ractivit beaucoup plus importante de la surface de silice. Les sites87 o les lectrons sont accumuls, sont chimiquement actifs et peuvent ragir avec leau en surface ou les silanols en librant des hydrognes :

La production dhydrogne est dpendante de la surface spcifique : plus elle sera importante, plus le rendement sera grand. Lhydrogne est libr sous forme atomique et peut rester pig dans le rseau de silice ou migrer et se recombiner avec dautres atomes dhydrognes pour former des molcules de dihydrogne ou ragir avec dautres dfauts produits par la radiation. Les radicaux silanols sont des espces trs ractives, qui favorisent la chimie-sorption despces molculaires la surface de la silice. Ils peuvent produire des peroxy-siloxanes87:

Ils peuvent aussi ragir avec un centre E :

En conclusion, lirradiation gamma de la silice prcipite amorphe peut rendre la surface de la charge extrmement ractive et peut aussi conduire la rticulation en surface de la charge par les groupes silanol en librant de lhydrogne88. 3.2.2. Consquences de lIrradiation sur les ATH Il existe peu dtudes sur lirradiation des charges ATH. A notre connaissance, une seule tude a montr que la gibbsite (une des phases cristalline des ATH) se dshydratait sous irradiation lectronique dans un TEM89. Rappelons que dans ce cas, la nature et les conditions dirradiation sont trs diffrentes puisque lirradiation est effectue sous vide. Les lectrons interagissent avec ce minral de diffrentes faons. Tout dabord, cette interaction contribue une augmentation de la temprature. Ensuite, la radiolyse conduit lexcitation locale des lectrons de valence ou une complte ionisation des atomes du minral, qui peut dtruire des liaisons chimiques, produire des gaz qui sont relchs dans le vide, rarranger les atomes dans le matriau. 3.2.3. Modification des interactions charge-matrice Ces interactions peuvent tre modifies de deux faons, soit par une dgradation des charges sous irradiation (cf. ci-dessus), soit par une volution de la matrice.

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Concernant la matrice, lirradiation de polymre conduit son oxydation. Cela peut tre intressant pour des matrices polyolfines telles que les EPDM, puisque les interactions charges-matrice pour de tels matriaux sont initialement faibles : la matrice est apolaire et les charges ajoutes telles que la silice sont hydrophiles. Lorsque le polymre est oxyd, il devient polaire, auquel cas dans le cas de polyolfines chargs silice, les interactions physiques charges-matrice peuvent ventuellement tre amliores. 3.2.3.1. Dans le cas des polymres chargs silice

A notre connaissance aucune tude ne concerne le vieillissement dEPDM chargs silice. A titre dexemple, on prsentera le cas des PDMS chargs silice90-91-92-93-94. Il est important de prciser que la prsence de silice dans llastomre, qui a une densit lectronique beaucoup plus importante, rsulte en une augmentation des phnomnes de scission ou rticulation du fait de la rtrodiffusion de la radiation incidente95. Le cas de ces matriaux est particulier du fait que la molcule (Si(CH3)2-O)n- peut tre ponte sur la surface de silice par des liaisons covalentes ou ventuellement par des liaisons hydrogne via des molcules deau adsorbe sur la surface des charges, ce qui permet de donner un rle de nuds de rticulation multifonctionnels aux charges. Ainsi la prsence dhumidit la surface de la silice a une influence directe sur les interactions charges-matrice96. Pour des tempratures suprieures 300C, la silice peut perdre de leau et devenir moins hydrophile dgradant ainsi les interactions.

Figure 21 : Evolution de la masse molculaire entre nuds de rticulation avec la dose dirradiation pour les silicones chargs silice irradis gamma sous air et sous vide94. Comme le montre la figure ci-dessus, les chantillons irradis sous rayonnement gamma sous vide montrent une immdiate augmentation du degr de rticulation, suivi dun plateau 250 kGy contrairement aux chantillons irradis sous air.

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Figure 22 : Evolution de la densit de rticulation pour les deux contributions : a) phase polymre et b) charges avec la dose dirradiation pour les deux types de vieillissement : sous vide et sous air94.

Une des mthodes pour sparer les contributions du polymre et des charges dans la densit de rticulation est la mthode de gonflement xylne/ammoniaque94-97. La figure 22 montre lvolution des deux contributions : la phase polymre et les charges qui sont responsables de la densit de rticulation apparente pour les deux vieillissements (sous vide et sous air). Ici seul le vieillissement sous air sera tudi. La phase polymre ne montre pas beaucoup de changement faibles doses pour les conditions sous air, puis une importante augmentation du degr de rticulation hautes doses. La prsence doxygne favorise la formation dhydroperoxydes et de peroxydes, qui a pour consquence daugmenter les scissions de chanes. La figure 22 b) montre une rduction de la densit de rticulation par les charges : une partie des liaisons hydrognes aux interfaces charges-matrice ont t rompues. Cette diminution semble grer le degr de rticulation apparent du matriau. A hautes doses dirradiation, cette tendance semble lgrement sinverser. Bien quil existe plusieurs tudes sur les changements structuraux de la silice lors de son irradiation, peu de travaux concernent les effets de la radiation sur les proprits dadsorption des surfaces de silice et des interactions entre polymre et charges. Comme il a t mentionn plus haut, lors de lirradiation de la silice, faibles doses dirradiation, ces espces sont piges dans la silice. Il est possible cependant que quelques espces puissent migrer la surface de la charge et causer des dommages dans la phase eau/OH prsente la surface de la silice. A doses dirradiation plus leves, les sites de pigeage sont complets et les espces paramagntiques supplmentaires migrent la surface de la silice et celles-ci peuvent ragir avec des radicaux libres existant sur les chanes polymres pour crer des liaisons covalentes la place des liaisons hydrognes observs avant vieillissement. Une autre possibilit est que les changements dhydratation la surface de la silice altrent les interactions polymre-charges. Ces rsultats intressants sont considrer avec prcaution puisquils utilisent la relation de Flory-Rhener pour des lastomres chargs, ce qui est dj discutable. En outre ils font lhypothse dun paramtre dinteraction constant au cours de lirradiation, or loxydation du polymre peut conduire sa modification. De plus, lors du vieillissement des polymres, bon nombre de produits doxydation sont forms et il est bien connu que ceux-ci peuvent ragir avec lammoniaque : cest une technique trs utilise en IR pour les quantifier.

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3.2.3.2. Dans le cas des polymres charges ATH

Synthse Bibliographique

Dans le cas des polymres chargs ATH, peu de donnes sont disponibles. A notre connaissance, seules deux tudes concernent lvolution des interactions charge-matrice lors du vieillissement de tels matriaux. La premire traite de la photo-oxydation dEPDM charg ATH98, et les auteurs ont montr par des observations de profils de fracture par microscopie lectronique balayage aprs vieillissement, que les charges avaient tendance saccumuler en surface et sorienter dans la mme direction. Daprs les auteurs, ceci peut tre expliqu par une faible compatibilit entre la charge et la matrice : en effet linteraction entre laluminium et les fonctions carbonyle (cres lors du vieillissement) et peroxyde contenues par la phase polymre est plutt mauvaise.

Figure 23 gauche : Evolution de la fraction de gel avec la dose dirradiation ; Figure 23 droite : Evolution de la rsistivit en fonction de lirradiation27 Une autre tude concernant le vieillissement par irradiation de polythylne-octne (POE) chargs ATH sest rvle tre trs intressante99. Le composite tudi contient 120 phr dATH et a t irradi temprature ambiante avec un dbit de dose de 0.6 kGy/h jusqu une dose maximale de 250 kGy. Les auteurs se sont plus particulirement intresss aux proprits dilectriques de ces matriaux. Linterface polymre-charge est une rgion discontinue pour de nombreuses proprits (mcanique, dilectrique, thermique) car ces deux matriaux ont des proprits trs diffrentes. Le POE est une matrice moins polaire, que les charges, par consquent lors dexprimentation dilectrique, les charges lectriques vont pouvoir saccumuler cette interface, ce qui permet daugmenter leffet de polarisation plus connu sous le nom de polarisation Maxwell-Wagner-Sillars. Celle-ci se manifeste par une perte dilectrique plus importante, et une plus grande permittivit. Ce matriau non rticul ltat non vieilli est soumis un phnomne de rticulation majoritaire de 0 100 kGy, ensuite la fraction de gel se stabilise pour les doses dirradiation plus leves, indiquant que rticulation et scissions de chanes sont en comptition. Lors de cette phase, une forte diminution de la rsistivit du matriau avec la dose dirradiation est noter, qui est attribue par les auteurs une destruction des interactions charges-matrice explique par la forte dgradation de la phase polymre (par scissions de chanes). Dans une certaine mesure, ces rsultats sont confirms par les observations MEB : dans les premiers stades dirradiation (doses infrieures 100 kGy) elles montrent une amlioration des interactions charges-matrice : les frontires charges-matrice deviennent plus diffuses. hautes doses dirradiation, la dgradation de la matrice est telle que la zone intermdiaire charge-matrice devient de plus en plus nette indiquant une dgradation de ces interactions.
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3.3. Consquences sur la microstructure et les proprits mcaniques

Synthse Bibliographique

A notre connaissance, aucune tude ne concerne ltude de lvolution de la microstructure et des proprits mcaniques lors du vieillissement par irradiation dEPDM chargs. A titre dexemple, les consquences de lirradiation lectronique pour des systmes PDMS charg silice99 puis POE chargs ATH seront prsentes. Leffet de lirradiation sur la microstructure cristalline peut tre illustr par ltude de Stevenson et al.99. Cette tude concerne les consquences du vieillissement par irradiation lectronique (sous atmosphre inerte) de formulations PDMS charg silice nanoscopique (30% massique). Langle de perte 1Hz en fonction de la temprature dchantillons irradis PDMS chargs silice est montr sur la figure suivante.

Figure 24 : Evolution de tan en fonction de la temprature 0,1Hz avec une rampe de temprature de 1K/min pour le systme PDMS charg silice traite pour diffrentes doses dirradiation. Les chantillons sont pralablement refroidis 6K/min jusqu 180C90 Pour les PDMS, la relaxation principale (transition vitreuse) est prsente approximativement 120C. A plus hautes tempratures, vers 40C, un second pic peut tre observ : il sera attribu la fusion de la phase cristalline. Ce pic de fusion est affect par lirradiation et disparait pratiquement pour des doses suprieures 500 kGy cest dire que la cristallinit diminue et quun tat amorphe est obtenu (aprs le refroidissement 6K/min avant la mesure). La disparition de la phase cristalline saccompagne dune augmentation du pic de transition vitreuse puisque la chute de module est plus importante au passage de cette transition (Les cristallites jouant le rle de nuds de rticulation ayant disparu). La diminution de la cristallinit a t galement confirme par des analyses de DSC. Les valeurs denthalpie de fusion et de cristallisation dpendent de la dose dirradiation et de la prsence ou non de la charge et de son traitement ventuel. La prsence de charges induit une plus grande sensibilit lirradiation, puisque lenthalpie de fusion du matriau vierge volue de 26J/g 0 kGy vers 20J/g 500 kGy, alors que la prsence de charges induit une diminution de lenthalpie jusqu une valeur 3J/g pour la silice non traite irradie la mme dose. Leffet du traitement initial de la silice est manifeste puisque le matriau charg silice non traite est totalement amorphe 500 kGy. Une diminution des tempratures de fusion est galement noter durant le vieillissement, signifiant une diminution de lpaisseur des
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cristallites. La mme observation peut tre faite pour les tempratures de cristallisation : ceci peut tre expliqu par la prpondrance du phnomne de rticulation observ pendant le vieillissement ralentissant toutes les cintiques de cristallisation.

Figure 25 : Tests de traction pour les mlanges PDMS/silice non traits non-irradis et irradis diffrentes doses (taux de dformation 0,05 s-1). La fin du test est due la rupture de lchantillon90 Concernant les proprits mcaniques, lirradiation induit une augmentation du module lastique et une diminution de llongation la rupture. La densit apparente de rticulation augmente avec la dose dirradiation, mais la sensibilit lirradiation est plus forte en prsence de silice. Cet effet est plus important lorsque la silice est traite, ce qui montre que les radicaux libres cres par irradiation augmentent la densit apparente de rticulation par leur recombinaison la surface de la charge. En rsum, lirradiation a un effet significatif de densification du rseau macromolculaire et amliore les interactions entre les nanoparticules et la matrice polymre. Stevenson et al.90 ont complt cette tude par des essais de traction cycliques (effet Mullins) et ont montr que linterface entre les particules et la matrice polymre joue un rle dominant dans le vieillissement par irradiation lectronique (sous vide) des lastomres silicons chargs. A chaque cycle (i.e. pour chaque pas de dformation), une augmentation du phnomne dissipatif associ leffet Mullins avec la dose dirradiation est noter. Ces rsultats sont en accord avec lhypothse de la formation de nuds de rticulation entre les charges et la matrice. Pour aller plus loin, les auteurs ont utilis la diffusion des X aux petits angles pour tudier la prsence de vides nanoscopiques ventuels durant lessai de traction. Bien que les chantillons deviennent blancs en fin dessai indiquant la prsence de vides microniques aux grandes dformations, ces expriences nont rien montr pour les faibles dformations. Les dommages crs lors des essais de traction peuvent tre alors dcrits comme un dsenchevtrement individuel des chanes linterface polymre/charge suivi par une rapide croissance des vides lchelle micronique et/ou par une dformation des agrgats. Dans le cas de POE charg ATH irradi, ltude des proprits mcaniques de ces matriaux et lobservation de profils de fracture par microscopie lectronique balayage a t effectue. En effet, au dessus de 100 kGy, une diminution du module lastique et de la contrainte la rupture ainsi quune augmentation de lallongement la rupture sont observes. Les auteurs nont pas donn dexplications ces volutions.

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Figure 26 gauche : Evolution du module lastique avec la dose dirradiation du matriau POE/ATH ; Figure 26 droite : Evolution de lallongement la rupture avec la dose dirradiation pour le mme matriau

4. Conclusions & Perspectives


Aujourdhui, il nexiste pas de modle permettant de dcrire le vieillissement des polymres en gnral. En effet, si la loi dArrhenius prsente un caractre universel, celle-ci savre non applicable dans de nombreux cas. Et les derniers modles mis au point sappliquent en gnral un type de matriau. En outre, pour des raisons de rsolutions analytiques, il est impossible de prendre en compte toutes les ractions possibles se produisant lors du vieillissement du matriau. Il est donc ncessaire de faire bon nombre dhypothses pour tablir la prdominance ou la faible importance de certaines ractions afin de limiter le problme. Et ce travail requiert la prise en compte de la combinaison de plusieurs paramtres propres au matriau vieilli (nature, microstructure) et aux conditions de vieillissement (temprature, atmosphre). De plus, le passage des mcanismes de vieillissement aux proprits macroscopiques se rvle particulirement dlicat. En effet il est clair que lvolution des proprits mcaniques au cours du vieillissement est rgie par les cintiques de rticulation et de scissions de chanes. En effet, pour des matriaux semi-cristallins comme les EPDM, si lvolution du module lastique au dessus de leur temprature de fusion de cristallites (90C) permet de dterminer la cintique de dgradation du matriau, le comportement la rupture semble plus complexe. Il parat donc indispensable de pouvoir quantifier le rseau tridimensionnel de llastomre au cours du vieillissement pour comprendre lvolution de son comportement la rupture. A 25C (en prsence dune phase cristalline), il est galement ncessaire de comprendre le rle de la phase de la cristalline, de connatre son volution au cours du vieillissement et dtablir la relation entre la dgradation ventuelle de cette phase et celle de la phase amorphe, ce qui permettra sans doute de mieux comprendre le comportement mcanique temprature ambiante (module lastique rupture). Dans le cadre dapplications industrielles, les polymres sont gnralement chargs. Il a t mis en vidence que les proprits mcaniques de ces matriaux rsultent dun complexe couplage charge-matrice (interactions charge-matrice et charge-charge) et que celles-ci ne peuvent malheureusement pas tre dduites facilement de celles de la matrice. En effet, les interactions charge-matrice ou charge-charge peuvent jouer un rle dterminant.

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Lors du vieillissement par irradiation, la prsence de charges peut induire des modifications diffrentes chelles : Du fait de leur faible permabilit, les charges peuvent modifier la diffusion de loxygne dans le matriau, il sera donc ncessaire de vrifier ce paramtre dans cette tude. Ensuite la dgradation de la matrice, voire celle des charges pourra directement influer sur le couplage charge-matrice si particulier des lastomres chargs. Cependant aucune tude ne concerne le vieillissement des EPDM chargs silice ou ATH et dans ces cas prcis, la nature des interactions charges-matrice est trs diffrente de celle observe pour les PDMS chargs silice par exemple. En effet, le renforcement dune matrice EPDM par des charges silice ou ATH est gnralement complexe du fait des faibles interactions polymre-charge et ncessite dans le cas dapplications industrielles lajout dagent de couplage. Mme si les mcanismes de dgradation des ces lastomres chargs sous irradiation devraient tre quasi-similaires de ceux observs pour la matrice, tout le problme rside dans lincidence de ces coupures de chanes ou rticulations dans de tels matriaux : est ce que les phnomnes de coupures de chanes ou de rticulation seront localiss ou contraire compltement alatoires ? Quelles seront les consquences sur les interactions charges-matrice, charge-charge et donc globalement sur les proprits mcaniques ? Comme la matrice tudie est semi-cristalline et quil a t mis en vidence que pour certains matriaux, lintroduction de charges peut modifier la cristallisation des matriaux, il sagira dun point vrifier. De plus comme lvolution de la phase cristalline durant lirradiation semble tre diffrente de la matrice du matriau charg, il parat galement dterminant de consacrer une partie de notre tude lvolution de la phase cristalline de nos matriaux pendant leur vieillissement par irradiation.

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A.P. LEGRAND et al., Hydroxyls of silica powder, Advances in Colloid and Interface Science, 3, 91, 1990 46 YANG X. et al., Surface acid-base properties and hydration/dehydration mechanisms of alumium (hydr)oxides, Journal of Colloid and Interface Science, 308, 395, 2007. 47 REICHERT W.F., GORITZ D., DUSCHL E.J., The double network, a model describing filled elastomers, Polymer , 34,1216, 1993. 48 MEDALIA A.I., Effect of carbon black on dynamic properties of rubber vulcanizates, Rubb. Chem. Technol., 1978 51:473 49 CHENAL J.M., CHAZEAU L., BOMAL Y., GAUTHIER C., New insights into crystallization of filled natural rubber, journal of polymer science: Part B: Polymer physics, 2007 45:955-62 50 MASENELLI-VARLOT K., VIGIER G., VERMOGEN A., GAUTHIER C., CAVAILLE J.Y., Quantitative structural characterization of polymer-clay nanocomposites and discussion of an ideal microstrcuture, leading to the highest mechanical reinforcement, Journal of polymer science: Part B: Polymer physics, 2007 45: 1243-1251 51 ZHU A.J., STERNSTEIN S.S., Nanofiller-polymer interactions at and above the glass transition temperature, Filled and nanocomposite polymer materials, Mater. Res. Soc. Proc., Warrendale, Pa., 2001 52 BERRIOT J, LEQUEUX F., MONTES H., PERNOT H., Reinofrcement of model filled elastomers :experimental and theorical approach of swelling properties, Polymer 2002 43 : 6131-6138 53 FRAGIADAKIS D., PISSIS P., BOKOBZA L., Glass transition and molecular dynamics in poly(dimethylsiloxane)/silica Nanocomposites, Polymer 2005 46: 6001-8 54 WAGNER M., Renforcement des lastomres par les charges : mobilit molculaire et spcificit des interactions linterface silice/caoutchouc styrne butadine, Thse, Universit de Haute Alsace, 1999. 55 GUTH E., GOLD O., On the hydrodynamical theory of the viscosity of suspension, Physical Review, 53, 322, 1938. 56 KERNER E.H., The electrical conductivity of composite media, Proc. Phys. Soc. London, SerB, 1956 69, 802 57 CHRISTENSEN R.M., LO K.H., Solutions for effective shear properties in three phases sphere and cylinder models, J. Mech. Phys. Solids, 1979 27:315 58 REYNAUD E., Etude des relations structure-proprits mcaniques des thermoplastiques renforcs par des particules inorganiques nanoscopique, Thse, INSA de Lyon, 2000 59 CHABERT E., Proprits mcaniques des Nanocomposites matrice polymre : Approche exprimentale et modlisation, Thse INSA de Lyon, 2002 60 KRAUS G., Advances Polymer Science, 1971 8:155 61 SHATERZADEH-YAZDI M., Etude et modlisation physique et mcanique du comportement viscolastique et plastique de composites particulaires matrice polymre, Thse INSA de Lyon, 1997 62 KLUPPEL M., SCUSTER R.H., HEINRICH G., Structure and properties of reinforcing fractal filler networks in elastomers, Rubb. Chem. Technol., 1997 70: 243 63 KLUPPEL M., SCUSTER R.H., HEINRICH G., Structure and properties of reinforcing fractal filler networks in elastomers, Rubb. Chem. Technol., 1997 70: 243 64 BRODNYAN J. G., Trans. Soc. Rheol. , 1959, 3 61 65 MEDALIA A.I., Effect of carbon black on dynamic properties of rubber vulcanizates, Rubb. Chem. Technol., 1978 51:473 66 ALBEROLA N.D., MERLE G., HEINRICH G., Structure and properties of reinforcing fractal filler networks in elastomer, Rubb. Chem. Technol., 1997 70: 243 67 PAYNE A.R., The dynamic properties of carbon black loaded natural rubber vulcanizates II, Journal of Applied Polymer Science, 6, 368, 1962. 68 HEINRICH G., KLUPPEL M., Recent advances in the theory of filler networking in elastomers, Advances in Polymer Science, 160, 1, 2002. 69 MULLINS L., Effect of stretching on the properties of rubber, Journal of Rubber Research, 16, 275, 1947.
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MULLINS L., TOBIN N.R., Theoretical model for the elastic behavior of filler-reinforced vulcanized rubbers, Rubber Chemistry and Technology, 30, 555, 1957. 71 YATSUYANAGI F., SUZUKI N., ITO M., KAIDOU H., Effects of secondary structure of fillers on the mechanical properties of silica filled rubber systems, Polymer, 42, 9523, 2001. 72 MAAS S., GRONSKI W., Deformation of filler morphology in strained carbon black loaded rubbers: a study by Atomic Force Microscopy, Rubber Chemistry and Technology, 68, 652, 1995. 73 BUECHE F., Reinforcement of elastomers, Ed G. Kraus Interscience Publishers, 1965 74 BUECHE F., Molecular basis for the Mullins effect, Journal of Applied Polymer Science, 4, 107, 1960. 75 DANNENBERG E.M., Molecular slippage mechanism of reinforcement, Trans. Inst. Rubber. Ind., 42, 1966 76 BOONSTRA B.B, Reinforcement of elastomers, Ed G. Kraus Interscience Publishers, 1965 77 AMBACHER H., STRAUSS M., KILIAN G.G., WOLFF S., Reinforcement in filler-loaded rubbers, Kautschuk Gummi Kunstoffe, 12, 1111, 1991. 78 NIELSEN L.E., J. Appl. Polym. Sci., 1966 10: 97 79 MONTEZIN F., LOPEZ CUESTA J.M., CRESPY A., GEORLETTE P., Flame retardant and mechanical properties of a copolymer PP/PE containing brominated compounds/antnomy trioxide blends and magnesium hydroxide or talc, Fire and materials 1997 21: 245-252 80 DUBNIKOVA I.L., BEREZINA S.M., ANTONOV A.V., Effect of rigid particle size on the thoughness of filled polypropylene, Journal of applied polymer science, 2004 94: 1917-1926 81 LAVENGOOD R.R., NICOLAIS L., NARKIS M., Technical report AD 891, 254, NTIS November 1971 82 CHAZEAU L., GAUTHIER C., VIGIER G., CAVAILLE J.Y., Relationships Between Microstructural Aspects and Mechanical Properties in Polymer Based Nanocomposites. Handbook of "organic-inorganic hybrid materials and nanocomposites, Pt2" Dr. H.S. Nalwa ed., American Scientific Publishers, 2004. 83 HALPIN J.C., BUECHE F., Fracture of amorphous polymeric solids: reinforcement, J. Appl. Physics. 1964 35: 3142 84 LAPRA L., Caractrisation molculaire et proprieties mcaniques des rseaux lastomres SBR renforcs par la silice, Thse Universit Pierre et Marie Curie, Paris IV, 1999 85 MAXWELL C., Treatise on electricity and magnetism, Oxford Univ. Press. London, 1873 86 GRISCOM D.L., Self-trapped holes in pure-silica glass: a history of their discovery and characterization and an example of their critical significance to industry, Journal of Noncrystalline Solids, 2006. 352: p.2601-2617. 87 PATEL M. et al., Gamma radiation induced effects on silica and on silica-polymer interactions in filled polysiloxane rubber, Polymer Degradation and Stability, 2006, 91: p. 406-413. 88 CATALDO F. et al., Gamma radiolyzed amorphous silica : a study with 29Si CP-MAS- NMR Spectroscopy, 2008, Radiation Physics and Chemistry, 2008. 77:p. 267-272. 89 KOGURE T., Dehydration sequence of gibbsite by electron beam irradiation in a TEM, Journal of American Ceramic Society, 1999, 82: p. 716-720. 90 STEVENSON I., et al., Influence of SiO2 Fillers on the Irradiation Ageing of Silicone Rubbers. Polymer, 2001. 42: p. 9287 - 9292. 91 CHIEN A., et al., Characterization of Radiation-Induced Aging in Silica-Reinforced Polysiloxane Composites. Radiation Physics and Chemistry, 2000. 59: p. 493-500. 92 PATEL M., et al., Gamma Radiation Induced Effects on Silica and on Silica-Polymer Interfacial Interactions in Filled polysiloxane Rubber. Polymer Degradation and Stability, 2006. 91: p. 406-413. 93 MAXWELL R.S. and BALAZS B., Residual dipolar coupling for the assessment of cross-link density changes in gamma-irradiated silica-PDMS composite materials. Journal of Chemical Physics, 2002. 116(23): p. 10492. 94 MAXWELL R.S., et al., The Effects of Gamma-Radiation on the Thermal, Mechanical, and Segmental Dynamics of a Silica Filled, Room Temperature vulcanized Polysiloxane Rubber. Polymer Degradation and Stability, 2003. 80: p. 443-450.
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MARK J.E. Physical properties of polymers handbook, American Institute of physics press, 1996, New York 96 PATEL M., MORRELL P., CUNNINGHAM J., KHAN N., MAXWELL R.S., CHINN S.C., Complexities associated with moisture in foamed polysiloxane composites, Polymer Degradation and Stability, 2008 93: 513-519 97 POMANTEER K.E. and LENTZ C., Reinforcement studies - Effect of silica structure on properties and crosslink density. Rubber Chemistry and Technology, 1975. 48: p. 795. 98 GUZZO M. and DE PAOLI M.A., The photo-oxidation of EPDM rubber: Part V - Mechanical properties degradation of vulcanized filled samples. Polymer Degradation and Stability, 1992. 38: p. 41. 99 KIM C. HE T., JIANG P., WEI P., HUANG X., JIN Z., Dielectric properties of gamma-irradiated POE highly filled with aluminum hydroxide, Polymer Engineering Science, 2006, 46: p. 1721-1727.

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1.

Prsentation des matriaux ........................................................................................................ 57 1.1. Les matriaux ........................................................................................................................ 57 La matrice...................................................................................................................... 57 Les charges .................................................................................................................... 57 La silice nanoscopique .............................................................................................. 57 Les trihydrates daluminium ATH ............................................................................. 58

1.1.1. 1.1.2. 1.1.2.1. 1.1.2.2. 1.2. 1.3. 2.

Les formulations .................................................................................................................... 59 Mise en uvre ....................................................................................................................... 60

Dispositif de vieillissement .......................................................................................................... 61 2.1. Vieillissement radiochimique ................................................................................................ 61 Description du dispositif................................................................................................ 61 Dosimtrie ..................................................................................................................... 62 Droulement de la premire campagne dirradiation temprature ambiante ........... 64 Droulement de la seconde campagne dirradiation 80C ........................................ 65

2.1.1. 2.1.2. 2.1.3. 2.1.4. 2.2. 3.

Vieillissement thermique ....................................................................................................... 65

Mthodes danalyses.................................................................................................................... 65 3.1. 3.2. Spectroscopie Infra-Rouge .................................................................................................... 65 Mesures de gonflement.......................................................................................................... 67 Mesures de gonflement dans un solvant : le xylne....................................................... 67 Utilisation de la thorie de Kraus ................................................................................. 68 Mesures de gonflement mixte : xylne/ammoniaque ..................................................... 69 Mesure de prise en eau .................................................................................................. 69

3.2.1. 3.2.2. 3.2.3. 3.2.4. 3.3. 3.4. 3.5.

Thermoporosimtrie .............................................................................................................. 70 Analyses thermiques diffrentielles (DSC) ........................................................................... 71 Essais de traction ................................................................................................................... 73

3.6. Diffusion des X aux petits angles (SAXS) et aux grands angles (WAXS) Mesures in-situ en traction .......................................................................................................................................... 74 3.6.1. 3.6.2. 3.7. SAXS ............................................................................................................................. 74 WAXS ........................................................................................................................... 77

Observations microscopiques ................................................................................................ 78

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1. Prsentation des matriaux 1.1. Les matriaux 1.1.1. La matrice Le polymre de base tudi est le NORDEL IP NDR 3722 P fourni par la socit Dow Chemical Company. Il sagit dun EPDM, terpolymre compos dthylne, de propylne et dun dine, le 5-thylidne 2-norborne. La composition massique indique par le fournisseur est la suivante : 70,5% dthylne, 29,5% de propylne et 0,5% de dine. Ces donnes ont t confirmes par des analyses de RMN du 13C. Du fait de son importante proportion en thylne, il sagit dun matriau semi-cristallin.

Figure 1 : Formule gnrale dun EPDM pour le dine : 5-thylidne 2-norbordne Les diffrentes formulations tudies ont t rticules par le peroxyde de dicumyle. Sa rfrence est le Perkadox BC-FF de Akzo-Nobel. Il sera incorpor au taux de 3phr dans toutes les formulations.

Figure 2 : Formule gnrale du Peroxyde de dicumyle 1.1.2. Les charges 1.1.2.1. La silice nanoscopique Une des charges tudies est la silice nanoscopique : il sagit dune silice de prcipitation hautement dispersible avec une surface spcifique voisine de 175 m2/g. La rfrence industrielle est Ultrasil VN3 de Degussa. Elle pourra tre traite avec un agent de greffage : le vinyltrimthoxysilane, le Z6300 de chez Dow Corning. Ce type de greffage a t choisi car le vinyltrimthoxysilane est un bon agent de couplage dans les lastomres chargs et quil favorise la cration de nuds de rticulation entre les chanes polythylne. Ramier et al.1 montrent loptimisation de la quantit dagent de greffage pour avoir un bon recouvrement de la silice et celle-ci a t estime 0,84 pied/nm2 (correspondant une quantit de 1,7 phr) pour une silice ayant les mme caractristiques que celles que nous avons choisies ; le pied de la silice est dfinie de la faon suivante :

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Figure 3 : Agent de Greffage 1.1.2.2. Les trihydrates daluminium ATH

Ces charges ont t fournis par la socit Nabaltec, deux types ont t choisis : un grade non trait et un grade trait vinylsilane, dont les noms industriels sont respectivement Apyral 40 CD et Apyral 40 Vs1. Le traitement utilis est quivalent celui ralis pour la silice.

13

8 Volume (%)

0,01

0,1

1 Taille (m)

10

100

-2

Figure 4 : Analyse granulomtrique des charges ATH (Apyral 40 CD)

1 m

Figure 5 : Photos MEB des ATH Des analyses granulomtriques sur ces charges ont t ralises (cf. Figure 4) : elles montrent une distribution de taille quivalente pour les deux grades, la taille moyenne est voisine de 2m, mais la distribution est relativement large. Ces charges sont obtenues par le procd
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Bayer, donc leur morphologies sont relativement bien contrles : il sagit de particules de forme hexagonale comme on peut le voir sur la figure ci-dessous.

1.2. Les formulations Les diffrentes formulations tudies dans cette thse sont reportes dans le tableau suivant, faute de temps seul un certain nombre ont fait lobjet dune tude approfondie. Lusage est dexprimer la quantit de charge ou de peroxyde en pce i.e. le nombre de parties pour 100 parties de matrice (ou phr : part number per hundred parts resin). La nomenclature utilise est la suivante : Pour les matriaux non chargs : E-NC et E-CR, avec E pour EPDM et NC ou CR pour respectivement non rticul et rticul. Pour les charges, on utilisera ATHU, ATHT, SiU et SiT pour respectivement ATH non trait, ATH trait, silice non traite et silice traite. Ainsi pour les formulations charges, la nomenclature sera la suivante : E-XX-YYYZZZ avec XX qui peut tre NC ou rien indiquant si le matriau est rticul ou pas, YYY la quantit de charges ajoute exprime en phr (pour la silice une seule fraction de charges sera tudie donc cette information ne sera pas renseigne dans la nomenclature), et ZZZ le type de charge. Les taux de charges ont t vrifis aprs la mise en uvre par des analyses thermogravimtriques. EPDM E-NC E-CR E-NC-150ATHU E-CR-32ATHU E-CR-150ATHU E-CR-150ATHT E-CR-SiU E-CR-SiT 100 100 100 100 100 100 100 100 Peroxyde 0 3 0 3 3 3 3 3 ATHU 0 0 150 32 150 0 0 0 ATHT 0 0 0 0 0 150 0 0 SiU 0 0 0 0 0 0 50 50 Agent de greffage 0 0 0 0 0 0 0 1,7

Tableau 1 : Formulations des diffrents lastomres tudis

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Par la suite, les fractions massiques et volumiques de matrice et de charges pourront tre utiles. N.B. : Masse volumique EPDM : 0,9g/cm3, masse volumique peroxyde : 1g/cm3, masse volumique ATH : 2,4g/cm3, masse volumique Silice nanoscopique : 2g/cm3, masse volumique agent de greffage : 1g/cm3

Fraction Massique Matrice E-NC E-CR E-NC-150ATHU E-32ATHU E-150ATHU E-150ATHT E-SiU E-SiT 1 1 0,4 0,76 0,4 0,4 0,67 0,67 Charges 0 0 0,6 0,24 0,6 0,6 0,33 0,33

Fraction Volumique Matrice 1 1 0,64 0,9 0,65 0,65 0,82 0,82 Charges 0 0 0,36 0,10 0,35 0,35 0,18 0,18

Tableau 2 : Fractions massiques et volumiques de matrice et de charges pour les diffrentes formulations. 1.3. Mise en uvre La mise en uvre se droule en trois tapes. 1) Le polymre est pralablement introduit dans le mlangeur : la temprature est fixe 80C et la vitesse de rotation 20 tr/min. Ensuite sont ajoutes les charges puis en dernier le peroxyde de dicumyle. Pour raliser le traitement vinylsilane de la silice, on commence par ajouter lagent de greffage avec 2/3 de la silice, puis le reste de la silice est ensuite ajout. La temprature du mlange est relativement basse : 80C, pour viter toute activation du peroxyde et le mlangeage dure environ 10 minutes. 2) Le mlange est ensuite travaill pendant 5 minutes dans le mlangeur cylindre jusqu obtenir une bande dpaisseur voisine de 2mm : la temprature du cylindre avant est fixe 85C, celle du cylindre arrire 80C et la vitesse de rotation 4 5 tr/min. 3) Ltape de rticulation est ralise sous presse. Les temps de cuisson ont t pralablement dtermins par des analyses menes avec un rhomtre MOSANTO suivant une procdure couramment utilise dans lindustrie : cet appareil permet de mesurer le couple en fonction du temps. De cette faon, le couple maximum est obtenu pour la raction totale de tous les sites rticulables . Dans notre cas, la dure de rticulation est dtermine pour 98% du couple maximum, ainsi le mme
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nombre de sites thorique pour chaque formulation a pu ragir. Dans le cas des matriaux chargs silice, la prsence de charges induit une importante augmentation de la viscosit du mlange pendant sa rticulation. Ceci peut tre expliqu par leffet hydrodynamique des charges, mais par dautres phnomnes impliquant notamment les interactions charge-charge et charge-matrice. Malheureusement, il nexiste pas de simple description ou modlisation de ce phnomne de renforcement, qui permet dvaluer la rhologie de ce type de matriau, les proprits de la matrice et plus spcialement sa densit de rticulation pendant la cuisson. Ainsi pour les lastomres chargs silice, le temps de cuisson dtermin par cette mthode est de 5 minutes alors quil est denviron 10 minutes pour les autres formulations, ce qui laisse penser que la phase polymre de ce composite est moins rticule. Une fois le temps de rticulation dtermin, le moule est pralablement chauff 170C, ensuite les chantillons sont dposs dans le moule et presss. Finalement le moule est refroidi jusqu 60C. Les chantillons obtenus sont des plaques de 1mm dpaisseur. 2. Dispositif de vieillissement 2.1. Vieillissement radiochimique 2.1.1. Description du dispositif

Figure 6 Coupe et vue de cot du dispositif avec 1 source (Echelle 1/10)

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Les irradiations par rayonnement gamma ont t effectues Arc Nuclart (Atelier Rgional de Conservation Nuclart) au CEA de Grenoble. Lenceinte dirradiation utilise est le dispositif INTI : celui-ci permet lirradiation en piscine sous atmosphre contrle dans un conteneur cylindrique tournant, assurant une trs bonne homognit des doses. Latmosphre lintrieur du conteneur dirradiation est renouvele constamment au cours de lirradiation par balayage de gaz, dans notre cas il sagit doxygne. Les sources installes en couronne autour du conteneur de 17 cm de diamtre utile restent fixes au fond de la piscine. Les sources utilises sont des sources scelles de 60Co, mettrices de rayonnement gamma. Pour nos besoins, le dispositif sera charg avec 3 sources de 60Co, permettant dobtenir un dbit de dose denviron 1 kGy/h dans lair sur une hauteur de plus de 35 cm. Les chantillons seront superposs sur un porte-chantillon en mtal de 33 cm de haut. Les plaques seront maintenues par du fil mtallique (kanthal : alliage fer, chrome, aluminium), permettant la circulation de latmosphre entre les plaques.

Dimension plaques polymre : 75mm x 75mm

Longueur grillage : 11cm

Largeur grillage : 10cm

Figure 7 Echantillons et porte-chantillons (schma de principe) 2.1.2. Dosimtrie Les dbits de dose rels ont t dtermins pralablement lirradiation des chantillons, laide de dosimtres de type PMMA (poly-mthylmthacrylate) lecture optique. Nous avons utilis plus particulirement les dosimtres de types Red Perspex fournis par HARWELL Dosimeters Ltd, fiables et prcis. Ils seront placs dans le conteneur charg de manire simuler les chantillons dans les conditions de lexprience. Pour cela, nous avons utilis le
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porte-chantillon charg avec des plaques simulant les chantillons (plaques de PVC de dimensions 75mmx75mmx1mm). Lus aprs 24 heures, ils permettront de dterminer trs prcisment le temps dirradiation ncessaire pour atteindre les doses de rfrences de 50, 165, 300 et 510 kGy.

Type de dosimtre Domaine de dose : Longueur donde pour la mesure de la densit optique : Reproductibilit de la variation dabsorbance sur un lot de dosimtre :

Red 4034 Perspex 5 kGy 50 kGy 530 nm

2%

Prcision typique attendue compte tenu de lensemble de la chane de 5 10 % mesure : Tableau 3 : Proprits des dosimtres Red Perspex La dosimtrie finale de lessai est obtenue en multipliant le temps rel dirradiation par le dbit de dose ainsi dtermin. La chane complte de lensemble des moyens de mesure permet datteindre une prcision de 10 % sur cette dose. Voici la dosimtrie obtenue :
ZONE 1 BIS

1,10

1,05

Dbit de Dose (kGy/h)

1,00

0,95

0,90

0,85

0,80

ZONE 1

ZONE 2

ZONE 3

0,75 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34

hauteur (cm)

Sur l'axe du conteneur Le long du conteneur

Figure 8 : Dosimtrie obtenue pour le dispositif INTI

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La figure 8 prsente les dbits de dose mesurs en fonction de la hauteur du conteneur. Sur laxe du conteneur signifie que les dosimtres ont t placs sur les diffrentes plaques de PVC et le long du conteneur que les dosimtres ont t disposs perpendiculaires aux plaques de PVC. Pour calculer les dbits de dose moyens pour chaque zone, nous avons utilis les donnes obtenues sur laxe du conteneur. Ainsi nous avons spar notre porte-chantillon en 4 zones. Voici les dbits de dose moyens pour chaque zone :

Dbit de dose (kGy/h) Zone 1 Zone 2 Zone 1 bis Zone 4 0,94 1,02 1 0,9

Tableau 4 : Doses moyennes obtenues pour chaque dose

Les chantillons dune mme dose ont t installs dans la mme zone, afin dassurer les mmes dbits la zone 1 sera dcoupe (de 0 8cm et de 18cm 20cm).

2.1.3. Droulement de la premire campagne dirradiation temprature ambiante 1er Retrait 2j 5h 26 min 50 54,4 53,5 48,2 272,9 418,9 510 300 Lot 165kGy 165 2me Retrait 12j 6h 39min 3me Echantillons Retrait 19j 39min 4me Retrait 23j 5h 41min

Echantillons Temps (J/h/min) Zone 1 Zone 2 Zone 1 bis Zone 3 Lot 50 kGy Lot 300kGy Lot 50kGy Lot 510kGy

Dbut 0 0 0 0 0

Tableau 5 : Doses (en kGy) subies par les diffrents lots au cours des sances dirradiations

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Les chantillons ont t installs dans le porte-chantillon lui-mme dpos dans le dispositif. Les essais ont t mens sous atmosphre contrle (oxygne) avec circulation, et temprature ambiante, le dispositif tant thermostat par leau de la piscine (environ 18C). Lirradiation a t lance pour atteindre la premire dose de rfrence 50 kGy. A lissue de cette premire priode dirradiation, les chantillons correspondants cette dose ont t prlevs du porte-chantillon. Lirradiation a ensuite repris jusqu atteindre un cumul de 300 kGy sur les chantillons rests dans le porte-chantillon. A lissue de cette seconde priode dirradiation, les chantillons correspondant cette dose cumule ont t prlevs. De nouveaux chantillons pour qui la dose cumule doit atteindre 165 kGy ont t alors mis en place. Lirradiation a repris pour atteindre cette dose et les chantillons correspondant cette dose ont t enlevs. Finalement les chantillons prsents depuis le dbut des irradiations ont t prlevs un peu plus tard pour obtenir la dose 510 kGy. Au total, ce sont 36 chantillons qui ont t irradis pour chacune des quatre doses (50 kGy, 165 kGy, 300 kGy et 510 kGy), suivant le tableau exprimental ci-dessous.

2.1.4. Droulement de la seconde campagne dirradiation 80C Pour les mmes doses dirradiations avec un dbit de dose identique, dautres chantillons ont t irradis dans les mmes conditions : circulation doxygne en permanence, dpt et rcupration des chantillons mais lenceinte a t thermostate 80C. Les raisons du choix de la temprature dirradiation seront donnes dans le dernier article.

2.2. Vieillissement thermique Afin deffectuer une comparaison avec la campagne dirradiation 80C, une campagne de vieillissement thermique 80C a t ralise. Celle-ci sest effectue dans une tuve ventile pour des temps identiques ceux raliss lors de la campagne dirradiation. 3. Mthodes danalyses 3.1. Spectroscopie Infra-Rouge Les mesures de spectrophotomtrie infrarouge permettent de dterminer la nature des groupements chimiques partir des modes de vibration des liaisons prsentes dans le matriau tudi. Il sagit dune mthode danalyse trs utilise pour caractriser le vieillissement des polymres. Pour des chantillons chargs, la spectroscopie infrarouge en transmission ne peut pas tre utilise. Ainsi loxydation des matriaux lors du vieillissement est suivie par sepctroscopie IR en mode rflexion ATR (Attenuated Total Reflexion). Lappareil utilis est un spectromtre Thermo Nicolet Nexus ; le cristal utilis pour la rflexion est un diamant. Pour chaque analyse, une acquisition de 32 scans est effectue et la rsolution nominale est de 4 cm-1. Dans le cas de la radio-oxydation dEPDM, une augmentation de labsorbance dans la rgion des hydroxyles (3800-3000 cm-1) est observe2, qui correspond la formation dalcools, dacides et dhydroperoxydes. Lapparition dune bande carbonyle2 est galement observable avec une absorption maximale 1713 cm-1 et plusieurs paulements 1785, 1755,
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1740 et 1695 cm-1. Malheureusement, cette technique danalyse ne permet pas de faire des mesures quantitatives, c'est--dire quil nest pas possible de comparer les niveaux doxydation des diffrents matriaux (non chargs, chargs ATH, et chargs silice). En fait, la profondeur de pntration ainsi que le nombre de rflexions sont fortement dpendant de la nature du matriau et donc fortement influence par la nature des charges. De plus, un phnomne de diffusion peut avoir lieu en prsence des charges. Dans le cas o loxydation du polymre est contrle par la diffusion doxygne dans lchantillon, il peut en rsulter une distribution htrogne des produits doxydation dans le matriau conduisant un profil doxydation au sein du polymre2. La micro-spectroscopie IR consiste analyser le polymre selon une direction perpendiculaire la direction du gradient de distribution des produits doxydation. Pour pouvoir effectuer cette analyse, il faut au pralable dcouper au microtome un chantillon dpaisseur convenable (50-100 m) dans lpaisseur du film (cf. figure 9).

Figure 9 : Schma de principe de la dcoupe au microtome dun polymre pour analyse par micro-spectrophotomtrie IR3 Lchantillon ainsi obtenu est dispos sous lobjectif du microscope coupl au spectrophotomtre IRTF et lchantillon est successivement analys dans son paisseur. Labsorbance du produit doxydation considr peut tre mesure dans toute lpaisseur et le profil doxydation sil y en a un peut tre dtermine (cf. Figure 10).

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Figure 10 : Exemple de types de profils de produit doxydation obtenus par microspectrophotomtrie IRTF : (a) Absence de profil doxydation, (b) Profil doxydation2. Les analyses ont t effectues au CNEP Centre National dEvaluation de Photoprotection (Clermont Ferrand). Les chantillons ont t microtoms basse temprature (-50C) : des films dpaisseur de 40m environ ont t obtenus. Lappareil utilis est un microscope Continum coupl un banc optique Nexus de la marque Nicolet. Pour chaque analyse, une acquisition de 32 scans a t ralise et la rsolution tait de 4 cm-1. Le faisceau danalyse a t focalis sur des zones de 50 m de largeur. Les spectres sont enregistrs partir du bord de la coupe, puis par dplacement successifs, avec un pas de 50 m, vers le bord oppos. Lvolution de la raie 1713 cm-1 caractristique des produits carbonyles a t choisie pour la dtermination du profil doxydation. Dans les figures prsentes, les absorbances mesures dans lpaisseur ont t normalises par rapport celle mesure en surface.

3.2. Mesures de gonflement 3.2.1. Mesures de gonflement dans un solvant : le xylne Les mesures de gonflement dans un solvant se sont rvles particulirement utiles pour caractriser la dgradation des rseaux lastomres. Mis en prsence dun solvant adquat, les rseaux lastomres gonflent. Cette aptitude dpend des interactions entre les molcules de solvant et les chanes, et de la longueur des chanes entre nuds de rticulation. Du fait des interactions charge-matrice, lajout de charges est quivalent laddition de nuds de rticulation, ce qui perturbe le gonflement du polymre. Protocole Un chantillon denviron 0.3-0.4 g sous forme de paralllpipde de masse initiale Mi avec une fraction de masse de charges est introduit dans le xylne pendant 8 jours, pour atteindre lquilibre de gonflement. Le composite est ensuite pes ltat gonfl Ms, puis sch sous vide 60C pendant un jour et nouveau pes Md. Le taux de gonflement calcul correspond au rapport de volume gonfl du polymre rticul dans le composite aprs extraction des chanes libres et du volume sec. Il scrit :
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Q 1

polymer xylene

Ms Md Md 1

Pour les matriaux non chargs et chargs ATH, comme la fraction soluble ne contient pas de charge, la fraction soluble Fp (%) est value de la faon suivante :
Fp Mi Md Mi 1 100 2

Pour les lastomres chargs silice, des analyses thermogravimtriques (Appareil TGA F3 deNetzch) sur les chantillons schs aprs gonflement ont montr la prsence de charges dans les fractions extraites. Ainsi on dfinira la fraction totale extraite du gonflement Fs (%) avec la relation suivante :

Fs

Mi

Md Mi

100

De plus ces analyses ont permis destimer la fraction de harges prsente dans lchantillon initial et dans lchantillon sch aprs gonflement. Etant donn le faible ratio extrait faibles doses dirradiation et les incertitudes exprimentales, la part de charges prsente dans ce ratio est difficile dfinir. Cest pour cette raison dailleurs, que ces rsultats seront donns pour des fractions extraites Fs suprieures 20%. La fraction de polymre soluble Fp (%), ainsi que le ratio de charges extrait normalis la quantit initiale de charge Ff (%) et la part de charge prsente dans la fraction totale extraite Ff (%) sont donns par les relations suivantes :

Fp

Mi 1
i

1 Mi

Md

3.2.2. Utilisation de la thorie de Kraus La thorie de llasticit caoutchoutique ainsi que la thorie de gonflement des rseaux lastomres de Flory-Rhener ont t largement utilises et le succs de ces techniques pour les lastomres non chargs a suscit de nombreuses extensions pour une application aux matriaux chargs. Malheureusement, lintroduction de particules rigides dans un rseau lastomre conduit de nombreuses complications. Une des plus basiques est lincapacit de tels matriaux atteindre des dformations qui sont affines avec les dimensions de lchantillon. Kraus4 a calcul leffet de la prsence de particules sur le gonflement en faisant lhypothse que les gonflements de la matrice non charge et de la phase polymre dans le composite sont quivalents, dune part lorsque aucune interaction nest prsente entre la phase polymre et ces particule et dautre part lorsque ces particules sont compltement lies au polymre. Il a montr que pour bon nombre de matriaux, lhypothse dune interaction est vrifie. Dans le cas des EPDM chargs, les interactions charge-matrice sont relativement faibles. Cependant celles-ci peuvent voluer lors du vieillissement par irradiation. Pour tudier cet aspect, le point de vue de Kaus a t adopt. Son modle empirique prvoit une relation linaire entre le ratio de gonflement (dans un solvant, ici xylne) avec le ratio,

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o , f et c sont respectivement la proportion massique de

charge, les masses volumiques des charges et du composite :


Q Q0 1 m
f c f c

Q0 et Q sont respectivement les taux de gonflement de la matrice non charg et de llastomre charg. Aucune expression analytique nest donne pour le paramtre m, il sagit dun paramtre libre dpendant de la nature des charges et du polymre. Mais si Q/Q 0 varie linairement avec le ratio f c , avec une valeur positive pour m, les 1 f c interactions charge-matrice sont prsentes. Si par contre Q/Q0 ne varie pas linairement avec le ratio f c , o si m est ngatif, les charges sont dans ce cas 1 f c compltement inadhrentes. Pour certains lastomres chargs, une seule fraction de charge a t tudie. Dans ce cas nous nous sommes intresss uniquement au ratio Q/Q0. En fait si celui-ci est infrieur un, m est positif et les interactions charge-matrice sont prsentes, dans le cas contraire les interactions sont trs pauvres. Ces rsultats doivent tout de mme tre considrs avec prcaution, car il faut connatre pour chaque interprtation ltat de rticulation de la phase polymre et de la matrice. En effet, les diffrentes interprtations donnes prcdemment ne sont valables que pour un degr de rticulation identique de la matrice non charge et de la phase polymre. Mais dans la suite de ce travail, nous verrons que cette mthode a apport des rsultats tout fait cohrents. 3.2.3. Mesures de gonflement mixte : xylne/ammoniaque Il est bien connu que le polymre sabsorbe sur la surface des charges (ceci est montr par exemple par la prsence de polymre li aprs solubilisation dun lastomre charg non rticul). Malheureusement, cette absorption conduit une fausse estimation du taux de gonflement de la phase polymre dans le composite. La prsence dune atmosphre sature en ammoniaque permet la rupture des liaisons physiques entre polymre et charge5-6-7-8 et supprime linfluence des charges sur les mesures de gonflement. Ainsi, le traitement aux fumes dammoniaque a t appliqu nos chantillons : les matriaux sont tout dabord introduits dans un dessicateur en prsence de fumes dammoniaque pendant trois jours, toutes les fonctions hydroxyles prsentes la surface des charges ragissent avec lammoniaque. Ensuite ils sont gonfls dans le xylne pendant une semaine. Le taux de gonflement est finalement dtermin de la mme faon que prcdemment avec les mmes paramtres et sera ensuite nomm Qa. Dans notre cas, cette mthode de gonflement doit tre considre avec prcaution : en fait, quand les lastomres sont vieillis par irradiation, des produits doxydation ont t forms et ceux-ci peuvent ragir avec lammoniaque (des traitements utiliss en spectroscopie infrarouge pour quantifier les groupes carboxylique cres pendant le vieillissement2). Cest pour cette raison dailleurs que cette mthode sera utilise uniquement pour les matriaux non vieillis. 3.2.4. Mesure de prise en eau Du fait de limportante fraction volumique de silice nanoscopique et de sa large surface spcifique, de leau peut tre adsorbe sur la surface de silice du fait de la prsence de
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silanols. Ainsi lutilisation de la mesure de prise en eau peut apporter des informations sur la surface de silice et ventuellement sur les interactions charge-matrice. Des chantillons parallpipdiques coups de faon identique offrant une surface constante sont tout dabord schs sous vide pendant 24h 100C pour enlever le maximum deau prsente la surface de la charge. Ensuite aprs avoir t pess Mdried, ils sont ensuite plongs dans de leau distille temprature ambiante pendant un mois et sont ensuite une nouvelle fois pess Mswollen. La reprise en eau Sw (%) est obtenue de la faon suivante :

Sw

M swollen M dried M dried

100

3.3. Thermoporosimtrie Une manire de quantifier lhtrognit des rseaux lastomres est lobservation des tempratures fusion et de cristallisation de solvants confins dans de tels matriaux. Ce type danalyse est bas sur le fait que des molcules de solvant contraintes dans des petits volumes peuvent former des petites cristallites lors du refroidissement, qui ont des tempratures de cristallisation plus faibles que celle du solvant libre9-10. De larges distributions de tailles de cavits produisent de larges distributions de tailles de cristallites et de tempratures de fusion11. Des analyses de calorimtrie diffrentielle (DSC) de molcules de solvant contraintes dans des pores de gels dlastomres mettent en vidence des pics de cristallisation, qui peuvent donner des informations prcieuses sur la distribution des tailles de pores. Ces analyses ont t effectues avec une DSC Perkin-Elmer Pyris Diamond. La temprature et le flux de chaleur de cet appareil sont calibrs avec une rfrence (Indium T f = 156.6C, H = 28.4 J/g 10C/min). Les rseaux EPDM (non chargs) pralablement gonfls dans le cyclohexane sont introduits dans des capsules daluminium, qui sont remplies avec le mme solvant. Les chantillons sont ensuite refroidis jusqu -50C 10C/min et maintenus pendant 2 min cette temprature, puis une remonte en temprature est effectue la mme vitesse jusqu 40C. Lors de cette remonte, un premier pic apparat correspondant au solvant pig dans llastomre gonfl : sa forme et sa position dpendent du degr et de lhtrognit de rticulation, puis un second pic, qui concerne la fusion du solvant libre. Dans le cas du cyclohexane, la fusion est situe 0C. La distribution des tailles de poches de solvant est obtenue en utilisant la relation de GibbsThomson :

2 SLTm0 Tm Tm 7 L Hf Tm reprsente la temprature de fusion du solvant pig dans les pores de llastomre, SL lnergie dinterface solide-liquide, Hf la chaleur de fusion du solvant (pour le cyclohexane : 6.3 J/g), L la taille du cristal et Tm0 la temprature de fusion du solvant (pour le cyclohexane : 0C). La distribution peut tre obtenue en drivant la relation prcdente. Comme SL est un paramtre inconnu, les distributions ont t exprimes en fonction du paramtre Lf, qui reprsente les poches de solvant les plus grandes et dont la temprature de fusion est Tf :
0

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dM dL

dH Tm 0 dT A Lf 1 H f Tm 0

avec A

Tf

3.4. Analyses thermiques diffrentielles (DSC) Toutes ces analyses ont t ralises avec une DSC Perkin-Elmer Diamond avec des chantillons denviron 7-8 mg pour les lastomres non chargs et 10-15mg pour les lastomres chargs. Le gaz de purge utilis est lazote. Lappareil est pralablement calibr avec la temprature et lenthalpie de fusion de lindium (156.6C, 28.45 J/g) en utilisant la mme vitesse de monte en temprature utilise pour nos expriences. Le domaine de temprature de cristallisation de notre EPDM est large12 : de -40C jusqu 60C. En fait, quand le polymre est refroidi de 80C -50C, un seul pic est observ pendant la rampe en temprature, comme le montre la figure 11 a). Si un traitement isotherme de quelques heures est effectu une temprature Tc pendant la descente en temprature, trois pics de fusion sont observs la remonte en temprature (cf. Figure 11 b)) : Le premier correspond la population de cristallites forme pendant le refroidissement de 80C jusqu Tc Le second concerne la population de cristallites cre pendant le traitement isotherme la temprature Tc Le troisime correspond la population forme pendant le refroidissement de Tc 40C Une srie dexpriences a t ralise pour valuer la temprature optimale de cristallisation, i.e. la temprature Tc qui permet dobtenir le plus important taux de cristallinit avec la cintique de cristallisation la plus rapide. La temprature trouve est 22C et la dure optimale du traitement pour obtenir un taux de cristallinit stable est 12 h. Ainsi le protocole du traitement thermique appliqu aux chantillons avant quils soient vieillis par irradiation temprature ambiante est le suivant (cf. Figure 11 c)): Une monte en temprature jusqu 80C pour effacer lhistoire thermique du matriau Et une rapide descente en temprature jusqu la temprature optimale de cristallisation (22C) et un maintien cette temprature pendant 12 h De plus, pour viter que la cristallinit ne soit affecte par les futurs traitements thermiques autour de cette temprature, en particulier la campagne de vieillissement dans la piscine 18C, et la conservation des chantillons aprs vieillissement 22C, les chantillons ont t recuits : monte en temprature 1C/min jusqu 38C et un maintien de 6h cette temprature. Ce traitement permet dobtenir un unique pic trs bien dfini pour les EPDM non
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chargs et un recouvrement de deux pics galement bien dfini pour les EPDM chargs. Dans les deux cas, ces matriaux possdent des populations de cristallites avec des tempratures de fusion suprieures 22C. Aprs vieillissement, les chantillons ont t conservs dans une enceinte climatise 22C.

Figure 11 : Cintique de cristallisation et de fusion de lEPDM Pour les matriaux vieillis par irradiation 80C, aucun protocole na t appliqu avant vieillissement, puisque 80C est au dessus de la temprature de fusion des cristallites. Par contre aprs la campagne, ils ont t refroidis jusqu 22C et conservs cette temprature. Pour tudier la cristallinit de ces matriaux aprs irradiation, ils sont refroidis de la temprature ambiante jusqu -50C 10C/min puis chauffs la mme vitesse jusqu 100C. Le refroidissement jusqu -50C est ncessaire pour viter lovershoot qui se serait superpos aux pics de fusion, si la rampe de chauffage avait commenc de la temprature ambiante. Mais ce refroidissement conduit lapparition dun pic supplmentaire, qui est observ entre -40C et 20C. Ainsi le taux de cristallinit Xc a t dfini partir de lenthalpie des pics prsents entre 22C et 60C Hf.
Xc Hf 1 Hf0 9

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avec la fraction massique de charges, et Hf0 est lenthalpie de fusion dun cristal parfait de polythylne (puisquon suppose que seuls les segments polythylnes peuvent cristalliser)

3.5. Essais de traction Les mesures aux grandes dformations ont t conduites par lintermdiaire du systme Vidotraction, dvelopp par la socit Apollor, et ce une vitesse de dformation vraie constante 0,01s-1 et deux tempratures : 25C et 80C (temprature suprieure la temprature de fusion des cristallites). Ces essais de traction uniaxiale ont t raliss sur une machine MTS, sur laquelle le systme vidotraction a t adapt. La cellule de force permet des mesures de force jusqu 100N. Les prouvettes sont maintenues durant lessai par des mors vis, les ttes dprouvettes sont renforces par des rondelles mtalliques dans le but de prvenir de la dformation des ttes et le glissement de lprouvette durant lessai. Le systme Vidotraction est compos dune camra CCD quipe de 2 objectifs avec son pied motoris, dclairages spcifiques et dun ordinateur. Le principe de fonctionnement du logiciel Vidotraction est bas sur le suivi de barycentres de taches (4 dans notre cas). Il permet au final dobtenir des courbes contrainte vraie-dformation vraie. Des prouvettes en forme dhaltre, dcoupes dans les plaques moules, offrent une longueur utile de 20mm pour une largeur de 4mm et dune paisseur voisine de 1mm. Quatre taches sont disposes, comme reprsentes sur la figure suivante, de manire mesurer la dformation dans la direction de traction (1) et celle dans la direction perpendiculaire (2).

Figure 12 : Eprouvette + Taches de Vidotraction Ces mesures permettent de suivre dune part la dformation vraie (1) mais aussi la contrainte vraie dfinie par :

F Svraie avec Svraie S0 1 2 10 On peut ainsi, pour chaque essai, tracer la courbe vraie = f(vraie). Pour chaque matriau, trois chantillons sont tests, sur les figures une seule courbe sera reprsente, mais les contraintes et les dformations la rupture avec les barres derreur seront renseignes dans un tableau part.
vraie

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Le module lastique 25C et 80C est estim partir de la pente lorigine de ces courbes de traction. Des essais de cycles de traction ont t effectus 80C. Lchantillon est tout dabord tir jusqu la dformation vraie 0.2, puis est relax 5 minutes, ensuite il est de nouveau tir jusqu 0.4 en dformation vraie. Cette exprience est rpte par incrment de dformation vraie de 0.2 jusqu la rupture de lchantillon. 3.6. Diffusion des X aux petits angles (SAXS) et aux grands angles (WAXS) Mesures in-situ en traction Les rayons X obtenus partir dune anode tournante Rigaku (40 kV 28 mA), sont collimats de manire ponctuelle et parallle grce un systme optique bas sur les miroirs de Gbbels dvelopp par la socit XENOX. Une raie monochromatique de la raie K- du cuivre ( = 1.54 ) est obtenue. Le domaine de diffusion est dduit partir de la distance dtecteurchantillon. Le vecteur de diffusion est directement corrl langle de diffusion 2 et la longueur donde :

sin

11

Dans nos expriences, le dtecteur est plac environ 1160 mm de lchantillon pour une diffusion des X aux petits angles (0.01nm-1<q<0.08 nm-1) et 50 mm pour une diffusion des X aux grands angles (0.5nm-1<q<2nm-1). Les spectres 2D sont enregistrs par une camra CCD Princeton Instrument PI-CSX et les images sont traites laide du logiciel Winview puis intgres grce au programme Fit2D dvelopp par lESRF de Grenoble. Les temps de pause sont de 5 minutes pour le SAXS et 20s pour le WAXS. Les donnes obtenues sont corriges en prenant en compte le fond continu, le bruit du dtecteur et lpaisseur de lchantillon. 3.6.1. SAXS

Figure 13 : Spectres SAXS pour le matriau E-CR non vieilli pendant un essai de traction

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A partir du profil dintensit diffuse (cf. Figure 13), il est possible de dterminer la longue priode LPB, correspondant la priodicit de lempilement des lamelles cristallines et des lamelles amorphes. Elle peut tre calcule partir du maximum dintensit diffuse corrige du facteur de Lorentz (Iq2 = f(q)) laide de la relation (cf. Figure 14) :
LPB 2 qmax 12

LPB reprsente la somme de lpaisseur moyenne dune lamelle cristalline lc et dune rgion amorphe interlamellaire la. Cette mthode ne permet pas daccder aux valeurs de la et de lc. Pour obtenir les paramtres structuraux lc et la, on peut utiliser la fonction de corrlation. Dans le cas de matriaux isotropes, la fonction scrit de la faon suivante partir des courbes dintensit I = f(q) :
I q q 2 cos qr dq r
0

13 I q q 2 dq
0

Avec r la distance dans lespace des rels. En pratique, les donnes ne sont pas enregistres de 0 linfini, mais seulement sur un espace limit. Ainsi la procdure dintgration implique lutilisation dune extrapolation aux trs petits angles laide dune loi empirique de la forme :

I (q)

Aq

14

Aux grands angles, les donnes sont extrapoles selon une loi physique de type loi de Porod :
I (q) B q2 C q4 14

Avec B reprsentant la qualit de linterface et C la constante de Porod (cf. Figure 14). La figure 15 prsente une fonction de corrlation typique. En plus de la longue priode LPB obtenue prcdemment, une autre estimation de ce paramtre peut tre ralise LPC et les paramtres la et lc peuvent tre dduits.

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0,25

qmax
0,20
extrapolation extrapolation

0,15

Iq

0,10

0,05

0,00

0,00

0,01

0,02

0,03

0,04

0,05
-1

0,06

0,07

0,08

0,09

0,10

q (nm )

Figure 14 : Fonction classique Iq2 en fonction de q

1,2 1,0 0,8 0,6

(r)

0,4 0,2 0,0 -0,2 -0,4 0 2

lc

la = LPC - lc

LPC
min

10

12

14

16

r (nm)

Figure 15 : Fonction classique de corrlation Une machine de traction permettant la dformation symtrique de lchantillon est utilise pour toujours sonder la mme zone dchantillon. Lessai est ralis temprature ambiante avec une vitesse de traction 6.7E-4 s-1. Les spectres sont enregistrs toutes les 5 minutes.

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3.6.2. WAXS

Figure 16 : Spectres WAXS du matriau E-CR non vieilli pendant un essai de traction

Figure 17 : Fonction classique I en fonction de q Le spectre WAXS du matriau E-CR non vieilli est prsent sur la figure 16. Aprs traitement du spectre, une courbe intensit en fonction de langle diffusion 2 est obtenue. En utilisant le logiciel eXPFIT, un pic de diffraction a pu 21.3 et une bosse amorphe ont pu tre dconvolus avec des lorentziennes. Sil sagit dune forme orthorhombique, comme pour un polyethylne classique, il y a deux pics de diffraction entre 20 et 25, i.e. pour les plans (110) et (200), mais le plan (200) reprsente un paulement dans le cas dun copolymre thylnepropylne12. Par contre dans le cas dune forme pseudo hexagonale, un seul pic est observ
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sur la gamme 20-25. Dans notre cas, tant donne la faible cristallinit du matriau (10%), il est difficile de conclure. Des mesures WAXS in-situ en traction 25C et 80C ont t ralises avec le mme dispositif. Les essais sont effectus temprature ambiante avec la mme vitesse. Lenregistrement est ralis toutes les 20s. Le ratio phase amorphe non oriente / phase amorphe oriente peut tre valu partir des intensits des bosses de diffusion des phases amorphes lquateur et au mridien (secteur angulaire de 30), la direction de traction est indiqu sur la figure 16 13. Les intensits de diffusion des phases amorphes lquateur et au mridien pralablement normes par rapport ltat non dform sont respectivement nommes Ia(mridien) et Ia(quateur) comme le montre la figure 16. Le ratio de phase amorphe orient est dfini par la relation :
I a ( mridien ) I a (quateur ) 100 16

I a ( mridien )

3.7. Observations microscopiques Des cryofractures ont t ralises sur les chantillons chargs ATH et silice avant et aprs vieillissement par irradiation temprature ambiante. Ces profils de fracture ont t observs avec un microscope lectronique balayage environnementale (ESEM, pour environnemental scanning electron microscopy). Ce type de microscopie sappuie sur deux innovations techniques : Lutilisation dun systme de pompage diffrentiel entre la colonne du microscope, qui reste dans un bon vide, et la chambre dobservation. Cela permet dimager des chantillons dans un environnement gazeux contrl, avec une pression pouvant atteindre 1330 Pa. La mise au point dun nouveau type de dtecteur, le GSED (gaseous secondary electron detector) fonctionnant grce une amplification du signal lectronique par le gaz prsent dans la chambre du microscope. Il permet de dtecter des lectrons secondaires mis par lchantillon sous une pression partielle de 13 1330 Pa. LESEM offre ainsi plusieurs avantages par rapport aux techniques classiques de microscopie balayage. En effet, linteraction des lectrons mis par lchantillon avec le gaz de la chambre prsente un effet secondaire intressant : les ions positifs forms vont venir compenser les charges ngatives qui peuvent saccumuler la surface des chantillons isolants. Il est alors possible dobserver en ESEM des chantillons isolants sans mtallisation pralable. Nos chantillons ont donc t observs sans tre mtalliss, les observations ont t ralises faible tension : la tension du filament a t fix 10 keV et sous une pression de vapeur deau (2.3 torr).

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Matriaux Conditions de vieillissement Techniques exprimentales

Rfrences

RAMIER J., et al., Grafting of Silica during the Processing of Silica-Filled SBR : Comparison between Length and Content of the Silane. Journal of Applied Polymer Science: Part B: Polymer Physics, 2006. 44: p. 143-152. 2 RIVATON A., CAMBON S., and GARDETTE J.L., Radiochemical Ageing of EPDM Elastomers. 2. Identification and Quantification of Chemical Changes in EPDM and EPR Films Gamma-Irradiated under Oxygen Atmosphere. Nuclear Instruments and Methods in Physics Research B, 2005. 227: p. 343 - 356. 3 CAMBON S., Etude du Mcanisme de Dgradation Radiochimique d'un Elastomre de Type EPDM. 2001, Universit Blaise Pascal: Clermont Ferrand. 4 KRAUS G., Swelling of Filler-Reinforced Vulcanizates. Journal of Applied Polymer Science, 1963. 7: p. 861-871. 5 POLMANTEER K.E. and LENTZ C., Reinforcement studies - Effect of silica structure on properties and crosslink density Rubber Chemistry and Technology, 1975 48: 795 6 CHIEN A., et al., Characterization of Radiation-Induced Aging in Silica-Reinforced Polysiloxane Composites. Radiation Physics and Chemistry, 2000 59: 493-00 7 WOLFF S., Chemical Aspects of Rubber Reinforcement by Filler Rubber Chemistry and Technology, 1996 69: 325-46 8 PAL P.K. and DE S.K., Studies on peroxide vulcanization of silica-filled EPDM rubber in presence of vinylsilane coupling agent. Polymer, 1984 25: 855 9 VALLAT M.F., R.F., DAVID M.O., A Structural Study of EPDM Networks - The Influence of the Crosslinking Mode on their Microscopic Structure. European Polymer Journal, 2004. 40: p. 1575 1586. 10 HONIBALL D., HUSON M.G., and MCGILL W.J., A nucleation theory for the anomalous freezing point depression of solvents in swollen rubber gels. Journal of Polymer Science: Part B: Polymer Physics, 1988. 26: p. 2413 - 2431. 11 QIN Q. and MCKENNA G. B., Melting of solvents nanoconfined by polymers and networks. Journal of Polymer Science: Part B: Polymer Physics, 2006. 44: p. 3475 - 3486. 12 LIU L.Z., HSIAO B.S., REN S., FU B.X., TOKI S., ZUO F., TSOU B., CHU. B., In situ WAXD study of structure changes during uniaxial deformation of ethylene-based semicrystalline ethylenepropylene copolymer, Polymer, 2006 47: 2884 13 MURAKIMI S., et al., Structural development of natural rubber during uniaxial stretching by in situ wide angle X-ray diffraction using a synchrotron radiation, Polymer, 2002. 43: p. 2117.

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Rsultats & Discussions

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Rsultats & Discussions

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ARTICLE 1: Evolution of EPDM networks aged by gamma-irradiation Consequences on mechanical properties
PLANES E., CHAZEAU L., VIGIER G., FOURNIER J. (Accept dans Polymer)

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Sommaire

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Abstract ................................................................................................................................................ 83 1. 2. Introduction ................................................................................................................................. 83 Experimental................................................................................................................................ 85 2.1. 2.2. 2.3. Materials ................................................................................................................................ 85 Ageing conditions.................................................................................................................. 86 Instruments ............................................................................................................................ 86 Swelling measurements ................................................................................................. 86 Tensile tests ................................................................................................................... 87 Thermoporosimetry ....................................................................................................... 87

2.3.1. 2.3.2. 2.3.3. 3.

Results........................................................................................................................................... 88 3.1. 3.2. 3.3. 3.4. Degradation kinetic ............................................................................................................... 88 Large strain behavior ............................................................................................................. 95 Network heterogeneity ........................................................................................................ 100 Simulation ........................................................................................................................... 102

4. 5.

Discussion ................................................................................................................................... 108 Conclusions ................................................................................................................................ 109

Acknowledgements ............................................................................................................................ 110 References .......................................................................................................................................... 111

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Du fait de son importante proportion en thylne, lEPDM tudi est lgrement semicristallin temprature ambiante (10%). Ainsi lun des premiers objectifs a t de comprendre les consquences dun vieillissement par irradiation temprature ambiante dEPDM non chargs sur leurs proprits mcaniques ltat amorphe (i.e. au dessus de la temprature de fusion de leurs cristallites). Afin de mieux comprendre les relations entre mcanisme de dgradation et proprits mcaniques dans cet tat amorphe (module lastique et rupture), ces matriaux irradis ont t compars des lastomres avec diffrents degrs de rticulation. De plus, comme ces matriaux sont soumis un phnomne majoritaire de scissions de chanes, un modle statistique de coupures de chanes a t labor pour avoir une ide de larchitecture du rseau lastomre dgrad par irradiation, de manire proposer une explication pour les comportements observs.

Abstract Different Ethylene Propylene Diene Monomer (EPDM) elastomers with different crosslink densities have been processed in order to evaluate the influence of gamma irradiation on their properties. In the case of a major phenomenon of chain scissions, the consequences are a decrease in the modulus but also a decrease in the strain at break. This decrease in the strain at break is opposite to what is expected for materials with increasing average chain length between crosslinks. To gain more insight into the network architecture, which is presumed to be responsible for this behavior, Charlesbys approach is applied. In tandem, a computational model of the degradation is developed for improved prediction of the evolution of the elastic modulus. Using these calculations, a novel interpretation of the ultimate properties of the elastomer as a function of its architecture is proposed.

1. Introduction Polymer materials in cables and accessories for nuclear engineering applications must typically be designed to withstand extreme environmental conditions. EPDM is one of the most common polymers for this type of application, used for instance in nuclear power plants. In this kind of application, polymer sheathing may be exposed to elevated temperatures and gamma irradiation which will accelerate its ageing and consequently degrade its useful application lifetime. The study of ageing effects due to gamma irradiation of EPDM elastomers under oxygen atmosphere has led to propose a mechanism of radio-oxidation [1,2]. This mechanism artificially induces an accelerated evolution of the mechanical properties material. Indeed, chain scissions occur, counterbalanced by a crosslinking mechanism which depends on the initial crosslinking of the material, which, in turn, leads to modifications of the macroscopic mechanical properties [3,4,5,6,7]. The consequence of such ageing, at temperatures higher than the melting temperature of the EPDM crystallites, is a decrease in the material stiffness. Moreover, the presence of crystallites at ambient temperature attenuates this effect [8,9]. Although a qualitative relationship between the macroscopic mechanical properties of the aged samples and the degradation time can easily be proposed, a true understanding of the consequences of degradation of elastomer network structure on its mechanical behavior is much more difficult. This difficulty comes from the fact that there remain several unanswered questions concerning the mechanical behavior of such materials. In particular, the role of network heterogeneities, such as that of crosslink density or the presence of free chains and
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dangling chains, is still under debate [10,11,12,13]. The role of the network imperfections is clearly evident in results from previous modeling efforts presented in the literature to date. One can cite the early work of Termonia [14,15], who studied the network connectivity and its mechanical properties, or the work of Grest et al. [16], where particular attention was paid to the influence of strand length, dangling ends and loops. Some experimental studies also infer that network imperfections such as free chains reduce the tensile strength and simply result in a diluted network [10]. Moreover, the pioneering work of Mark and his collaborators on the effect of the elastomer network architecture stress the importance of the distribution of chain lengths between crosslinks in the strength properties of elastomer [11, 12, 13]. Complementing previous experimental study of model elastomers, elastomer degradation by irradiation can provide additional experimental insights into the nature of underlying relationships between network microstructure and mechanical properties (elastic modulus, ultimate properties), since irradiation enables a controlled, progressive manipulation of this microstructure as a function of irradiation dose. Such an approach nonetheless requires a proper understanding of the microstructural evolution of the materials during ageing. Some information on this evolution can be obtained using Charlesbys approach [17,18]. Indeed, this enables to relate crosslinking and scission kinetic to the evolution of the sol fraction. However, the statistical principles behind Charlesbys approach prohibit explicit quantification of network imperfections. The only way to obtain such quantification is to model the network architecture and extract the pertinent parameters describing its real-world behaviour. Recent efforts have therefore been increasingly devoted to modeling the molecular dynamics of the formation of polymer networks via the crosslinking process. Among them, one can cite the recent work of Rottach [19,20,21] who extended his research to the crosslinking process of network during stretching. Though of obvious interest, this type of model is difficult to directly apply to the case of any particular experimental study. In the specific case of irradiation, it can in fact be more revealing to use a simpler description of the network architecture based on experimental data, in order to expose the direct relationship between mechanical properties of materials and their exposure to radiation. Thus, in this work, different EPDM networks are elaborated: pure gum (non-crosslinked EPDM) and EPDM crosslinked by peroxide, both aged by gamma irradiation at room temperature under oxygen atmosphere, and EPDM crosslinked by peroxide at various degrees. Note that, given the semi-crystalline nature of the EPDM at room temperature [9], the work described in the article concerns EPDM at 80C, i.e. above its melting temperature. The materials are tested by mechanical test, swelling behavior and thermoporosimetry. In addition, a modeling of the network architecture is presented, which enables a description of evolution in relation with the experimental data. Our results lead us to conclude that irradiation causes significant defects in the network structure. The level of defects is in fact so high in rubber materials that their mechanical properties can in fact no longer be correlated at all with the standard measures of crosslink density or length of chain between crosslinks.

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2. Experimental 2.1. Materials

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The EPDM elastomer (Nordel IP NDR 3722 P from Dow Chemical Company) is composed of 70% ethylene, 29.5% propylene and 0.5% ENB. An analysis by gel permeation chromatography (GPC) gives the following results:
Mw 39300 g mol , M n 5140 g mol .

EPDM plates (1mm) are produced with two formulations: pure gum (E-NC) and crosslinked elastomer (E-CR). The samples are processed following three steps. The first step involves mixing the matrix and introducing a crosslinking agent to the polymer. Specifically, after 5 minutes of mixing in an internal mixer, peroxide is added. Its dispersion is permitted for 10 min at low temperature (80C) to prevent any reaction of the crosslinking system. In order to obtain a better dispersion, the second step is mixing in an external mixer (cylinders) for 10 min at low temperature (80C). During the last step, the compound is pressed over a 10-minute period into 1-mm-thick films at 170 C, in order to promote a crosslinking reaction. The crosslinking agent we used is the dicumyl peroxide (Perkadox BC-FF from Akzo Nobel), introduced at 3 phr. The curing time (t98 at 170C) is determined from torque measurements performed with a MOSANTO analyzer. During curing of ethylene-propylene elastomer [22, 23], the peroxide decomposes into radicals at elevated temperature, which results in the formation of peroxy radicals. They can react with the polymer chains by abstraction of hydrogen atoms to produce macroradicals. Two types of chemical crosslinks are formed, one type via combination of peroxide-induced EPDM macroradicals and the other one via addition of the macroradicals to the residual double bonds of the termonomer. Actually, peroxide cure of EPM (without termonomer) is relatively inefficient. This is mainly due to scission reactions occurring on tertiary radicals created by H-abstraction in the propylene sequence. Moreover a total efficiency of peroxide is usually inhibited by occurrence of all kinds of auxiliary reactions, such as alternative peroxide decomposition pathways leading to inert products, combination of peroxide-derived radicals and/or disproportionation of radicals. Two elastomers with smaller crosslinking degrees are produced as a final result, by choosing different curing times: 2min, 3min. They will be called E-CR2min and E-CR3min (see Table 1). As the soluble fraction in all crosslinked samples is zero, we can assume that all chains are crosslinked. The samples are then artificially exposed to gamma radiation as described below.

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Table 1: Composition and swelling data of the studied materials (The proportions are expressed in phr: per hundred parts of matrix)

2.2. Ageing conditions E-NC and E-CR are exposed to -radiation of a 60CO source at a dose rate of 1 kGy/h at room temperature in an oxygen atmosphere for doses 50, 165, 300, 510 kGy (Arc Nucleart Grenoble France). The samples are stored under vacuum at room temperature. Radio-oxidation of EPDM macromolecules leads to the observation by IR spectroscopy of an increase in absorbance in the hydroxyl absorption region (3800-3000 cm-1) [1,2] corresponding to the formation of alcohols, acids and hydroperoxides. The formation of carbonyls can also be evidenced by the absorption maximum at 1713 cm-1 with several shoulders around 1785, 1755, 1740, and 1695 cm-1[1]. Analysis of the oxidation product distributions within the oxidized E-CR is made for E-CR-510, and the variations in absorbance at 1713 cm-1 are chosen to characterize the product distributions according to thickness. The oxidation profile is found flat for this dose, which indicates that, in these conditions of irradiation, the oxidation processes are homogeneously distributed within the sample. The samples will be named hereafter E-CR-XXX and E-NC-XXX with XXX denoting the radiation dose.

2.3. Instruments 2.3.1. Swelling measurements Samples with an initial mass Mi are introduced into a xylene composition over an 8-day period to permit them to achieve swelling equilibrium. Then the materials with swelled mass Ms are dried under vacuum at 60C for 24 hours and weighted in order to obtain their dry mass Md. The soluble fraction Fs and the swelling ratio Q are calculated from the following relations:
Fs 1 Md Mi 1

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Q 1
polymer xylene

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Ms Md Md

(2)

Matrix network chain density in the swollen materials can be estimated from swelling ratio in xylene Q using the Flory-Rehner equation [24]. This equation depends on the network functionality f (non-aged crosslinked samples have a functionality 4), and 1 the FloryHuggins polymer-solvent dimensionless interaction term. It is noteworthy that the functionality f is decreased as a result of material ageing. More importantly, the value of the Flory Huggins parameter is difficult to estimate, especially after material degradation, since the polarity of the chemical composition can be strongly affected. Moreover, the result calculated from the Flory-Rehner equation is strongly sensitive to this value. These two observations suggest considering with caution the crosslink density values deduced using this technique. Therefore, we will only consider the swelling ratio and the sol fraction as reliable data. We are supported in this choice by the recent paper of Valentin et al. [25] who clearly demonstrate the uncertainties in the determination of elastomer network characterized by swelling technique.

2.3.2. Tensile tests Tensile tests are performed on an MTS device with a temperature-controlled chamber. An image processing acquisition system (Apollor VideoTraction System) is used to obtain the true stress-strain curve. Experiments are carried out at 80C (above the melting temperature) with a 0.01 s-1 true strain rate. The samples are dumbbell-shaped with typical dimensions 20 x 4 x 1 mm3. For each material, three specimens are tested. In the figures shown only one test is reported, but the average stress and strain at break of the three specimens, with error bars, is given in figure 8. The elastic modulus E is calculated as the slope at the origin of the true strain - true stress curve. The shear modulus G is deduced from the tensile elastic modulus E, assuming that the material, like any rubber, is quasi-incompressible: The Poisson coefficient is therefore approximated to 0.5.

2.3.3. Thermoporosimetry One way of quantifying the heterogeneity of an elastomer network is by observation of the melting or freezing point of adsorbed solvent within the elastomer network. This technique is generally called thermoporosimetry. This experiment is based on the fact that solvent molecules constrained to small volumes form only relatively small crystallites upon crystallization and therefore exhibit lower crystallization temperatures [26]. Broad distributions of cavity sizes should give rise to broad distributions of crystallites sizes and thus crystallites melting points [27]. Therefore, differential scanning calorimetry measurements performed on swollen sample with solvent molecules constrained in the pores can give evidence of several crystallization temperatures, which are indicative of the pore sizes and of the distributions of these sizes.

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The samples are therefore swollen in cyclohexane. Then they are carefully extracted and put into an aluminum crucible fully filled with the same solvent. The melting behavior of the solvent in the samples is studied using a Perkin-Elmer Pyris Diamond differential scanning calorimeter (DSC). The temperature and heat flow of the DSC are calibrated using a standard reference (Indium). A cooling scan is first run at 10C/min from room temperature to 50C and the instrument held isothermally at 50C for 2 min. This is followed by a heating scan at 10C/min up to +40C. While increasing temperature from 50C to +40C, a first peak appears for swollen network which corresponds to the melting of the cyclohexane entrapped in the network. Then a second strong peak corresponding to the melting point of the free cyclohexane (in excess) is visible at around 0C. We will return to the analysis procedure of the experimental results later in this article.

3. Results 3.1. Degradation kinetic The evolutions of Q and of soluble fraction Fs with the irradiation dose for E-CR are shown in figure 1a). Between 0 and 50 kGy, we can only note a little evolution of F s while Q remains constant. This means that chain scissions and crosslinking are in competition. After 50 kGy, chain scissions seem to be the most important phenomenon: Q rapidly increases with the irradiation dose as well the soluble fraction Fs. The evolutions of Q and Fs with the irradiation dose for E-NC are also shown on the figure 1b). Fs decreases with irradiation dose, then stabilizes and begins to increase at 510 kGy. Q follows the same evolution. Between 0 and 300 kGy, the major phenomenon is crosslinking while at higher doses the main occurring process is chain scission. The minimum Q value (Q = 25) is still large compared to the initial Q value of unaged E-CR (at 0 kGy, Q=3.7). This means that the crosslinking process of E-NC by irradiation is rapidly counterbalanced by chain scissions. These results are in agreement with the evolution of the experimental elasticity moduli of ENC and E-CR as a function of the irradiation dose, which are presented in Figure 2. The major chain scission phenomenon occurring under irradiation is evidenced for E-CR as a rapid decrease in the modulus of elasticity. The modulus slightly increases at the first dose (50kGy), confirming the occurrence of an initial crosslinking. In the case of E-NC, first an increase in the modulus is observed, significant of a major crosslinking phenomenon. Then above 165 kGy, chain scissions mainly take place as evidenced by the modulus decrease.

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Figure 1: Evolution of the swelling ratio Q and the soluble fraction Fs with an increasing irradiation dose for a) E-CR and for b) E-NC (Continuous and dashed lines are guidelines)

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Figure 2: Evolution of the shear modulus G at 80C with an increasing irradiation dose for E-NC and for E-CR. Using affine network theory, the active chains concentration c can be deduced from the modulus G, following the equation [24]:
c

G (1 Fs ) RT

1/ 3

(3)

Figure 3 presents the evolution of deduced active chain concentration of E-CR sample. As chain scissions dominate beyond 50 kGy, and in order to estimate the chain scission kinetic action independent of the crosslinking process, we have chosen to fit the experimental c data by an exponential decay law at radiation doses above 50 kGy:
c 0

exp

Gs
0

(4)

where D is the radiation dose.

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Figure 3: Evolution of the apparent crosslink density versus irradiation dose with the phenomenological fits for E-CR and E-NC Note that for small radiation doses, this law can be approximated as:
Gs D (5) with 0 the initial active chain density and Gs the chain scission yield (mol/J) of the chains belonging to the network. The parameters deduced from the fit are: 0 = 4.15x10-4 mol/cm3 and Gs = 8.1x10-7 mol/J. Kelidj et al.[28] have estimated from their kinetic model a chain scission yield for two polyethylenes studied by Decker et al.[29] irradiated at 0.292 Gy.s-1 (1.05 kGy.h-1) with different crystallinity ratios: 50% and 75%. The values are respectively 3.3x10-7 mol/J and 2.6x10-7mol/J. They can be compared to the Gs value deduced from our fit. In our case, the chain scission yield is higher. This difference could be explained by the lower crystallinity of our samples compared to that in the previous studies. Indeed, in the crystalline regions the macromolecules have very small mobility and the oxygen is almost unable to diffuse; diffusion constants for crystalline phase are small, around 8 or 9 orders of magnitude smaller than in the amorphous region. For that reason, chain scissions mostly take place in the amorphous regions. Taking into account the crystallinity of our materials (around 11%), our chain scission yield related to the amorphous part (9.1x10-7mol/J) is between the values deduced from the Decker data (6.6x10-7mol/J and 10.4x10-7mol/J respectively). An alternative explanation is as follows: The studied rubber is a copolymer with a non-negligible fraction of propylene and this termonomer is more sensitive to chain scissions [30]. The 0 value deduced from our fit can be seen as the assumed initial crosslink density value of an E-CR that would have given the experimental crosslinking density evolution as a function of the irradiation
c 0

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dose, if only the chain scission processes had taken place. Such value corresponds to a molar mass between crosslinks of 2200 g/mol (calculation made with an EPDM density of 0.9). Figure 3 also presents the apparent crosslinked density of E-NC deduced from equation (3), as a function of the irradiation dose. In this case, the crosslinking process is significant and precludes a similar curve fit. However, the material degradation can be seen as the successive occurrence of a crosslinking process, which leads to a material with a given crosslink density, submitted afterwards to a degradation process similar to that occurring in the E-CR sample. The crosslinking process is assumed to be governed by the gap between the actual crosslink density 0 and an equilibrium crosslink density 0eq. This can be empirically modeled by the formula:
0

'

0 eq

1 exp

2Gc
oeq

(6)

with Gc the crosslinking yield (proportion of crosslinked monomer units per energy unit). The factor of two in the exponential represents the fact that one crosslink induces two monomer units. From this the assumption can be made that the scission kinetic is the same as for E-CR. Under this assumption, the apparent active chain density c of E-NC is:
'exp Gs D
0 eq 0 eq

1 exp

2Gc D
0 eq

exp

Gs D
0 eq

(7)

The corresponding fit is very satisfactory and is presented on figure 3. The parameters deduced from the fit are 0eq = 2.7x10-4 mol/cm3, which is assumed to be constant, and Gc = 1.15x10-6 mol/J. The maximal active chain density obtained by peroxide cure, and deduced from E-CR was previously found to be 4.15x10-4 mol/cm3. Both values are of the same order. Thus, within the assumption of this phenomenological model, the number of crosslinking sites potentially activated by gamma-irradiation is on the same order as that generated by peroxide crosslinking. Note that this phenomenological approach implicitly makes the strong assumption that the crosslinking process involved during the degradation mechanism would lead, without the concomitant occurrence of chain scissions, to a crosslinking of the network without any sol fraction (since otherwise one must account for the possible scission of chains of the sol fraction). To gain further insight into the kinetic degradation of the E-CR material, the CharlesbyPinner approach is used [17]. It provides a simple expression relating sol fraction Fs to irradiation dose D, in the specific case of an initial random distribution of the molar weight of the polymer chains under the assumption that crosslinking and scission occur at random.
Fs Fs p ( D) q ( D) 1 (8) q( D)u1

Where D is the irradiation dose, q(D) is the proportion of crosslinked monomer unit and p(D) is the number of chain scissions per monomer unit. The parameter u1 is related to the initial distribution:
u1 M n / w (9)

With M n and w the average number molar weight and the molar mass of the polymer unit.
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The relation (8) holds whether or not main-chain fracture occurs simultaneously with crosslinking. Indeed this relation allows one to consider a material undergoing simultaneous crosslinking and scission as it first experienced scission, only then followed by crosslinking. This relation is only valid in the case of an initial random distribution. For other distributions, there is no analytical expression. The relation remains valid, however, for large numbers of scissions, since the initial distribution tends to be a random after a large number of scissions.

Figure 4: Evolution of Fs

Fs versus irradiation dose, compared with relation (8)

In our study, as shown previously, the E-CR material is submitted to a competition of the phenomena of crosslinking and chain scissions between 0 and 50 kGy. After 50 kGy, the major phenomenon is scissions. Thus the proportion of crosslinked monomer q(D) is taken independent on D, as a constant qf. The value of this constant can be estimated from the elastic modulus data. The average molar mass between crosslinks of the modeled E-CR is estimated equal to 2200g/mol through the previous extrapolation at 0kGy of the active chain concentration (cf. figure 3). .This is equivalent to considering an initial average chain length between crosslinks Nc of 66 units (calculation made with an EPDM unit with a molar mass of 32.6g/mol). We can also make the assumption (as Charlesby did [17, 18]) that p(D) is proportional to irradiation dose. Thus the relation (8) becomes affine in D:

Fs

Fs

p0 D qf

1 (10) q f u1

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with p0 a constant. As shown in the figure 4, the experimental evolution of Fs

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Fs versus

irradiation dose is in good agreement with the relation (10). Taking for p0 q f a value of 1.1x10-3 kGy-1, a chain scission yield Gs-charlesby can be deduced: It is found that 5.2x10-7 mol/J is in good agreement with the previous value Gs (8.1x10-7 mol/J). This value is also in agreement with the work of Decker et al. [29] taking in account the crystallinity ratio. The number of scissions per monomer unit as a function of the irradiation dose calculated using the deduced p0 value is presented in figure 5. Returning to figure 4, we note that the intercept point of the affine fit is 8.2x10-2. Within the assumption of an initially random distribution of the polymer, an average number molar weight of the unlinked polymer can be estimated to be approximately 26000 g/mol. This value is larger than that of our polymer ( M n 5140 g mol ), but this discrepancy could be explained by the fact that the initial molar weight distribution of the polymer is not random, in other words that the equation (10) is not valid for low radiation doses. From the same fit of figure 4, we can also calculate the irradiation dose required to reach the complete degradation of the polymer, that is, when the soluble fraction is equal to 1. The extrapolated value is 1750 kGy.

Figure 5: Number of chain scissions as a function of the irradiation dose p(D), deduced from Charlesby and from the simulation and the experimental soluble fractions for E-CR Charlesby [17] also proposed a relationship between the average weight between crosslinks Mc in the gel, the sol fraction and the crosslink density:
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Mc w q 1 Fs (11)

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From this relation and the work of Flory [24], it is possible to derive the shear modulus GCharlesby of the E-CR material:

GCharlesby

RT 1 Fs Mc

1/ 3

(12)

As shown in figure 2, equation (12) does not describe properly the evolution of the shear modulus of E-CR. Ergo, while Charlesbys approach is very convincing for the description of the sol fraction evolution, its Mc calculation cannot aid in predicting the modulus. This is not unexpected since equations (11)-(12) do not take in account the irregularities of the network provoked by the chain scission process. The sol fraction used in equation (12) is not entirely representative of the inactive chains, because the dangling chains do not take part in the network mechanical properties (if entanglement effects are neglected). Moreover the average molar weight between active crosslinks Mc is underestimated: Active chains may include inactive crosslinks, therefore their effective length should be calculated from the length between active crosslinks alone. (Note that the increase predicted by Charlesby is due to the fact that chain scissions first occur in the longest chains which automatically lead to a decrease in Mc.) An accurate prediction of the modulus must include consideration of these aspects.

3.2. Large strain behavior Consequences of irradiation on the mechanical behavior of E-NC and E-CR at large strain are presented on figures 6, 7, and 8 respectively. In agreement with results previously obtained with E-NC (from 0 to 165 kGy), the stress level for a given strain increases. This confirms that the predominant phenomenon taking place is in fact crosslinking. Subsequently, from 165 kGy to 510 kGy, chain scissions predominate, resulting in a decrease in the stress level. Note that the non irradiated E-NC flows in the clamps. This was expected since the testing temperature is much higher than the glass transition temperature of the polymer. This indicates that the entanglements contribution to the stiffness of the irradiated materials can be neglected at 80C. Concerning the rupture behavior, the formation of crosslinks and chain scissions under irradiation does not significantly influence the elongation at break, though the evolution of the stress at break follows the same trend as the evolution of the elastic modulus.

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Figure 6: Large deformation behaviors at 80C of E-NC

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Figure 7: Large strain behaviors at 80C of E-CR

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Figure 8: Average stresses and strains at break for tensile tests at 80C of E-NC and of E-CR Concerning E-CR samples, the evolution of the stress level at a given strain with the irradiation dose is also in agreement with the previous results. However, except with the ECR aged at 50kGy, ageing under irradiation leads to a decrease in the elongation at break and to the disappearance of a strain hardening phenomenon prior to rupture. In figure 9 we compare E-CR2min, E-CR3min, E-NC-165, E-CR-0, 300, and 510. As reported in table 2, though their moduli are comparable, E-CR2min, E-CR3min and E-CR-300 exhibit very different rupture behaviors, the latter having much smaller stress and strain at break. E-CR510 and E-NC-165 also have roughly the same modulus, but the true strains at break are different (with a 2.5 ratio). It seems quite reasonable to conclude that there is no direct correlation between modulus and rupture behavior. The swelling ratios of the same samples are also reported in the same table. They also demonstrate an absence of correlation between Q and the rupture behavior.

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Figure 9: Large deformation behaviors at 80C of irradiated elastomers and of crosslinked rubbers with different curing time In summary, the mechanical measurements at small deformations are in agreement with the swelling measurements, but the evolution of the rupture behavior cannot be explained by a decrease in active chain concentration alone. During ageing the degradation exhibits induced defects such as dangling chains, free chains, and network heterogeneities that may in fact be primarily responsible for the rupture behavior observed. Studies of Mark et al. [11,12] suggest that a large proportion of short chains leads to a brittle behavior. This stresses the need for better characterization of network heterogeneities.

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Table 2: Average stresses and strains at break of materials presented in figure 7 compared to their soluble fraction Fs and their swelling ratio Q

3.3. Network heterogeneity

The network heterogeneity has been characterized by thermoporosimetry. Figure 10 presents the DSC curves of the swollen (in cyclohexane) irradiated E-CR, E-NC-165, E-CR-2min and E-CR-3min. The melting peaks are shifted towards higher temperatures with increasing radiation dose, indicating that the size of solvent pockets increases. With E-NC-165, even though it has the highest modulus of the irradiated E-NC series, the melting peak overlaps the free solvent peak, meaning that the solvent pockets are very large. This is in alignment with the previous results showing that E-NC irradiated is only very slightly crosslinked. Thus for this kind of material, the distribution of pockets sizes cannot be accurately evaluated.

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Figure 10: a) DSC-Analysis of the E-CR-0, 300, 510 and E-NC-165 swelled in cyclohexane, b) Normalized distributions of the solvent pocket sizes I for different materials The distributions of pocket sizes are extracted from the following treatments. The GibbsThomson equation describes the melting temperature of liquids confined into a porous medium Tm [27] as follows: 2 SLTm0 Tm0 Tm (13) L Hf

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where SL is the solid-liquid interface energy, Hf is the bulk heat fusion (6.3 J/g), L refers to the crystal size (here the solvent pocket size), and Tm0 is the melting temperature for the bulk material (i.e. solvent), 0C. The distributions can be obtained by differentiating the equation (13). As SL is unknown, we have expressed these distributions as function of a parameter Lf. Lf is the highest pocket size measured in all the samples. This pocket size corresponds to a melting temperature Tf. M is the sample weight. 2 dH Tm 0 T dM A dT (14) dL Lf With A

1 H f Tm 0 T f

(15)

The results from the analysis are presented in figure 10 b). The normalized distribution of the solvent pocket sizes I is calculated using the following relation:
I 1 dM AM dL (16)

The average size of the solvent pockets as well as their size distribution increases with the radiation dose. Two peaks are visible for the most irradiated material. E-CR3min and ECR2min have a wide distribution of solvent pocket sizes. Thus, an increasing curing time leads to an increase in the crosslink density and a narrower distribution of the chain length in between crosslinks. E-CR2min presents the largest distribution. E-CR3min and E-CR-510 have comparable distributions, even though their mechanical properties are very different. Thus, sole consideration of distribution alone is insufficient to explain rupture behavior. It is noteworthy that E-CR-510 and E-CR3min have a very different sol fraction, 20% and 0% respectively. The sol fraction can be formed of short portions of chains, but also of chain agglomerates which are mechanically inactive. This might very well be the reason behind the difference in mechanical properties of those materials. In order to have more insights on this aspect, a modeling approach of the elastomers architecture is necessary.

3.4. Simulation A model was developed to describe the degradation kinetic of the studied elastomer networks. Similarly to Termonias work [14, 15], this network can be modeled by way of nodes and links, where tetrafunctional nodes describe the elastomer crosslinks, and the links of polymer chain between those nodes. Each link is defined by its ending nodes and its length, i.e. the number of constitutive units, with a unit being assimilated into a monomer. To avoid border effects, periodicity of the network is implemented: The nodes of one edge are linked to the nodes of the opposite edge (see figure 11). A scission reaction corresponds to the statistically random breakage of one unit in the network, meaning that the more probable breakage of the long chains can be accounted for. (Note that the breakage is applied to the chain units and not to the nodes.) In parallel, a calculation is performed to calculate the average length of the dangling chains. This calculation keeps the memory of the length of broken chains so that
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they can be submitted to successive breakages. This enables the calculation of the part of the sol fraction which is due to successive breakages of a link. The second part of the sol fraction is the fraction of the isolated link agglomerates that are not linked to the polymer network. Moreover, the polymer network resulting from the degradation can be seen as a network backbone grafted by a more or less complex branched structure. This network backbone is numerically obtained by iterative elimination of all chains having a free end. This process enables the calculation of the molar mass distribution of the branches either linked or unlinked to the network. The molar mass distribution between active nodes of the chain constituting the clean network backbone is then deduced by considering that the chains are part of the same chain if they are linked to each other by a bifunctional node. In other words, the dangling chains linked to this node are ignored in the calculation of the average molar mass of the active network.

Figure 11: Scheme of model network The model parameters are the number of nodes, the molar distribution of the links (i.e. the distribution of their number of units), and the number of scissions. Calculations were performed with 4900 nodes (9800 links). In order to check and improve the statistic, six simulations were perfromed and the results presented are the average of these. Moreover, it

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has been checked that the use of only 625 nodes gives the same mean estimations, but with a larger standard deviation. The presented model does not include any crosslinking process. The latter can be considered by increasing the initial crosslink density of the network submitted to the degradation kinetic. As shown previously, E-CR degradation primarily consists of chain scissions, except during the first stage of degradation, where slight crosslinking occurs. Therefore, one can consider the degradation kinetic of this material as the chain scission process of an E-CR initially slightly more crosslinked than the real initial material. From the previous extrapolation at 0kGy of the modulus (cf. figure 3), we consider an initial average chain length between crosslinks Nc of 66 units. So this model accounts for a total of 646800 units (66 x 9800). Additionally, the calculation needs the knowledge of the distribution of the number of units between crosslinks in the initial material. The crosslinking process is initiated by peroxide. The latter is assumed to be randomly distributed in the unlinked EPDM. This means that the crosslinking can be assumed to occur between chains with the conformational state following the Gaussian statistic. Thus, the probability P(r) for the distance between two crosslinks having a distance r will obey:
P(r ) 4 r2 2/3 r2
3/ 2

exp

3r 2 2 r2

(17)

with

r 2 being the average distance between two crosslinks given by:


r2 CEPDM Nc b2 (18)

where CEPDM (CEPDM = 6.4) is the EPDM characteristic ratio, which in turn is an average value of the characteristic ratio of the polyethylene and the polypropylene (CPE = 6.8 and CPP = 5.5 [31]). b is the length of the monomer unit of EPDM, which in this case is the same as polyethylene: b = 0.308 nm. In our case, Rc is determined to be 13 nm. Figure 12 presents the calculated evolution of the total sol fraction, and of the sol fraction made of chains containing at least two nodes and considered to be free chain agglomerates, versus the number of scissions per the initial total number of units Ns. As we expect, the calculation indicates that the sol fraction at the beginning of the degradation process is mainly comprised of chain portions coming from dangling chains. As the number of scissions increases, free chain agglomerates rapidly become significant in the sol fraction: for 20% of soluble fraction, 9.2% is comprised of free chain agglomerates.

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Figure 12: Calculated total sol fraction, free chain agglomerate fraction and average molar mass between crosslinks as a function of the number chain scissions per unit (calculation performed with an initial average length of active chains of 66 units) The calculations also predict the molar mass, and the number of free chain agglomerates and branches (belonging to the backbone) (cf. Figure 13) [24]. The scissions lead to a rapid increase in the number of branches followed by a stabilization for a number of chain scissions per unit around 10-2. At this level of damage, a large number of branches become separated from the network backbone and end up as free chain agglomerates. However, both types of agglomerates show an increase in size.

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Figure 13: Size and number per unit of the free agglomerates and of branches grafted to backbone as a function of the number of chain scission per unit Ns obtained from simulation at a given sol fraction can be compared to the experimental results from the same sol fraction required to extract an equivalent radiation dose. Figure 5 shows a non-linear relationship at the beginning of the crosslinking process. Conversely, a linear relationship is evidenced above 50 kGy. The deduced slope, equal to 1.2x10-8 scission per unit per gray enables to us to estimate a chain scission yield. It is found a Gs-sim equals 3.9x10-7 mol/J. This value is very close to that deduced from the Charlesbys model. Thus, this numerical model is roughly equivalent to the Charlesbys one for radiation doses above 50 kGy. The very high scission value needed at the beginning of the simulated degradation process in order to obtain the correct sol fraction value is due to the fact that the initial simulated network does not contain any dangling chains, in contrast to Charlesbys approach, which implicitly assumes their presence. Thus, the formation of sol fraction from such a network needs first the scission of chains, prior to the formation of soluble chains arising from the created dangling chains. Once such a process has been taken into account by a large initial scission kinetic, it can be considered, for sufficiently high dose (above 50 kGy), that the network characteristics simulated by our approach are roughly similar to those of the network modeled by Charlesbys approach. From the calculated average molar mass Lav (expressed in unit number) of the network backbone, an average network density can be deduced, and ultimately the modulus of the calculated network (using the relation (12)) [24]:

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Gsim RT FBackbone wLav
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(19)

FBackbone is the fraction of active chain in the gel. This means that we assume here that the dangling chains of the backbone are considered to form part of the soluble chains.

Figure 14: Normalized distribution of chain lengths calculated for E-CR as a function of irradiation dose (for a volume of 689000 units, results average of six calculation runs) Figure 2 presents the modulus Gsim deduced from the simulation as a function of the radiation dose. As seen on the same figure, the simulated results correctly reproduce the modulus decrease. Note that there is an underestimation of around 20% between the calculated result and the experimental data in the dose range [50 kGy- 400 kGy]. This can be easily explained by the uncertainty in the initial crosslink density of the material. Actually, this value is probably underestimated since it is calculated with the assumption of no dangling chains; the real material necessarily contains these dangling chains. Whatever the radiation dose, making the assumption that the material at doses greater than or equal to 50kG is correctly simulated, the calculation indicates that around 20% of the gel is comprised of dangling chains. It is reasonable to consider that their content in the non-irradiated material is of the same order. As discussed in several studies [10,31,32], a presence of dangling chains in a network results in a reduction of the active chain concentration. Actually their effect is complex: Dusek et al. [33] or Mark et al. [10] have shown that they act as a kind of diluent which is however less mobile than a low-molar-weight compound or sol. Therefore, the crosslink density, and thus the
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average number of units in between crosslinks of non-irradiated material used in the calculation (deduced from the modulus extrapolation at 0 kGy with an assumption of 0% sol fraction) is likely underestimated by 10-20%. Such a correction would lead to a very good model of the modulus evolution of E-CR.

Figure 14 shows the simulation of the distribution of the molar mass between active crosslinks in the E-CR degraded network for the different radiation doses. As expected, chain scissions lead to the appearance of supplementary peaks centered on values equal to multiples of the initial average length of the chain in the E-CR network. Thus this simplified model correctly accounts for the trends observed in thermoporosimetry: an increase in the average molar mass between crosslinks of the network, an increase in their distribution width towards the larger length, and the appearance of a modulation of the distribution.

4. Discussion The decrease in the average crosslink density should increase the strain at break of the E-CR. This is experimentally observed in the case of less crosslinked E-CR2min and E-CR3min. Indeed, compared to virgin E-CR, these samples have a larger strain at break correlated to their average crosslink density deduced from modulus measurement. Conversely, for irradiated E-CR, the average crosslink density decreases while the strain and stress at break decrease. Therefore the average crosslink density is not the only pertinent parameter required to predict rupture behavior: One must also consider the architecture of the network. The decrease in homogeneity of the network can be evaluated from the experimental results of thermoporosimetry, which are qualitatively in agreement with the calculated distribution of the average molar mass between active nodes. However it is noteworthy that E-CR3min and E-CR-300 have similar elastic modulus at 80C and the same results in thermoporosimetry (i.e. a similar distribution of elastic network heterogeneity), whereas their rupture behavior is very different. The main difference between these materials is the sol fraction. The calculations have shown that this sol fraction contains more and more free chain agglomerates as radiation dose increases. Simultaneously, degradation leads to creation of larger and larger branches grafted to the network backbone. Thus the network architecture becomes very irregular. This means that the network contains an increasing number of weakened zones, which can lead to crack initiation. This phenomenon is concomitant with an increase in the average length of the active chains of the network. However, given the distributed character of these chain lengths, the elongation at break is likely controlled by the shortest chains, percolating through the whole sample. Thermoporosimetry and calculations clearly show the modification of the initial distribution into a multimodal one, in which the fundamental mode corresponds to the initial population. At the start of the degradation process, this population controls the elongation at break, while obviously at elevated radiation doses, the memory of this population vanishes while longer populations lead to an increase in elongation at break. By appreciating these mechanisms, one can propose an underlying cause for the rupture behavior of all the samples. The elongation and stress at break of E-CR first decrease with radiation doses, because of the more numerous weak crosslinks in the network. Up to 300 kGy, this effect is insufficiently
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counterbalanced by the increase in the average chain length in the network, since the network is still mainly constituted of the initial population of chains. On the other hand, the slight increase in the strain at break observed in the case of the most irradiated sample (E-CR-510) might be due to the degradation being severe enough to completely destroy the percolation of these initial chains. In the case of E-NC, the evolution of the rupture behavior with radiation dose is the result of the concomitant crosslinking and bond-breaking processes. Unfortunately, the same simulation approach cannot be similarly applied to E-NC due to the important crosslinking process occurring in the same time as the chain scission one. However, the irradiated materials can be envisioned as an initial network whose the stress and strain at break is controlled by an initial average length, one which decreases with the radiation dose, submitted to a degradation processes which creates large free agglomerates. Thus, the E-NC-50 is a loose network, with an expected large strain at break, but with a large sol fraction, having numerous weakened zones, which decrease the strain at break. Then further irradiation leads to more crosslinks in the initial network, which would be expected to decrease the strain at break, although kept in check by the chain scissions. Thus, at higher doses, the irradiated material can be seen as an initially crosslinked network with an average mass between crosslinks larger than that of the E-CR-0 network. This should lead to a strain at break much larger than that of this material. But the presence of sol fraction, i.e. of weakened links, leads to a decrease in strain at break to a smaller value, which is still above E-NC-510.

5. Conclusions Different EPDM elastomers with different crosslink densities were processed in order to evaluate the influence of gamma irradiation on their properties. Depending on the initial crosslink density of sample, irradiation can lead to supplementary crosslinking of polymer chains. This mechanism is important for initial unlinked sample. For samples with initial high crosslink density, this mechanism also occurs at the lowest radiation doses and becomes negligible at high doses, where chain scissions mainly occur. These different phenomena are correctly accounted for by the Charlesby-Pinner modeling approach for doses equal or above 50kGy. This model indicates that, within the experimental conditions of our study, the chain scission mechanism involved in the degradation of the crosslinked EPDM is proportional to the radiation dose. In the case of the initially unlinked EDPM, the experimental results at high radiation doses suggests that the scission mechanism follow the same kinetic, i.e. a proportionality between scission and radiation dose. Assuming such a scission kinetic, a crosslinking kinetic can be estimated, and is found to be not proportional to the radiation dose. This mechanism saturates when the crosslinking density is close to that estimated for nonirradiated crosslinked EPDM. This suggests that the crosslinking mechanism should be very similar to that induced by either irradiation or by chemical (peroxide) curing. Concerning the initially crosslinked material, the consequences of the chain scissions are a decrease in the modulus of elasticity, but also in the strain at break. This behavior is opposite to that expected for materials with increasing average chain length between crosslinks. This surprising phenomenon is attributed to the presence of defects in network. Thermoporosimetry measurements were performed to characterize these defects, in particular the distribution of the average molar mass between crosslinks. They show an increase in the distribution towards longer chains with increasing radiation dose, and for the highest radiation
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doses studied, a multimodal distribution. However, the experimental distributions found in the case of virgin networks with low crosslink density is much larger than that obtained with the most irradiated material, whereas their strains at break are more elevated than that observed for the aged sample. Thus it seems that the type of heterogeneity evidenced by such measurement cannot fully explain the evolution of the rupture behavior under ageing. To produce new insights, a model has been developed enabling simulation of the chain scission mechanism of an elastomer network. It successfully enables prediction of the evolution of the elastic modulus of the material, based on an estimation of average chain length between active crosslinks. The appearance of the multimodality of the average molar mass between crosslink distributions for high radiation doses is also predicted. This model furthermore predicts the proportion of free chains, of free chain agglomerates and of branches linked to the network backbone. From this information on the evolution of the network architecture, two key parameters have been identified for the rupture behavior and its evolution with ageing. The first is the average molar mass between crosslinks, which controls the rupture of a network in the absence of defects. The second is the proportion of weakened zones comprised of large free agglomerates, and large branched chains in the mechanically active network backbone, which degrade the rupture property.

Acknowledgements It is a pleasure to acknowledge the joint research program COPOLA between EDF, NEXANS France, LABORELEC, CEA, INRA and CNRS. The authors also thank J.C. Majeste for GPC analyses, Cedric Lorthioir for helpful discussions and Julian de Marchi for corrections of the english.

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1. RIVATON A, CAMBON S, GARDETTE JL. Nuclear Instruments and Methods in Physics Research B 2005; 227: 343-356 2. RIVATON A, CAMBON S, GARDETTE JL. Nuclear Instruments and Methods in Physics Research B 2005; 227: 357-368 3. CELETTE N, STEVENSON I, DAVENAS J, DAVID L, VIGIER G. Nuclear Instruments and Methods in Physics Research B 2001; 185: 305-310 4. CELETTE N, STEVENSON I, DAVID L, VIGIER G, SEYTRE G. Polymer International 2004; 53: 495-505 5. ASSINK RA, GILLEN KT, SANDERSON B. Polymer 2002; 43:1349-1355 6. CELINA M, GILLEN KT, WISE J, CLOUGH RL. Radiation Physics and Chemistry 1996; 48:613-626 7. ASSINK RA, CELINA M, GILLEN KT, CLOUGH RL, ALAM TM. Polymer Degradation and Stability 2001; 73:355-362 8. BATEJA SK. Journal of Applied Polymer Science 1983; 28:861-872 9. PLANES E, CHAZEAU L, VIGIER G, CHENAL JM, STUHLDREIER T. Submitted to Polymer 2009 10. ANDRADY AL, LLORENTE MA, SHARAF MA, RAHALKAR RR, MARK JE. Journal of Applied Polymer Science 1981; 26: 1829-1836 11. MARK JE, TANG MY. Journal of Polymer Science: Polymer Physics Edition 1984; 22: 1849-1855 12. LLORENTE MA, ANDRADY AL, MARK JE. Journal of Polymer Science 1981; 19: 621-630 13. MADKOUR T, MARK JE. Polymer Bulletin 1993; 31: 615-621 14. TERMONIA Y. Macromolecules 1989; 22:3633-3638 15. TERMONIA Y. Macromolecules 1990; 23:1481-1483 16. GREST GS, KREMER K. Macromolecules 1990; 23: 4994-5000 17. CHARLESBY A, PINNER SH. Proc. Roy. Soc. Lond. 1959; A249:367-386 18. CHARLESBY A. Proc. Roy. Soc. Lond. 1954 A222:542-557 19. ROTTACH DR, CURRO JG, GREST GS, THOMPSON AP. Macromolecules 2004; 37:5468-5473 20. ROTTACH DR, CURRO JG, BUDZIEN J, GREST GS, SVANEBORG C, EVERAERS R. Macromolecules 2006; 39:5521-5530 21. ROTTACH DR, CURRO JG, BUDZIEN J, GREST GS, SVANEBORG C, EVERAERS R. Macromolecules 2007; 40:131-139 22. VALLAT MF, RUCH F, DAVID MO. European Polymer Journal 2004; 40: 1575-1586 23. ORZA RA, MAGUSIN PCMM, LITVINOV VM, VAN DUIN M, MICHELS MAJ. Macromolecules 2007; 40: 8999-9008 24. FLORY PJ, REHNER J. Journal of Chemical Physics, 1943; 11: 521-526 25. VALENTIN JL, CARRETO-GONZALEZ J, MORA-BARRANTES I, CHASSE W, SAALWACHTER K. Macromolecules 2007; 11: 4717-4729 26. HONIBALL D, HUSON MG, MCGILL WJ. Journal of Polymer Science: Part B: Polymer Physics 1988; 26: 2413 31 27. QIN Q, MC KENNA GB. Journal of Polymer Science: Part B: Polymer Physics 2006; 44: 3475 3486 28. KHELIDJ N, COLIN X, AUDOUIN L, VERDU J, MONCHY-LEROY C, PRUNIER V. Polymer Degradation and Stability 2006; 91(7):1593-1597 29. DECKER C, MAYO FR, RICHARDSON H. Journal of Polymer Science: Polymer Chemistry Edition 1973; 11: 2879-2898
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30. COLIN X, RICHAUD E, VERDU J, MONCHY-LEROY C. Conference IRAP 2008, Kinetic modelling of radiochemical ageing of ethylene-propylene copolymers Submitted to Radiation Physics and Chemistry 31. SPERLING LH. Introduction to physical polymer science - Second edition. Wiley interscience, 1992. 32. VILLAR MA, VALLES EM. Macromolecules 1996; 29: 4081-4089

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Ces complments concernent uniquement le matriau E-NC. Tout dabord, nous montrerons comment appliquer la thorie de Charlesby-Pinner pour ce matriau. Puis nous prsenterons les rsultats obtenus partir du modle labor dans larticle pour le matriau non rticul E-NC.

1. Utilisation de la thorie Charlesby-Pinner pour le matriau E-NC La thorie de Charlesby-Pinner peut tre utilise pour le matriau E-NC. En utilisant la mme cintique de coupures de chanes dtermine p(D) pour le matriau E-CR, il est possible de dterminer la cintique de rticulation q(D) pour le matriau E-NC partir de la relation suivante :
q( D) p0 D 1/ u1 Fs ( D) Fs ( D) 1

0,012 Cintique de rticulation q(D) 0,01 0,008 0,006 0,004 0,002 0 0 100 200 300 Dose (kGy) Dduite de Charlesby Fit Dduite de l'extrapolation 400 500 600

Gc=1.15x10-6 mol/J

GC-Charlesby = 6.2x10-7 mol/J

Figure 1 : Evolution de la cintique de rticulation q(D) en fonction de la dose dirradiation dduite de Charlesby et de lextrapolation La figure 1 prsente la cintique de rticulation dduite pour le matriau E-NC. Cette cintique peut tre facilement fitte par la loi suivante :
q( D) qc 1 exp 2 Gc
Charlesby

qc

qc est gal 0.013, ce qui correspond un nombre moyen dunits entre nuds de 76 et une concentration de chanes actives de 3.6x10-4 mol/cm3. Ainsi ce niveau de rticulation obtenu par irradiation est vraiment proche de celui dtermin pour le matriau initial E-CR. Ceci suggre que le nombre potentiel de sites actifs pour la rticulation est le mme quelque soit le mode de rticulation (irradiation ou chimique). Le rendement de rticulation GC-Charlesby peut
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tre dtermin partir de la pente lorigine, soit 6.2x10-7 mol/J. Cette valeur est vraiment trs proche de celle obtenue par extrapolation (1.15x10-6 mol/J). De plus comme pour le matriau E-CR, il est possible destimer la dose correspondant la dgradation complte, la valeur trouve est 1500 kGy.

2. Rsultats de simulation supplmentaires pour le matriau E-NC La mme simulation peut tre applique au matriau E-NC : la seule difficult est la prise en compte du phnomne de rticulation, qui a lieu en mme temps que le phnomne de scissions de chanes. Cependant, comme lapproche de Charlesby, ce modle peut fournir des informations sur le processus de dgradation mis en jeu lors du vieillissement par irradiation et en particulier sur les rles respectifs des phnomnes de scissions de chanes et de rticulation. Pour cela, diffrentes hypothses sont ncessaires. Notre premire hypothse est que les phnomnes de rticulation et de scissions sont indpendants les uns des autres. Notre seconde hypothse est que le nombre de scissions de chanes par unit Ns dans lchantillon E-NC est le mme que pour le matriau E-CR. De plus, le matriau E-NC est suppos chaque dose comme tre le rsultat des coupures de chanes dun rseau fictif totalement rticul avec aucune fraction soluble. La densit de rticulation de ce matriau fictif est dduite de la simulation, puisque cette dernire permet une relation directe entre lvolution de la densit de rticulation et celle de la fraction soluble. Cette dduction est fournie en ngligeant linfluence de la distribution de la longueur des chanes entre nuds. A partir de cette approche, nous pouvons aussi dduire un nombre de coupures de chanes fictif Nsf qui est ncessaire pour obtenir le matriau rsultant partir du matriau fictif. Ainsi la densit de rticulation et la fraction soluble du matriau E-NC avant dtre soumis au phnomne de scissions de chanes peuvent tre dduites chaque dose par la modlisation des coupures de chanes du matriau fictif initial par le nombre de coupures de chanes par unit Nsf-Ns. Les diffrentes valeurs dduites de ce calcul sont reportes dans la table 1. De plus, cette table prsente la masse molaire moyenne entre nuds et la fraction soluble du matriau E-NC avant et aprs les coupures de chanes. Les calculs confirment que le processus de rticulation pendant la dgradation du matriau conduit hautes doses sans le phnomne de scissions de chanes, une rticulation totale du matriau (i.e. avec aucune fraction soluble) avec une masse molaire moyenne entre nuds de 100 units. Il faut noter que cette valeur est 30% plus leve que celle calcule par lapproche de Charlesby, mais tant donn les diffrentes hypothses du calcul, ceci peut tre considr comme satisfaisant.

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Table 1: Valeurs dduites de la simulation pour la cintique de dgradation du matriau ENC

Figure 2: Distributions normalises des longueurs de chanes entre noeuds pour a) le matriau E-CR et pour b) le matriau E-NC (pour un volume de 689000 units, rsultats moyenns sur 6 calculs) De plus, la figure 2 montre la simulation de la distribution de la masse molaire entre nuds actifs du rseau dgrad du matriau E-CR pour les diffrentes doses dirradiation. Comme attendu, les coupures de chanes conduisent lapparition de pics supplmentaires centrs sur les multiples de la longueur moyenne entre nuds initiale du rseau E-CR. Donc ce modle simplifi permet de rendre compte de la tendance observe en thermoporosimtrie : une augmentation de la masse molaire moyenne entre nuds, une augmentation de la largeur de la distribution des longueurs entre nuds du rseau, et lapparition dune distribution bimodale hautes doses dirradiation. Pour llastomre E-NC, tant donn la raction de rticulation ayant lieu dans ce matriau pendant sa dgradation sous irradiation, le calcul, avec les hypothses faites pralablement, montre une distribution des longueurs entre nuds plus large pour la dose 50
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kGy que pour les autres doses dirradiation (cf. Figure 2). Ceci correspond une prsence plus importante dagglomrats de chanes libres et de branches greffes. Dans le cas du matriau EPDM non rticul initialement, lvolution du comportement la rupture avec la dose dirradiation est le rsultat du processus concomitant des phnomnes de rticulation et de scissions de chanes. Les matriaux irradis peuvent tre envisags comme un rseau initial, dont la contrainte et la dformation la rupture sont contrles par la longueur moyenne initiale entre nuds (celle dduite du calcul, i.e. qui diminue avec la dose dirradiation), soumis un processus de dgradation qui cre dimportants agglomrats libres. Donc, le matriau E-NC-50 constitue un rseau trs dgrad, avec une grande dformation la rupture attendue, mais avec une importante fraction soluble, avec de nombreuses zones fragilises, qui ont pour consquences de diminuer lallongement la rupture (cf. Figure 6 article). Ensuite, lirradiation conduit un degr de rticulation plus lev du rseau initial, ce qui induit une diminution de lallongement la rupture, mais cet effet est contrebalanc par les scissions de chanes. Donc, hautes doses dirradiation, le matriau irradi peut tre considr comme un rseau initial avec une longueur moyenne entre nuds voisine de 100 units (cf. Table 1), i.e. 50% plus leve que celle estime que pour le matriau E-CR-0. Ceci devrait conduire une dformation la rupture plus leve que celle observe pour le matriau E-CR-0. Mais la prsence de fraction soluble induisant lexistence de liens fragiles au sein du matriau conduit une diminution de lallongement la rupture (cf. Figure 6 article).

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Article 2

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Article 2: Crystalline microstructure and mechanical properties of crosslinked EPDM aged under gamma irradiation
PLANES E., CHAZEAU L., VIGIER G., CHENAL J.M., STUHLDREIER T. (accept dans Journal of Polymer Science : Part B Polymer Physics)

Sommaire
Abstract .............................................................................................................................................. 121 1. 2. Introduction ............................................................................................................................... 121 Experimental.............................................................................................................................. 123 2.1. 2.2. 2.3. Materials .............................................................................................................................. 123 Irradiation conditions .......................................................................................................... 123 Instruments .......................................................................................................................... 123 Tensile tests ................................................................................................................. 123 Differential scanning calorimetry ................................................................................ 124 SAXS measurements ................................................................................................... 125 In-situ SAXS measurements during stretching ....................................................... 127

2.3.1. 2.3.2. 2.3.3. 2.3.3.1. 3.

Results & Discussions ................................................................................................................ 127 3.1. 3.2. 3.3. Microstructure of unaged sample and undeformed sample ................................................. 127 Microstructure evolution during stretching of unaged samples .......................................... 132 Consequences of gamma irradiation ................................................................................... 135

4.

Conclusions ................................................................................................................................ 137

Acknowledgments.............................................................................................................................. 138 References .......................................................................................................................................... 139

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Aprs avoir tudi les consquences du vieillissement sur la phase amorphe de lEPDM, nous nous intressons dans ce deuxime article aux proprits de ces mmes matriaux irradis ltat semi-cristallin (i.e. temprature ambiante). La comprhension de ces proprits a ncessit une caractrisation fine de la microstructure semi-cristalline. Elle est galement prsente de mme que son volution avec lirradiation.

Abstract The morphology and the mechanical properties at room temperature of crosslinked EPDM irradiated or not have been studied. It has been shown that these materials are composed of two phases: semi-crystalline zones with a crystallinity ratio of 20% and mainly amorphous zones. The semi-crystalline zones percolate through the film and therefore control the mechanical properties of the material below the melting temperature. As irradiation (in the tested range of irradiation dose) and crosslinking degree have no significant influence on the arrangement and proportion of the crystalline lamellae, all samples have nearly the same mechanical behavior at small strains. At large strains, the interactions between amorphous and crystalline parts in semi-crystalline zones play the main role in the mechanical response; irradiation, by degradation of these interactions, leads to a smaller hardening phenomenon and a decrease in elongation at break. From an application point of view, in spite of the low crystallinity fraction of these materials, the presence of an important number of crystallites, as evidenced by SAXS measurements, strongly limits the consequences of irradiation on the mechanical properties. However the mechanical reinforcement strongly depending on the presence of these crystallites, it is therefore highly sensitive to temperature: this can be an important issue for these materials applications since their use temperature is close to the crystallite melting temperature.

1. Introduction

Polymers are in some cases used in environments where they may be exposed to high-energy radiation, for instance, in nuclear power plants. Over the years, the effects of high-energy radiation on polyethylene have been extensively studied [1, 2, 3, 4, 5]. Irradiation causes important changes that often occur simultaneously, that is crosslinking and chain scissions. Many factors such as the polyethylene (PE) type, the absorbed dose, and irradiation conditions - temperature, dose rate, and the irradiation atmosphere - largely influence these processes. Given the semi-crystalline nature of polyethylene, the influence of the crystalline morphology on the irradiation mechanism and its evolution during this irradiation are issues to also consider. Although crystallites can also be sensitive to gamma irradiation, the polymer parts mainly affected by the degradation are in the amorphous state, because of the weak permeability of oxygen in crystallites [3]. Thus, the crystalline part of the material essentially influences the degradation intensity by reducing the polymer fraction concerned by the degradation mechanism, i.e. the amorphous one. Nevertheless, Bateja [2] has reported that
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with an increasing radiation dose (at relatively small doses) in the open air, the degree of crystallinity of polyethylene increases. Indeed, chain scissions in the amorphous regions can create small chains which can crystallize at temperature lower than the cristallisation temperature of the unaged polymer. Therefore, the crystalline part, if not involved in the degradation mechanisms, seems to be involved in the structural evolution of the material during/after degradation. Ethylene-Propylene-Diene monomer elastomer (EPDM) is usually preferred to PE for cable application. Like PE, it is a semi-crystalline matrix, the crystallinity level of which depends on its content of ethylene monomer entities. An usual ethylene content of 70% leads to a crystallinity level of around 10% [6]. This is much less than common linear polyethylene in which the crystallites represent the major part of the material. This means a material more sensitive to irradiation [7]. Indeed, as the crystallite thickness is very small, this leads to melting temperature which can be relatively low and closer to the room temperature, and therefore to the temperature at which irradiation is usually performed. Such crystalline morphology is of main importance in the mechanical properties of the polymer. Indeed, Celette et al. [5] have shown that the semi crystalline nature of EPDM at room temperature strongly attenuates the effect of degradation. In spite of a large degradation of the polymer evidenced above the melting temperature, they found only small difference in properties when measured at room temperature. This suggested few modifications of the crystalline phase during irradiation. However, it was not demonstrated by a microstructural characterization of the material. Thus, the aim of this work is to relate the microstructural modifications induced by irradiation to the mechanical properties of the material, those including the stiffness and the ultimate properties. The degradation mechanisms of the studied materials have been presented in a previous paper [7]: EPDM elastomers have been aged by gamma irradiation at room temperature under oxygen atmosphere and their mechanical properties have been studied at 80C. Except a crosslinking process in its early stage of degradation, the latter mainly consists of chain scission whose the consequences are a decrease in the modulus and more generally in the material stiffness, and a degradation of the ultimate properties. Moreover, the rupture behavior can be related to the initial crosslink density (as far as the degradation mechanism has not totally destroyed all the shortest chains) and the sol fraction, this one including at high irradiation doses, portion of active chains and free agglomerates of initially active chains. Thus, this article completes such results by a study of the mechanical properties and microstructure of the material at room temperature, i.e. below the melting temperature, as a function of the irradiation dose.

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2. Experimental 2.1. Materials

The studied EPDM elastomer is a statistic copolymer and is composed of 70% ethylene, 29.5% propylene and 0.5% ethylenedienenorbornene (ENB). An analysis by size exclusion chromatography (SEC) gave the following results: Mw 39300g/mol, Mn 5140 g/mol and Ip=7.65. The samples are processed following three steps. The first step is the mixing of the matrix and the incorporation of crosslinking agent in the polymer. First the matrix is introduced in the internal mixer. After 5 minutes of mixing, 3 phr of dicumyl peroxide (Perkadox BC-FF from Akzo Nobel) are added: its mixing is performed for 10 min at low temperature (80C) to prevent any reaction of the crosslinking system. In order to obtain a better dispersion, the second step is the mixing in an external mixer (cylinders) for 10 min at low temperature (80C). During the last step, the compound is pressed as 1-mm-thick films at 170C during 10 minutes to promote crosslinking reaction. The curing time (t98 at 170C) is determined from torque measurement performed with a MOSANTO analyzer. Two types of EPDM materials have been processed: uncrosslinked and crosslinled ones. They will be called hereafter E-NC and E-CR materials respectively. An EPDM elastomer has also been processed with a smaller curing time, 2 min, to obtain a material with a lower crosslinking degree. It will be called hereafter E-CR2min.

2.2. Irradiation conditions

E-CR samples are exposed to -radiation of a 60CO source at a dose rate of 1 kGy/h in an oxygen atmosphere for doses 50, 165, 300, 510 kGy (Arc Nucleart Grenoble France): the water temperature of the pool, where exposures are performed, is around 18C. Afterwards, the samples are stored under vacuum at about 22C. The samples will be named hereafter ECR-XXX with XXX the irradiation dose.

2.3. Instruments 2.3.1. Tensile tests

Tensile tests are performed with an MTS 1/ME device equipped with a temperature controlled chamber. An image processing acquisition system (Apollor VideoTraction System) is used to obtain true stress-true strain curves. Experiments are conducted at 25C with a true strain rate 0.01 s-1. Three specimens are tested for each material. The samples are dumbbell-shaped with gauge dimensions 20 x 4 x 1 mm3. On figures only one test is reported, but another figure with the average stresses and strains at break of the three specimens and error bars is also presented. The elastic modulus E at 25C and at 80C is calculated as the slope at the origin of the true strain-true stress curve.

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2.3.2. Differential scanning calorimetry

All measurements are made with a Perkin-Elmer Diamond calorimeter, with 7-8 mg of material encapsulated in standard aluminum pans. Dry nitrogen is used as the purge gas. The instrument is calibrated with indium using a scan rate corresponding to the heating rate of the experiments. The crystallization temperature domain of our EPDM is large [6]: from about -40C up to 60C. Indeed, when the polymer is cooled from 80C to -50C, one wide peak can be observed during the heating ramp, as shown in scheme 1 a). If an isothermal treatment of several hours at the temperature Tc is performed during cooling, three melting peaks are obtained during the heating scan (cf. figure 1 b)): One, which corresponds to the crystallite population formed during cooling from 80C to Tc. A second one, which concerns the crystallite population formed during the isothermal treatment at Tc. And a third one, which corresponds to the crystallite population, created during the cooling from Tc to -40C. Test series have been performed to evaluate the optimal crystallization temperature, i.e. the temperature Tc which leads to the highest crystallinity ratio with the fastest crystallization kinetic. The optimized isothermal treatment for 12h at 22C enabled generating stable cristallinity. Thus, the thermal treatment applied to all samples is the following (cf. figure 1 c)): A heating ramp up to 80C to erase the thermal history A rapid cooling down at 50C/min to the optimal crystallization temperature 22C and storage during 12h at this temperature Moreover, in order not to affect the crystallinity by any further treatments around this temperature, in particular during the ageing in the irradiation pool at 18C, and the storage at 22C after irradiation, the samples are annealed by a heating ramp at 1C/min up to 38C and maintained at this temperature during 6h. Then they are cooled down to 22C and stored at this same temperature. This treatment enables to get a crystallite population with a well defined peak with a melting temperature above 22C. To study the materials cristallinity after their irradiation, samples are cooled from room temperature down to 50C at the cooling rate of 10C/min and heated up to 100C at 10C/min. The cooling from room temperature to -50C is necessary to avoid the overlap of the DSC starting overshoot with the melting peaks. But this cooling induces supplementary crystallization and the formation of an additional melting peak, which can be observed between -40C and 20C. Therefore, the weight crystallinity ratio Xcw is defined from enthalpy of the melting peaks between 22C and 60C Hf. Hf X cw 1 Hf0 Hf0 is taken equal to 290 J/g [8], which is the value for perfect polyethylene crystal, since it is assumed that only polyethylene segments can crystallize. This weight crystallinity ratio can be converted in volume crystallinity ratio Xcv using the density value of the crystalline polyethylene (1.006 g/cm3 [8]) and the amorphous part of this copolymer. The latter is estimated from the amorphous polyethylene (0.855 g/cm3 [8]) and amorphous polypropylene (0.854 g/cm3 [8]) densities and is taken equal to 0.855 g/cm3.

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Figure 1: Crystallization and melting DSC curves of EPDM

2.3.3. SAXS measurements

Small-Angle X-ray Scattering (SAXS) are carried out on a device equipped with a copper rotating anode ( = 1.54 ) with Gobels mirror point collimation system and 2D detector (Princeton Instrument SCX2D). The scattering vector domain is deduced from the detectorsample distance. The scattering vector is directly correlated to the scattering angle 2 and the wavelength :

q 4 sin 2 In our experiments, the detector-sample distance is fixed at 1160mm and the corresponding q domain is: 0.01 to 0.08 nm-1. The patterns are acquired during 5 minutes for SAXS measurements and they are corrected from background scattering and thickness.

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Figure 2: SAXS patterns of E-CR-0 during stretching: a)unstretched b)at 0.9 true strain

From SAXS patterns (cf. Figure 2), the long period LPB characteristic of the regular stacking of crystal blocks and amorphous layers can be evaluated. Using Braggs law and the position of the maximum qmax, LPB is calculated following: 2 LPB 3 qmax LPB represents the sum of the average thickness of the crystal lamellae lc, and of the interlamellar amorphous areas la. This method does not directly provide any values for la or lc. The correlation function is used in order to obtain the structural parameters: la, lc. Linear correlation function is calculated by a cosine transformation of the intensity curves I(q) [9, 10].
I (q)q 2 cos(qr )dq (r )
0

4 I (q)q dq
0 2

where r represents the distance in real space. In practice, data are not recorded from zero to infinity but over a restricted q-range. Therefore, the procedure of integration to infinity involves the use of a polynomial extrapolation in the scattering region of the beamstop, i.e. at low scattering angle, such as:

I (q) Aq 5 And at large scattering angles, the data are extrapolated with the Porods law: B C I (q) 6 q2 q4
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where B and C represent the interface quality and the Porod constant respectively[11]. From the correlation function, in addition to the LPB values obtained from Lorentz corrected SAXS profile, another estimation of this parameter, called hereafter LPC, can be performed from the position of the first maximum of the correlation function. Moreover a volume crystallinity ratio can be obtained from this curve.

2.3.3.1.

In-situ SAXS measurements during stretching

A homemade stretching machine allowing the symmetric deformation of the sample was used to probe by X-ray the same sample area during stretching at 0.04 min-1 strain rate and at room temperature. The two-dimensional (2D) SAXS patterns were recorded every 5min. The long periods in the stretching direction and perpendicular to the stretching direction were computed by a radial integration of the 2D SAXS patterns over sectors of 20 around the meridian and the equator, i.e. the directions parallel and normal to the tensile axis (cf. figure 2). 3. Results & Discussions 3.1. Microstructure of unaged sample and undeformed sample

The crystalline phase of E-CR is characterized by DSC. The curves are presented in figure 3. The melting peak located at 45C is very large. This indicates crystals with a large thickness distribution that would be due to the broad sequence distribution of ethylene moiety along the polymer chain. Moreover the position of the melting peak is similar for E-CR and E-CR2min. The melting peak of E-NC is larger and depressed by 2C with regard to the others materials. Given the measurements uncertainties of 0.2%, the weak difference of crystallinity ratio found for the different materials are significant. The volume crystallinity datas reported in table 1 are 9.1%, 9.8%, and 10.7% for E-CR, E-CR2min and E-NC respectivel These ratios are correlated to the crosslink density of materials: the less crosslinked the rubber, the higher the crystallinity. This was expected since it is known that crosslinks hinder the crystallization growth [12]. Following the literature [13, 14], this crystallinity ratio should correspond to a fringed micelles morphology. To have more insights on the morphology, SAXS experiments have been performed.

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Figure 3: DSC analyses for the studied materials


Sample name E-CR-0 E-CR-50 E-CR-165 E-CR-300 E-CR-510 E-CR2min E-NC Xcw(%) 0.2 10.6 10.3 10.4 11.9 10.9 11.4 12.4 Xcv(%) 0.2 9.1 8.9 9 10.3 9.4 9.8 10.7 Tf1/Tf2 (C) 45 45 44/53 48/57 50/59 45 43 Xci(%) 25 24 23 21 22 21 23 LPB (nm) 12.9 13 12.5 14.2 13.2 13.5 14.2 LPC (nm) 10.8 11.2 11.5 13.5 11.7 12 13 lc (nm) 2.7 2.7 2.7 2.9 2.6 2.7 2.7 la (nm) 8.1 8.5 8.8 10.6 9.1 9.3 10.3 (J/m2) 0.09 0.09 0.09 0.09 0.08 0.09 0.09

Table 1: Results deduced from DSC analyses and SAXS experiments The SAXS pattern of E-CR in the undeformed state (cf. Figure 2) shows an isotropic scattering ring which indicates a periodic structure. Thus this SAXS peak can be attributed to alternating crystalline and amorphous lamellae. This means that the microstructure is more organized than that suggested by the works of Bensason et al. and Minick et al. [13, 14]. However, the correlation peak is not pronounced, which indicates that it is a structure with an important disorder. In addition, the crystallite organization of this type of copolymer was also evidenced in a paper of Liu et al. [6] and will be confirmed by the in situ SAXS experiments during stretching presented later.
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The long periods deduced from Braggs law and from the correlation function (LPB and LPC respectively) are reported in table 1. Both methods give similar results and the values are nearly independent on the crosslink density of E-NC (LPB equals to 13.5 1 nm). lc values, determined from the correlation curves, are reported in the same table and they are also similar for the three EPDM materials. These values (2.7nm) are much lower than those obtained for a medium or low density polyethylene (PE) (around 10-20 nm [15, 16]). This explains the low melting temperature. From the Gibbs-Thomson relation, the surface energy can be deduced:
Hf
0

lc

Tf 0 Tf
0

Tf

where Tf0 is the melting temperature of an infinite crystal, Hf0 is the melting enthalpy per unit mass of an infinite crystal, is the crystalline density and lc is the thickness of the crystals. In the case of PE, Tf0 = 140C, Hf0 to 290 J/g and = 1.006 g/cm3 at room temperature. Taking the same data for the three EPDM materials of the study, the found value for three EPDM materials is 0.09 J/m2 (cf. Table 2). It is closed to the value found by Kazmierczak et al. [17] for PE (0.09 J/m2) or by Darras et al. [15] for ethylene-butene random copolymers (0.06-0.1 J/m2). This value suggests that the microstructure is similar to that of PE. Moreover, some microstructural information can be extracted from the calculation of the crystallinity ratio. The crystallinity ratio can be deduced from SAXS by two methods. The first one, Xci is directly deduced from the lc/LPC ratio: lc X ci (%) 100 8 LPC The second one, Xcc is deduced from the minimum value of the correlation function following [9]:

9 1 min The first methods gives values around 23% (2%), while the second method gives slightly inferior values of 17%, whatever the EPDM materials. Xcc determined from min underestimates generally the true value of the crystallinity. Thus the two methods give very similar results. These values are much higher than the Xcv values deduced from DSC analyses (around 10%). This promotes the idea of the existence of two phases: one rich in crystalline lamellae called hereafter semi-crystalline zone and another one very poor in crystalline lamellae called hereafter amorphous zone. We can estimate the volume fraction of the semicrystalline zone sc, assuming that the crystallinity ratio of the semi-crystalline zone is given by Xci or Xcc, i.e. is about 20% and roughly zero for the amorphous zone:
sc

X cc

min

(%)

X cv X ci

100

10

Whatever the uncertainties on the chosen Xci values, sc is around 50%. With the values of table 1, 43%, 57% and 65% are found for E-CR, E-CR2min and E-NC respectively, i.e. a value which increases when the crosslink density decreases. It is impossible from SAXS measurements to characterize the distribution of these zones in the material. However the elastic modulus provides some insights on this distribution.

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Sample name E-NC E-CR2min E-CR-0 E-CR-50 E-CR-165 E-CR-300 E-CR-510

Soluble fraction * (%) 100 03 0 3 2.9 3 5.7 3 8.8 3 20.6 3

Swelling ratio * 5.7 0.6 3.7 0.4 3.7 0.4 4.1 0.4 4.8 0.5 6.2 0.6

Elastic modulus at 80C (MPa) 1.5 0.2 2.9 0.3 3.1 0.3 2.6 0.3 2.1 0.2 1.2 0.1

Elastic modulus at 25C (MPa) 8.2 0.8 7.8 0.8 5.8 0.6 5.8 0.6 5.8 0.6 6 0.6 5.9 0.6

Table 2: Composition of different materials with their soluble fraction (*these experimental data are extracted of the paper of Planes et al.7)

Figure 4: Evolution of the elastic modulus at 25C with the crystallinity ratio Xc for E-CR, E-CR2min and E-NC (the dashed line is a guideline for the eyes)

Table 2 gives the modulus values at 80C and at 25C for the three EPDM materials. The elastic modulus at 80C is directly related to the crosslink degree of the amorphous phase; it is
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not measurable for E-NC. At 25C the reinforcement provided by the crystallites is evidenced, in particular for uncrosslinked EPDM. In spite of the low crystallinity ratio, the small size of the crystallites suggests that they are numerous. Consequently, they can be assimilated to crosslinking nodes, which play a predominant role in the mechanical properties. Moreover the modulus is correlated to the crystallinity ratio Xcv (cf. Figure 4). It is noteworthy that at this temperature E-NC shows the highest modulus. If the semicrystalline zones were not continuous in this material, the elastic modulus at 25C value would be very low (especially if one considers the low molecular weight of the studied EPDM). Therefore the semi-crystalline zones percolate. All sc and Xc values being in the same range for the three EPDM materials, it is reasonable to consider that this is true for all of them. The parallel and series models can be studied. The series model does not work since the E-NC material has a much higher modulus than the amorphous phase. The parallel model, which assumes that the amorphous zones are mechanically parallel to the semi-crystalline ones, gives:

sc

Ec

SC

Ea

11

Where Ec is the elastic modulus of semi-crystalline zone and Ea is the modulus of the amorphous zone.Taking for sc 0.65 and for E the experimental value of 8.2, and considering Ea as negligible, the deduced value for Ec is 13 MPa. This is between two and three times lower than the value found in our laboratory for a PE with a crystallinity ratio Xci equals to 20% [18]. This suggests that the mechanical behavior of the studied materials should be described by a combination of series and parallel models. This will be confirmed by in situ SAXS experiments during tensile tests presented in paragraph 3.2. In addition, several studies have reported that it is impossible to put butylenes branches within crystallites [19]. So it can be assumed that the crystalline lamellae are essentially constituted of polyethylene. This has two consequences: firstly the amorphous part in the semi-crystalline zone is enriched in propylene, and secondly because of statistic distribution of propylene sequences along the chain; tight folds are unlikely, leading to the existence of numerous tie molecules.

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3.2. Microstructure evolution during stretching of unaged samples

Figure 5: Large strain behavior at 25C and at 80C (in insert) of studied materials

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Figure 6: Average strains and stresses at break of three specimens tested with error bars for tensile tests at 80C and at 25C

Figures 5 and 6 present the true strain - true stress curves at room temperature; figure 2 b) presents the corresponding SAXS patterns of E-CR measured in situ. The behavior observed in SAXS is similar to that of PE: the pattern ovalization is followed by the appearance of two maxima occurring perpendicular to the stretching direction. The figure 7 (LPB as a function of true strain) illustrates the evolution of LPB (deduced from Braggs law) in the stretching direction and perpendicular to this direction during the uniaxial deformation. The calculated results for E-CR-0 show that LPB in the stretching direction increases from 13 nm to 15 nm (i.e. about 15% changes) at a 0.3 true strain. At the same strain, perpendicularly to the stretching direction LPB decreases of about 10 %. Thus, the semi crystalline phase is deformed, but at a level lower than the macroscopic deformation. Therefore, the mechanical behavior of this two phases material should be described by a series/parallel model, as discussed in previous section. The tensile deformation enlarges the average spacing between the crystalline lamellae, which are oriented perpendicularly to the stretching direction (by
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stretching of the amorphous phase between crystalline lamellae), while it decreases the average spacing between the lamellae oriented parallel to the stretching direction. The magnitude of this phenomenon is larger than that usually observed on polyethylene. This is due to the large amount of amorphous phase in the semi-crystalline zone. Between 0.3 and 0.6 true strain, the structure turns into a fibrillar structure (figure 7). Conversely to PE, no necking is observed during this transition. This can be explained by two facts: (i) the temperature of the c relaxation occurring in the crystalline phase [20, 21] which controls the crystalline shearing should be much lower than for classical PE. In the case of PE, this temperature is around 50C at 1Hz. The c relaxation is directly related to the crystalline lamella thickness. From the results of Popli et al. [20] and from the lc values previously deduced from SAXS (2.7 nm), it can be estimated that the c temperature of our copolymer is lower than room temperature. Roughly speaking it means that the stretching of our samples at room temperature is equivalent to stretching PE samples closed to their melting temperature (around 100C). (ii) The large number of tie molecules leads to a very homogeneous distribution of the stress along the crystalline lamellae and prevents strain localization.

Figure 7: Evolution of the long period LPB in the stretching direction and perpendicular to the stretching direction during stretching for E-CR-0

The strains at break at room temperature are larger than at 80C (see figures 5 and 6). Indeed the crack propagation is more difficult in fibrillar structure than in a wholly amorphous material. Conversely to what is observed at 80C, the E-NC stress-strain curve at 25C shows a hardening, but this hardening is still lower than the one observed for E-CR (figure 5).
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According to the theory of rubber elasticity, the presence of this hardening at room temperature for the uncrosslinked EPDM can be explained by the presence of crystallites, which act as crosslinking nodes. However, the difference in hardening between E-NC and ECR materials is small which indicates that the chemical crosslinking of the amorphous phase is not the main responsible of the observed hardening.

3.3. Consequences of gamma irradiation

E-CR has been submitted to different irradiation doses as explained in the experimental section. The irradiated samples have been characterized by DSC. The thermogramms presented in figure 3 show the appearance of a new melting peak at 54C for 165 kGy, which vanishes for the highest irradiation dose. Moreover, above 165 kGy dose, an increase in the temperatures of the two melting peaks can be observed. This can be the signature of either the formation of a second crystallite population and the growth of both crystallite populations (as evidenced by the increase in their melting temperature) or to a process of melting-recrystallization-melting [22, 23] occurring during the DSC heating ramp. Nevertheless these two melting peaks correspond to two crystallite populations with very similar thicknesses: from Gibbs-Thomson equation, taking the same value for surface energy (0.09 J/m2), we find 2.7 and 2.9 nm for the melting temperatures of 45C and 55C respectively. Thus DSC is very sensitive to any change of lamella thicknesses especially in the case of very small thicknesses. Therefore it can be concluded that the microstructure evolution during irradiation is very small, in spite of the small changes observed in DSC. This is confirmed by SAXS experiment, since lc and LPC (or LPB) are found quasi-constant whatever the irradiation dose (cf. Table 1). The crystallinity ratio Xcv is almost constant with a slight maximum, around 12%, for 300 kGy dose (cf. Table1). This is probably due to a slight chemically induced crystallization process up to 300 kGy assisted by chain scissions, which promotes the growth of crystallites. Note that these phenomena have been also reported in the case of polyethylene materials where they are found to be more important [2, 3], probably because of an initially higher crystallinity ratio. At elevated irradiation dose (510 kGy), Xcv begins to decrease: it could be explained by an eventual beginning of the crystallites degradation [3]. Nevertheless, it can still be concluded that irradiation does not induce important modification of the crystallinity ratio and of the proportion of semicrystalline and amorphous zones. Conversely, the amorphous parts of these zones are highly affected as evidenced by the evolutions of the sol fraction and of the swelling ratio with an increasing irradiation dose (cf. table 2).

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Figure 8: Evolution of the elastic modulus at 25C and at 80C with an increasing irradiation dose (The lines are guidse for the eyes) The figure 8 presents the evolution of the elastic modulus at 25C with an increasing irradiation dose. For comparison, the moduli at 80C are reported on the same figure. The evolution of elastic modulus at 25C with the irradiation dose is very limited (5.9 0.2 MPa), especially when compared to that obtained at 80C, when the modulus decreases of a factor around two. This decrease, as well as the presence of an increasing sol fraction with irradiation dose, is related to the degradation of the polymer network (cf. Table 1). Thus, in spite of the small crystalline content, the crystallites strongly limit the irradiation consequences on the modulus variation at 25C. Note that a slight maximum can be noticed for the 300kGy dose, in agreement with the variation of crystallinity ratio; though such comment must be considered with caution since the discussed variation are small. Figure 5 gives the true stress - true strain curves of the different samples at 25C. Up to a true strain of 1, all curves are nearly superimposed. Conversely, the rupture behavior of the material seems largely influenced by the irradiation dose. Irradiation leads to a large decrease in the elongation and stress at break. Given the uncertainties of the measurement, samples irradiated at 165kGy, 300kGy and 510 kGy give about the same strain and stress at break, the 50kGy sample giving intermediate values. Hardening seems also to decrease with the irradiation dose; however this phenomenon can also be partly masked by the early rupture of the samples. At true strain < 1, one can consider that the mechanical behavior is controlled by the phase arrangement, this one being very similar whatever the irradiation dose or even whatever the crosslinking degree. At larger strains, the fibrillar structure and the interconnecting regions between the fibrils depend on the tie molecules, the crosslinking degree, and the entanglement density. These parameters strongly evolve during irradiation. This is evidenced by the behavior at 80C recalled in insert of Figure 5. Especially, it is well
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known that a decrease in tie molecule concentration, induces a weaker hardening and a more brittle behavior of semi-crystalline polymers [24, 25]. The most irradiated sample (510 kGy) has a modulus at 80C comparable to that of E-CR2min, i.e. an average crosslink density comparable to that of the E-CR2min. Nevertheless at 25C the strain at break of E-CR-510 is lower than the one of E-CR2min (cf. Figure 5). Two explanations can be given: (i) the properties of the amorphous zones are very different: indeed at 80C the strain at break of ECR2min is 2.5 higher than for E-CR-510; therefore the microcracks of the amorphous zones could pilot the rupture of the material at 25C ; ii) the irradiation has induced a decrease in tie molecules concentrations in the semi-crystalline zone; this phenomenon can be enhanced by their chemical nature : the presence of propylene sequences in the chain provoke their ejection out of the crystallite and can promote the formation of tie molecules. These propylene sequences are likely more sensitive to irradiation: their scission is favored compared to that of ethylene. If now we compare E-CR2min and E-CR-0, the rupture behavior is nearly the same at 25C while it is very different at 80C. The amorphous zones present at 25C should have the same mechanical properties than the amorphous phase at 80C. Thus this result suggests that the rupture behavior at 25C is actually not governed by the amorphous zones properties but by the semi-crystalline zones and the concentration of tie molecules. As these two materials have similar crystallinity ratios, it seems that the key parameter of rupture behavior is the concentration of tie molecules.

4. Conclusions

The morphology and the mechanical properties of EPDM irradiated or not, have been studied. It has been shown that these materials are composed of two phases: semi-crystalline zones with a crystallinity ratio of 20% and mainly amorphous zones. The semi-crystalline zones are percolates through the film and therefore control the mechanical properties of the material in its semi-crystalline state for small deformations. At true strain < 1, the arrangement and the proportion of crystallites control the mechanical properties. As irradiation (in the tested range of irradiation dose) and crosslinking degree have only a small influence on these arrangements and proportions, all samples have nearly the same mechanical behavior. At large strains, the interactions between amorphous and crystalline parts in semi-crystalline zones through tie molecules seem to play the main role in the mechanical response. The concentration in tie molecules decreases with an increasing irradiation dose, which explains a smaller hardening phenomenon and a decrease in elongation at break. From an application point of view, it is shown that despite the low crystallinity fraction of these materials, the presence of a large number of crystallites strongly limits the consequences of irradiation on the mechanical properties when the materials are tested in the semi-crystalline state. However the mechanical reinforcement mainly depending on these crystallites, it is therefore very sensitive to temperature: this can be an important issue for applications such as cables for nuclear power plants, since their use temperature is close to the crystallite melting temperature.

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Acknowledgments It is a pleasure to acknowledge the joint research program COPOLA between EDF, NEXANS France, LABORELEC, CEA, INRA and CNRS. The authors also thank J.C. MAJESTE for GPC analyses.

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References 1. CHARLESBY, A.; VON ARNIM, E.; CALLAGHAN, L. Int J App Rad Isotopes 1958, 3, 226-231. 2. BATEJA, S.K. J App Polym Sci 1983, 28, 861-872. 3. ASLANIAN, V.M.; VARDANIAN V.I.; AVERTISIAN M.H.; FELEKIAN S.S.; AYVASIAN S.R. Polymer 1987, 28, 755-757 4. GEETHA, R.; TORIKAIA, A.; YOSHIDAD, S.; NAGAYAB, S.; SHIRAKAWA, H.; FUEKI, K. Polym Deg Stab 1988, 23, 91-98. 5. CELETTE, N.; STEVENSON, I.; DAVENAS, J.; DAVID, L.; VIGIER, G.; Nucl Inst Meth Phys Res B 2001, 185, 305-310. 6. LIU, L.Z.; HSIAO, B.S.; REN, S.; FU, B.X.; TOKI, S.; ZUO, F.; TSOU, B.; CHU, B. Polymer 2006, 47, 2884-2893. 7. PLANES, E.; CHAZEAU, L.; VIGIER, G.; FOURNIER, J. Accepted in Polymer. 8. Polymer Handbook; BANDRUP, J.; IMMERGUT, E.; GRULKE, E. Eds.; Wiley: New-York, 1999. 9. Small Angle X-Ray Scattering; GLATTER, O.; KRATKY, O. Eds.; Academic Press, 1982. 10. GODERIS, B.; REYNAERS, H.; KOCH, M.H.J.; MATHOT, V.B.F. J Polym Sci Part B: Polym Phys 1999, 37, 1715-1738. 11. KOBERSTEIN, J.T. ; MORRA, B. ; STEIN, R.S. J App Cryst 1980, 13, 34-45. 12. CHENAL, J.M.; CHAZEAU, L.; BOMAL, Y.; GAUTHIER, C. J Polym Sci Part B: Polym Phys 2007, 45, 955-962. 13. BENSASON, S.; MINICK, J.; MOET, A.; CHUM, S.; HILTNER, A.; BAER, E. J Polym Sci Part B: Polym Phys 1996, 34, 1301-1315. 14. MINICK, J.; MOET, A.; HILTNER, A.; BAER, E.; CHUM, P. J Polym Sci Part B: Polym Phys 1995, 58, 1371-1384. 15. DARRAS, O.; SEGUELA, R. Polymer 1993, 34, 2946-2950. 16. HUMBERT, S. ; LAME, O. ; VIGIER, G. Polymer 2009, doi:10.1016/j.polymer.2009.05.017 17. KAZMIERCZAK, T.; GALESKI, A.; ARGON, A.S.; Polymer 2005, 46, 8926-8936. 18. HUMBERT, S.; LAME, O.; VIGIER, G. to be published 19. OLEINICK, E.F. Polym Sci Series C 2003, 45, 2139-2264. 20. POPLI, R.; GLOTIN, M.; MANDELKERN, L. J Polym Sci: Polym Phys Ed 1984, 22, 407- 448. 21. NITTA, K.H.; ASUKA, K.; LIU, B.; TERANO, M.; Polymer 2001, 42, 1219-1226. 22. GROENICKX, G.; REYNAERS, H.; BERGMANS, H.; SMETS, G. J Polym Sci: Polym phys Ed 1980, 18, 1311-1324. 23. VANDERMIERS, C.; MOULIN, J.F.; DAMMAN, P.; DOSIERE, M. Polymer 2000, 41, 2915-2923. 24. SEGUELA, R. J Pol Sci Part B: Polym Phys 2005, 43, 1729-1748. 25. CAZENAVE, J.; SEGUELA, R.; SIXOU, B.; GERMAIN, Y. Polymer 2006, 47, 3904-3914.

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Annexe 2 : Essais de traction in-situ sous WAXS 25 C et 80 C pour les EPDM non chargs

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Afin dapprofondir ltude du comportement mcanique temprature ambiante des lastomres non charg EPDM, des mesures de traction in-situ sous WAXS (diffusion des X aux grands angles) ont t ralises 80C et 25C sur des lastomres non irradis et irradis. Dans larticle 21, il a t montr que cet EPDM est compos de deux phases (en quantits quasi-quivalentes) : une zone semi-cristalline dont la cristallinit est voisine de 20% et une zone essentiellement amorphe. Cette zone semi-cristalline est continue dans le matriau et gouverne ainsi les proprits mcaniques du matriau.

Figure 1 : Spectres WAXS du matriau E-CR non vieilli pendant un essai de traction 25C et 80C Comme le montre la figure ci-dessus, les essais de traction in-situ en WAXS temprature ambiante du matriau E-CR montre un important phnomne dorientation. En intgrant sur des secteurs de 30 ( lquateur et au mridien) et en dconvoluant la bosse amorphe et le pic cristallin, il est possible dobtenir le ratio de phase orient en fonction de la dformation (cf. 2me Partie). Comme il la t montr dans larticle 21, aprs 0.3 en dformation vraie, le matriau devient fibrillaire, par consquent la courbe ratio de phase amorphe oriente versus dformation vraie nest reprsente que jusqu cette dformation. Daprs la figure 2, on peut constater que lorientation de la phase amorphe est relativement rapide et le but de cette annexe est donc dtudier les effets du degr de rticulation du matriau et du vieillissement par irradiation sur lorientation de la phase amorphe pendant lessai de traction.

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30 Part de phase amorphe oriente (%) 25 20 15 10 5 0 0 0,05 0,1 0,15 Dformation vraie 0,2 0,25 0,3

Annexe 2

Figure 2 : Evolution de la part de phase amorphe oriente en fonction de la dformation vraie pour le matriau E-CR non vieilli Compte tenu des rsultats de larticle 21, nos lastomres contiennent deux parties amorphes : la zone amorphe et les rgions amorphes prsentes dans la phase semi-cristalline. Ainsi lorientation observe 25C est une moyenne de lorientation de ces deux phases. Lune des premires questions est didentifier quelle est la partie amorphe qui soriente ds le dbut de la dformation. Ainsi les mmes expriences ont t ralises 80C lorsque le matriau est totalement amorphe. La figure 2 montre les spectres WAXS du mme matriau 80C pour les dformations vraies 0, 0.15, 0.3, et 0.4. Le rsultat est tout fait diffrent puisquaucune orientation nest observe durant la dformation. Ainsi aux faibles dformations, lorientation observe lors des essais de traction 25C est essentiellement due celle des rgions amorphes prsentes dans la phase semi-cristalline. Taux de Elastic cristallinit Xc modulus at (%)** 25C (MPa)** E-NC 100 12.40.2 8.20.8 E-CR2min 03 1.50.2 11.40.2 7.80.8 E-CR-0 03 2.90.3 10.60.2 5.80.6 E-CR-50 2.93 3.10.3 10.30.2 5.80.6 E-CR-165 5.73 2.60.3 10.40.2 5.80.6 E-CR-300 8.83 2.10.2 11.90.2 60.6 E-CR-510 20.63 1.20.1 10.90.2 5.90.6 Tableau 1 : Fraction soluble, modules lastiques 80C et 25C des matriaux tudis (* ou ** ces donnes exprimentales proviennent respectivement des articles 12 et 21) Dans la figure 3, la part de phase amorphe oriente 0.15 en dformation vraie est reprsente en fonction de la dose dirradiation. A titre de comparaison, les mmes paramtres pour les matriaux E-CR2min et E-NC ont t indiqus. Comme le montre les matriaux non irradis, lorientation est de plus en plus importante lorsque le degr de rticulation augmente. En effet la prsence de nuds de rticulation dans la phase amorphe permet la formation de molcules liens supplmentaires entre les cristallites et ceci contribue une orientation de la
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Fraction soluble (%)*

Elastic modulus at 80C (MPa)**

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phase amorphe plus rapide. (Pour le matriau non rticul E-NC, un lger phnomne dorientation est visible). Dautre part, lorsque la dose dirradiation est augmente, une diminution de lorientation de la phase amorphe est observe. On peut remarquer que les matriaux E-CR-510 et E-NC montrent une orientation quivalente alors que le premier chantillon montre un module lastique 80C plus lev que le second (Table 1). Ceci peut tre expliqu de deux faons. Dune part, le matriau E-NC a un taux de cristallinit suprieur llastomre E-CR-510. Ainsi les matriaux non irradis comblent les faiblesses de leur zone amorphe, par un supplment de cristallites, qui conduit une orientation plus leve. Dautre part, pour les matriaux irradis, la prsence dimportantes fractions solubles constituant des zones de faiblesse et la dgradation des molcules liens1 induisent des htrognits dans le rseau lastomres. Ces dfauts peuvent expliquer une orientation plus faible de la phase amorphe et la faible transmission des contraintes dans cette phase.
Part de phase amorphe oriente (%) 25 20 15 10 5 0 0 100 200 300 Dose (kGy) Vieillissement par irradiation E-NC E-CR2min 400 500 600

Figure 3 : Evolution de la part de phase amorphe oriente (%) 0.15 en dformation vraie avec la dose dirradiation Comparaison avec les matriaux avec diffrents degrs de rticulation

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Rfrences
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Article 1 Article 2

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Article 3

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Article 3: Influence of fillers on mechanical properties of ATH filled EPDM during ageing by gamma-irradiation
PLANES E., CHAZEAU L., VIGIER G., FOURNIER J., STEVENSON-ROYAUD I.

Sommaire
Abstract .............................................................................................................................................. 148 1. 2. Introduction ............................................................................................................................... 148 Experimental.............................................................................................................................. 149 2.1. 2.2. 2.3. Materials .............................................................................................................................. 149 Ageing conditions................................................................................................................ 150 Instruments .......................................................................................................................... 151 IR spectroscopy ........................................................................................................... 151 Swelling measurements ............................................................................................... 151 Swelling in xylene ................................................................................................... 151 Ammonia fumes treatment + swelling in xylene ..................................................... 152 Microscopy .................................................................................................................. 152 Tensile tests ................................................................................................................. 153 Differential scanning calorimetry ................................................................................ 153

2.3.1. 2.3.2. 2.3.2.1. 2.3.2.2. 2.3.3. 2.3.4. 2.3.5. 3.

Results......................................................................................................................................... 154 3.1. 3.2. 3.3. 3.4. Preliminary characterization of non irradiated materials .................................................... 154 Oxidation ............................................................................................................................. 156 Degradation kinetic ............................................................................................................. 156 Consequences on mechanical properties at 80C ................................................................ 160 At small deformations ................................................................................................. 160 At large deformations .................................................................................................. 162

3.4.1. 3.4.2. 3.5. 3.6. 4.

Evaluation of the filler influence on the degradation kinetic .............................................. 165 Consequences on mechanical properties at 25C ................................................................ 169

Conclusions ................................................................................................................................ 173

Acknowledgment ............................................................................................................................... 174 References .......................................................................................................................................... 175

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Une fois la dgradation de la matrice non charge caractrise lors du vieillissement par irradiation temprature ambiante (cf. Articles 1 et 2), linfluence des charges a t tudie dans les deux articles suivants. Ici il est propos dtudier dabord leffet dune charge micronique ATH partir de deux formulations, lune sans agent de couplage, lautre avec cet agent. Les consquences du vieillissement sur les proprits mcaniques ltat caoutchoutique (i.e. 80C) et ltat semi-cristallin (i.e. 25C) sont prsentes.

Abstract The influence of the presence of fillers in the degradation mechanisms and on the evolution of the mechanical properties is studied with ATH filled EPDM. The presence of an important fraction of fillers accelerates the degradation process under irradiation. Above the melting temperature of the EPDM, this induces a decrease in the apparent mechanical reinforcement of the fillers. This also promotes decohesion mechanisms which enables an increase in the strain at break with irradiation dose, conversely to the decrease in the strain at break observed for unfilled matrix. The use of a filler treatment does not seem to modify the acceleration effect of the filler on the degradation. However the consequence is to delay the appearance of decohesion mechanisms. At room temperature, i.e. below the melting temperature, all the consequences of ageing by gamma-irradiation for the range of irradiation doses tested are strongly attenuated by the presence of a semi-crystalline microstructure, the morphology of which being not too strongly modified by irradiation.

1. Introduction

EPDM rubbers, because of their excellent electrical insulation properties, are widely used in wire and cable coatings. The increasing demand for EPDM in electrical applications is also due to its excellent resistance to degradation and easiness to accept large amounts of fillers. Thus formulations which used aluminium trihydroxide (ATH) as fillers with good mechanical and ageing resistance, with flame retardancy and smoke suppression characteristics have been developed. These polymer materials used in cables and accessories can be exposed to severe environmental conditions. An example would be cables in nuclear power plants which may be exposed to elevated temperatures and gamma irradiation. These conditions are known to cause their ageing and consequently their degradation over time. Ageing by gamma irradiation of crosslinked EPDM elastomers has been studied for unfilled rubbers [1, 2, 3, 4]. Chain scissions and crosslinking mechanisms have been evidenced, depending on the irradiation condition and on the polymer formulation. However, the influence of fillers such as ATH on the degradation mechanisms and then its consequences on the mechanical properties have been scarcely investigated [5, 6, 7]. Nevertheless, fillers can influence the degradation mechanism. They can modify the polymer degradation by trapping radicals or degradation by-products which can interact with intermediate chemical species involved in the matrix degradation. They can also be degraded
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and lead to the formation of supplementary degradation by-products, which can interact with the matrix degradation process. Moreover, whether they are still inert or not during the matrix degradation, this matrix degradation can induce a modification of the filler-matrix interaction: this may have consequences in the reinforcement efficiency of the filler, and therefore be involved in the consequences of the degradation in the overall properties of the composite. For instance, the study of the photo-oxidation of EPDM filled ATH [8] has shown different changes of stress and elongation at break for filled and unfilled samples which were assigned to the modification of the filler-matrix interactions. In addition, the semi-crystalline state of the studied EPDM must be taken into account. Indeed, as reported in literature, fillers can modify the crystallinity of composites and they can form a mixed network with crystallites. This structure induces a large reinforcement efficiency [9]. Moreover in a previous study it has been shown that the crystallite presence in an unfilled EPDM limits the consequences of irradiation on the mechanical properties in the semi-crystalline state [10]. When these filled materials are aged by gamma irradiation, the evolution of the crystalline microstructure can be different than that observed for unfilled matrix. For example, more recently, it was found that the low flux of neutron promotes in ATH filled EDPM the growth of crystalline zones [11], which leads to an increase in the elastic modulus [12]. Thus, in this paper, it is proposed to study the effect of the presence of ATH filler on the evolution of the mechanical properties of ATH filled crosslinked EPDM after ageing by gamma irradiation at room temperature. Since the filler-matrix interaction seems to play a crucial role during ageing, formulations with coupling agent are also investigated. In addition, uncrosslinked formulations have also been studied to have better insight on the degradation process. At last, in order to understand the role of the semi-crystalline phase, the consequences of ageing on the mechanical properties are studied both in the rubbery state (i.e. at 80C) and in the semi-crystalline state (at room temperature).

2. Experimental 2.1. Materials The EPDM elastomer studied (Nordel IP NDR 3722 P from Dow Chemical Company) contains 70% ethylene, 29.5% propylene and 0.5% ENB. The crosslinking agent is the dicumyl peroxide (Perkadox BC-FF from Akzo Nobel). EPDM is filled with ATH, which is a micronic filler of an average size of 1.3m meaning a specific surface area of 3.5m2/g. The basic structure forms stacked sheets of linked octahedrons of aluminum hydroxide. The octahedrons are composed of aluminum ions with a +3 charge bonded to six octahedrally coordinated hydroxides with a -1 charge. The hydroxides can be assimilated to crystal water. Generally, there is free bound water at the filler surface [13, 14]. This filler is an anti-flame agent: during thermal degradation, it undergoes endothermic dehydration releasing water, which leads to formation of a thermally stable ceramic material, i.e. alumina trihydroxide Al2O3. The formation of a surface layer of Al2O3 acts as a shield to heat and mass transfer between the polymer and the flame. The fire retardant effectiveness of ATH is however very poor, i.e. high loadings, generally superior to 50%, are necessary to reach a suitable fire retardant effect. Two types of ATH have been chosen for this study: ATH without surface treatment (Apyral 40CD from Nabaltec) and ATH surface treated with a vinylsilane (Apyral
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40VS1 from Nabaltec). This surface treatment is made of a reactive foot with three ethoxy groups, which react with the silanol of the filler surface, and an alkyl chain with a vinyl function, which can react with the matrix during crosslinking. The silane treatment is done to improve the filler-matrix interactions [15, 16]. The treated ATH will be named hereafter ATHT and the untreated one ATHU. The compositions of the different formulations and their name can be found in Table 1. For the uncrosslinked formulations, only one type of filler: ATHU and one filler ratio has been studied: 150 phr, that is 150 weights ratios for 100 weight ratios of EPDM, which corresponds to a weight fraction of 60% and a volume fraction of 35%. For the crosslinked rubbers, two ATHU ratios have been studied: 32 phr, which corresponds to a weight fraction of 24% and a volume fraction of 10% and 150 phr. The material based on treated ATH is crosslinked and the filler content is 150 phr (E-CR-150ATHT). The samples are processed following three steps. The first step is the mixing of the matrix and the incorporation of fillers and crosslinking agent in the polymer. First the matrix is introduced in the internal mixer and mixed for 2 minutes, and then the fillers are introduced. If the elastomer has to be crosslinked, peroxide is added after 5 minutes of mixing, its dispersion is obtained after mixing 10 min, at low temperature (80C) to prevent any reaction of the crosslinking system. In order to obtain a better filler dispersion, the second step is the mixing in an external mixer (cylinders) for 10 min at low temperature (80C). During the last step, the compound is pressed as 1-mm-thick films at 170 C to promote crosslinking reaction. For the crosslinked materials, the curing time (t98 at 170C) is estimated from torque measurement performed with a MOSANTO analyser: the crosslinking is carried out for 10 min (i.e. the same time as for the unfilled material). For the uncrosslinked materials, this time is fixed to 3 min, i.e. the time needed to obtain the sample shape.

E-NC E-NC-150ATHU E-CR E-CR-32ATHU E-CR-150ATHU E-CR-150ATHT

EPDM (phr) 100 100 100 100 100 100

Peroxide (phr) 0 0 3 3 3 3

ATH (phr) 0 150 0 32 150 150

Filler volume fraction (%) 0 35 0 10 35 35

Table 1: Composition of the studied materials

2.2. Ageing conditions

All samples are exposed to gamma-radiation of a 60Co source at a dose rate of 1 kGy/h in an oxygen atmosphere for doses 50, 165, 300 and 510 kGy (Arc Nucleart Grenoble France):
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the water temperature of the pool, where exposures are performed is about 18C. Afterwards, they are stored under vacuum at about 22C. The samples will be named hereafter E-NCZZZ, E-NC-XXXATHY-ZZZ, E-CR-ZZZ, E-CR-XXXATHY-ZZZ with XXX the filler ratio, Y for the filler type (U for untreated or T for treated), and ZZZ for irradiation dose.

2.3. Instruments 2.3.1. IR spectroscopy

In order to evaluate the degree of oxidation of the materials, analyses by IR spectroscopy were performed. Firstly, changes in carbonyl concentration were followed by a Thermo Nicolet Nexus FT-IR spectrophotometer with the technique Attenuated Total Reflectance (ATR) accessory using 32 scans and a resolution of 4 cm-1. IR spectroscopy in the transmission mode could not be used because the samples are absorbing. Secondly, oxidation (carbonyl) profiles were deduced from IR-microspectroscopy using a Continum microscope coupled to a Nexus Nicolet optical bench (32 scans, resolution of 4 cm-1). A slice of sample of about 40 m was cut by cryo-microtom in the thickness direction. Then IR spectra were measured on this slice every 50 m to have an oxidation profile along the sample thickness. These analysis were conducted in CNEP - Centre National dEvaluation de Photoprotection Clermont Ferrand (France).

2.3.2. Swelling measurements 2.3.2.1. Swelling in xylene

The swelling measurements are very useful to characterize the network degradation. In the case of unfilled rubbers, the swelling restriction is due to crosslinks connecting the polymer chains, which avoid their extension and their diffusion. Swelling provides information on the matrix network chain density (determined from the swelling ratio) and the percentage of soluble fraction (i.e. the proportion of chains which do not belong to the network). Because of the filler-rubber interactions, fillers can play the role of additional crosslinks. Besides, their presence, via filler-filler interactions can also restricts the swelling. Therefore it is hazardous to relate the swelling ratio to the matrix network chain density and the results on the measurements will be considered only as qualitative. The swelling procedure is as follows: samples with an initial weight Mi and a filler weight fraction are introduced in xylene for 8 days to achieve the swelling equilibrium; then the swollen material with a weight Ms is dried under vacuum at 60C during 1 day and finally weighted to obtain the dried mass Md. The swelling ratio Q of the polymer and the soluble fraction Fs are calculated taking into account the non swelling of the fillers, and the fact that the soluble fraction does not contain fillers (it was checked afterwards for all the samples), from the following relations: Md polymer M s Q 1 1 xylene M d 1
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Mi Md 100 2 Mi Mi In the case of filled rubbers, Kraus has developed an empirical approach which enables to characterize the strength of the filler-matrix interactions [17]. He proposed the following equation: Q f c 1 m 3 Q0 1 f c where Q, Q0, , f and c are the swelling ratio of the composite and of the unfilled matrix, the filler weight ratio, the filler density and the composite density respectively. No analytical expression is given for m which is in practice a free parameter varying with the nature of the interactions between fillers and matrix. But if Q/Q0 varies linearly with the ratio , with a positive value for m, the filler-elastomer interactions are 1 f c f c Fs

significant. Conversely, if Q/Q0 does not vary linearly with the ratio f c , 1 f c and if m is negative, the fillers are not adherent and their dewetting is likely. When only one mass fraction is studied like in the case of ATHT filler, one can still consider the ratio Q/Q 0. Thus a ratio inferior to one suggests good filler matrix-interactions, while a ratio superior to one is significant of bad interactions. 2.3.2.2. Ammonia fumes treatment + swelling in xylene

It is well known that polymer adsorbs on the filler surface (as shown for instance by the presence of bound polymer on the filler surface after solubilisation of the uncrosslinked matrix). This adsorption leads to a false evaluation of the matrix swelling ratio. Ammonia atmosphere cleaves physical linkages between filler and polymer [18, 19, 20, 21] and suppresses the filler influence in the polymer swelling measurements. Thus, ammonia fume treatment is applied to the different samples following this procedure: samples are put in a dessiccator in presence of ammonia fumes during three days; all free hydroxyls functions, existent on the filler surfaces, react with the ammonia. Finally the swelling ratio is determined with the previous method with the same parameters: the swelling ratio of polymer matrix determined by this measurement, corrected of the soluble fraction, will be named Qa. However, this swelling method must be used with caution: indeed, when the elastomers are aged by gamma-irradiation, some oxidation products are formed. These products can in turn react with the ammonia (it is a well known treatment used in IR spectroscopy to quantify the carboxylic groups created during ageing [1, 2]). Therefore, this method will be only used for unaged samples.

2.3.3. Microscopy Evidences of good filler dispersion within the matrix were provided by images obtained in an Environnemental Scanning Electron Microscopy (FEI XL 30 FEG ESEM). This ESEM is equipped with a Field Emission Gun which enables observation at low voltage (1 kV), so that sample metallization can be avoided. Prior to their observation, the samples were fractured in

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liquid nitrogen. The used detector collects secondary electron and the observation of the sample fracture surface is performed in high vacuum.

2.3.4. Tensile tests

Tensile tests are performed on an MTS device equipped with a temperature controlled chamber. Experiments are conducted at 80C and at 25C with a true strain rate 0.01 s -1. An image processing acquisition system (Apollor VideoTraction System) is used to obtain the true stress-true strain curves. The samples are dumbbell-shaped with dimensions 20 x 4 x 1 mm3. Average stresses and strains at break from three tested samples and error bars are given in figure 12. The elastic modulus E is calculated from the slope of the linear initial portion of the tensile test curve. Tensile test cycles are also performed at 80C, i.e. above the crystallite melting temperature. Firstly the sample is stretched up to a true strain of 0.2, relaxed during 5 minutes, then stretched again at a higher true strain; this experiment is repeated with an incremental 0.2 true strain, up to the sample rupture.

2.3.5. Differential scanning calorimetry

All measurements were carried out with a Perkin-Elmer Diamond calorimeter, with 10-15 mg of material encapsulated in a standard aluminum pan. Dry nitrogen is used as the purge gas. The instrument is calibrated with indium using a scan rate corresponding to the heating rate of the experiments. The crystallization temperature domain of our EPDM is large [10]: from about -50C up to 60C. Indeed, when the polymer is cooled from 80C to -50C, one wide peak can be observed during the heating ramp. If an isothermal treatment of several hours at the temperature Tc is performed during cooling, three melting peaks are obtained during the heating scan: The first one corresponds to the crystallite population, formed during cooling from 80C to Tc. The second one concerns the crystallite population formed during the isothermal treatment at Tc. The third one corresponds to the crystallite population, created during the cooling from Tc to -50C. A test series has been performed to evaluate the optimal crystallization temperature, i.e. the temperature Tc which leads to the highest crystallinity ratio with the fastest crystallization kinetic. The found Tc is 22C and the isothermal treatment to obtain a stable crystallinity ratio is equal to 12h. Thus, the thermal treatment applied to all samples is the following: - A heating ramp up to 80C to erase the previous thermal history - A rapid cooling down to the optimal crystallization temperature 22C and storage during 12h at this temperature

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Moreover, in order not to affect the crystallinity by any further treatments around this temperature, in particular the ageing in the pool at 18C, and the post-irradiation at 22C, the samples are annealed with a heating ramp of 1C/min up to 38C and maintained at this temperature during 6h. Then they are cooled down to 22C and stored at this same temperature. This treatment enables to get a unique well defined melting peak for unfilled EPDM materials and a double peak for ATH filled EPDM. Thus these materials have one or two crystallite populations with melting temperatures above 22C. To study the materials cristallinity after their irradiation, they are cooled from room temperature down to 50C at a cooling rate of 10C/min and heated up to 100C at 10C/min. The cooling from room temperature to -50C is necessary to avoid a DSC peak overshoot overlaping the melting peaks. However this cooling induces the formation of an additional melting peak, which can be observed between -40C and 20C. That is why the crystallinity ratio Xc is defined from enthalpy of the melting peaks between 22C and 60C Hf: Hf Xc 4 1 Hf0 where the weight ratio of fillers and Hf0 is taken equal to 290 J/g [22], i.e. the value for perfect polyethylene crystal, since it is assumed that only polyethylene segments can crystallize. Indeed, since polyethylene segments are predominant, most of crystallinity comes from the crystallization of these segments.

3. Results 3.1. Preliminary characterization of non irradiated materials Q0 Q Q/Q0 Qa Fp(%) E-NC 100 E-NC-150ATHU 100 E-CR 3.7 1 3.5 0 E-CR-150ATHU 3 0.81 3.5 0 E-CR-150ATHT 2.8 0.77 2.9 6.5 Table 2: Swelling ratios Q, Q0 and Qa obtained by the two swelling methods, and sol fractions Fp (%), of the unaged materials. Table 2 gives the swelling ratios Q, Q0, Qa and the soluble fraction Fp of the different samples. As said previously, it was checked by thermogravimetric analyses that the sol fractions obtained with filled elastomers do not contain fillers. Both uncrosslinked materials are totally soluble in xylene, even at large large filler content (E-NC-ATHU150-0), evidencing the absence of any filler percolating structure. This is expected in the case of micron fillers, which have a low specific surface [23]. Such absence of rigid structure of filler is also expected in the crosslinked materials. Concerning these materials (E-CR-ATHU and E-CR-ATHT), the polymer phase of the filled rubbers has a swelling ratio inferior to the matrix one. The ratio Q/Q0 of the samples filled with treated and untreated ATH are given in Table 2. Whatever the materials, they show a ratio below one, significant of some filler-matrix interaction. In E-CR-ATHU these interactions are probably physical ones. In E-CR-150ATHT, the silane treatment induces additional covalent bonds between the polymer and the filler (all over the filler surface),
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which explain the lower Q/Q0 ratio. Indeed, this formation of covalent bonds between filler and matrix is mainly evidenced at large strains or in swelling experiments, in which the elastomer matrix is deformed at a significant level [24, 25]. Such effect is also confirmed by the observation of the fracture profile of both materials. Figure 1 shows holes at the surface of E-CR-150ATHU with neat interfaces between fillers and matrix, revealing weak filler-matrix interactions, whereas fracture profile of E-CR-150ATHT looks very different with continuity between the matrix and fillers, suggesting stronger filler-matrix interactions. Moreover it can be noted that E-CR-150ATHT contains a significant soluble fraction (ca.6%). This can be explained by the fact that a part of the peroxide is used for the coupling reaction between fillers and matrix, leading to a less efficient matrix crosslinking.

Figure 1: MEB images of fracture profiles of E-CR-150ATHU-0 and of E-CR-150ATHT-0

The ammonia treatment of E-CR-150ATHU leads to an increase in its swelling ratio: this one, corrected of the filler presence, is equal to that of the unfilled matrix E-CR submitted to the same treatment. This, in addition to the absence of sol fraction, suggests that the matrix crosslink density is the same in both materials. Conversely, the ammonia treatment applied to the treated ATH filled samples has no significant effect on the swelling ratio. It was expected since the covalent bonds are not affected by the ammonia treatment. The tensile moduli of the filled and unfilled crosslinked samples are plotted in Figure 4 b. The modulus increase measured with 32 phr of ATH corresponds to a factor 1.2. This was expected for a composite in which the fillers can be considered as dilute particles: the reinforcement is of the same order as that predicted by the generalized self consistent scheme of Christensen and Lo [26, 27] which predicts a value of 1.3. (The difference between the theoretical and experimental values is within the experimental uncertainties). 150 phr of ATH (35vol. %) leads to an experimental reinforcement of a factor around 3.5. This value is slightly higher than the one predicted by Christensen and Lo model, which gives a value of 3.1 (calculation performed with a filler modulus above 1GPa). An explanation could be a higher effective form factor of the filler (which are assumed to be spherical in the Christensen and Lo model), leading to a better reinforcement of the material. Such assumption might be supported by the lower value found for the reinforcement factor calculated for E-CR150ATHT, ca.3.2, since the filler treatment is known to promote a better filler desagglomeration; even if this lower reinforcement factor might also be due to the lower
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initial crosslink density of the matrix of this material. In any case, it can be concluded, that the reinforcement obtained with 150 phr of ATH is of the order of 3.5. Figure 5 presents the tensile curves of the different samples. As expected, 32 phr of untreated ATH induces a very slight increase in stress, with a negligible variation of the ultimate properties. The introduction of 150 phr of untreated ATH leads to a strong increase in the stress level at a given strain with an increase in the stress at break and a decrease in the strain at break, as usually observed for micron size filled composites [28, 29]. The use of the filler treatment leads to a very strong hardening during stretching. The materials with treated and untreated fillers have the same strain at break but the stress at break of E-150ATHT is much higher i.e. around 8 MPa. Thus, as said before, the presence of the filler-matrix covalent bonds is mainly evidenced at large strain, the fillers acting like multifunctional crosslinks. The effect of filler treatment is also observed in the cycle tensile tests at 80C (cf. Figure 6). For each incremental true strain, the cycle area, significant of the material damage, between two successive curves, is plotted versus true stress. A same cycle area i.e. a same rupture energy, is obtained at a true stress higher for E-CR-150ATHT-0 than for E-CR-150ATHU-0. This evidences the role of strong filler-matrix bonds created by the silane treatment which delays the material damage.

3.2. Oxidation

After the radio-oxidation of EPDM, an increase in absorbance in the hydroxyl absorption region (3800-3000 cm-1) was observed [1, 2] corresponding to the formation of alcohols, acids and hydroperoxides. The formation of carbonyl can be evidenced by an absorption maximum at 1713 cm-1 accompanied by several shoulders around 1785, 1755, 1740, and 1695 cm-1 [1]. The measurements by IR spectroscopy (ATR) have shown that in the case of ATH filled EPDM, the same oxidation products are generated. For all materials (unfilled and filled), an increase in hydroxyl and carbonyl absorption regions can be observed with an increasing irradiation dose, but it was not possible to quantify these products by ATR and thus to compare the oxidation level of the different elastomers. Indeed, the IR beam depth penetration and the number of reflections in the samples can be influenced by the presence of fillers. Moreover, scattering phenomena can occur. However, the use of IR - microspectroscopy on sample slice can provide the oxidation product distribution within the sample thickness. The variations in absorbance at 1713 cm-1 are chosen for this characterisation. For E-CR-510 and E-150ATHU-510, i.e. at the maximal irradiation dose, the oxidation profiles are nearly flat; this indicates that in the irradiation conditions of this study, the oxidation processes are homogeneous within the sample thickness.

3.3. Degradation kinetic

Uncrosslinked materials: Figure 2 presents the swelling ratios Q and Q0 versus the irradiation dose. For the E-NC material (Figure 2 a), Q decreases with irradiation dose up to 165 kGy, then stabilizes up to 510 kGy. This evidences that this material is submitted to both
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phenomena of crosslinking and chain scissions. The first is preponderant at the beginning of irradiation, whereas the latter becomes preponderant at high irradiation doses. As shown in Figure 3, the soluble fraction Fp follows the same evolution. The same evolution can also be observed for E-NC-150ATHU material. However, at high irradiation doses, the soluble fraction Fp is higher than the one of E-NC, suggesting that the degradation is more important for the filled material. Crosslinked materials: For E-CR (Figure 2 b), between 0 and 50 kGy, no variation of Q and a slight increase in the soluble fraction Fp (Figure 3) is observed. Then for higher irradiation doses, the soluble fraction rapidly increases as well as the swelling ratio. The material filled with 32 phr of ATH presents the same evolution, with a swelling ratio slightly lower due to a small swelling restriction induced by the ATH-matrix interaction. All these results suggest an identical polymer degradation with or without 32 phr of ATH. The polymer chains are submitted to chain scission mechanisms, in competition for the lowest dose (below 165 kGy) with a slight crosslinking mechanism which becomes negligible at high irradiation dose [10]. As also seen previously with uncrosslinked materials, the irradiated E-CR-150ATHU shows an increase in the sol fraction with irradiation dose, which is more important than the one observed for unfilled matrix (E-CR) at high irradiation dose. Thus, for crosslinked as well as uncrosslinked materials, the presence of an important fraction of ATH seems to promote the material degradation. This will be discussed in section 3.4. Concerning the treated fillers, the sol fraction increases more slowly than in the case of E-CR150ATHU. This leads at 510 kGy to the same value of the sol fraction for both E-CR150ATHT and E-150ATHU. Within the assumption that the degradation mechanism is similar for both samples, one could have expected a more rapid increase in the sol fraction versus irradiation dose for the material with treated fillers. Indeed E-CR-150ATHT is likely less crosslinked than E-CR-150-ATHU and it is known that the sol fraction increase due to the degradation of the material is inversely proportional to its crosslink density [30]. The same value of the sol fraction at 510 kGy of E-CR-150ATHU and of E-CR-150ATHT materials means (i) either that the chain scission phenomenon is counterbalanced by some residual crosslinking reaction, induced by residual silanes which have not reacted at the polymermatrix interface or by a crosslinking of the initially non crosslinked sol fraction by irradiation (like observed in the case of uncrosslinked EPDM under irradiation [24]), (ii) or that the filler treatment inhibits the acceleration of the degradation mechanisms promoted when the fillers are not surface treated.

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Figure 2: Evolution the swelling ratio during irradiation a) for uncrosslinked materials (ENC, E-NC-150ATHU) (dashed lines are guide for the eyes) b) for crosslinked materials (ECR, E-CR-32ATHU, E-CR-150ATHU, E-CR-150ATHT) (dashed lines are guide for the eyes)

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Figure 3: Evolution the soluble fraction Fp during irradiation a) for uncrosslinked materials (E-NC, E-NC-150ATHU) (dashed lines are guide for the eyes) b) for crosslinked materials (E-CR, E-CR-150ATHU, E-CR-150ATHT) (dashed lines are guide for the eyes for E-CR150ATHU and for E-CR-150ATHT)

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3.4. Consequences on mechanical properties at 80C 3.4.1. At small deformations

Uncrosslinked materials: Figure 4 presents the evolution of the elastic modulus at 80C versus irradiation dose for the different samples. For the uncrosslinked samples unfilled or filled (cf. figure 4 a)), the crosslinking phenomenon between 0 and 165 kGy induces an increase in the elastic modulus at 80C. Moreover, for the E-NC-150ATHU material, the reinforcement factor (for instance 3.6 at 50 kGy) obtained by this crosslinking process is in agreement with that measured for E-NC-150ATHU. After 165 kGy, the elastic modulus decreases with an increasing irradiation dose indicating that unfilled and filled materials are submitted to a major phenomenon of chain scissions. However, it can be noted that the elastic modulus of E-NC-150ATHU at high irradiation doses is closed to that of E-NC. Given the reinforcement factor, this is another indication that the matrix is more rapidly degraded in presence of fillers. Crosslinked materials: Given the measurement uncertainties, it can be noticed that 32 phr of ATH leads to an increase in modulus usually expected with this filler content, whatever the irradiation dose (cf. figure 4 b)). However it can be noticed that the filler reinforcement factor decreases from 1.2 to 1.1. Such comments must be made with caution given the measurements uncertainties. However it is confirmed in the case of higher filler content: the modulus decrease of E-CR-150ATHU material is more important with an increasing irradiation dose than in the case of the E-CR material. The reinforcement efficiency decreases from around 3.5 for non irradiated sample down to around 2.4 for aged samples. This confirms the more rapid degradation at high irradiation doses of the polymer phase in presence of ATH. Though a different evolution of the sol fraction for E-CR-150ATHU and ECR-150ATHT materials, a similar evolution of elastic modulus is found for theses filled rubbers. Whatever the irradiation dose, the modulus of E-CR-150ATHT is below that of ECR-150ATHU. As said in section 3.2, the filler treatment can promote a better filler dispersion which can lead to lower effective aspect ratio of the fillers that is a lower reinforcement. However a less rapid decrease in the elastic modulus for E-CR-150ATHT material at beginning of irradiation can be noticed. This can be related to the quasi-constant sol fraction of this material for doses below 300 kGy, which confirms the crosslinking phenomenon at the beginning of irradiation.

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Figure 4: Evolution of the elastic modulus at 80C with the irradiation dose a) for uncrosslinked materials (E-NC, E-NC-150ATHU) (dashed lines are guide for the eyes) b) for crosslinked materials (E-CR, E-CR-32ATHU, E-CR-150ATHU, E-CR-150ATHT) (dashed lines are guide for the eyes) for E-CR-150ATHU and for E-CR-150ATHT)

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3.4.2. At large deformations Figures 5 and 13 present the tensile curves of the irradiated crosslinked samples. With untreated fillers, irradiation leads to a decrease in the stress at a given strain. This is obviously due to the polymer degradation. All the materials filled with untreated fillers have a totally different rupture behavior compared to the unfilled materials which show a degradation of their ultimate properties with irradiation (i.e. a decrease in both stresses and strains at break). Their elongation at break is largely increased with irradiation dose while the stress at break is kept constant. These differences in ultimate properties must be related to the possibility or not of energy dissipation provided by the fillers through decohesion mechanism. Note that the behavior of E-32ATHU, not presented here, is similar to that of E-150ATHU sample except that the reinforcement is, as expected, smaller. The consequences of irradiation on the tensile properties of E-150ATHT show two sequences. Firstly, like for untreated fillers, irradiation leads to a decrease in the stress levels. In the same time, the elongation at break tends to decrease, as observed in the case of the unfilled matrix. Thus, the silane treatment hinders matrix decohesion, which means that at the early stage of degradation, the matrix controls the rupture properties. For high doses, like in the case of untreated fillers, the deformation at break increases. This could be an indication of a partial degradation of the filler-matrix covalent bonds, or at least, of the degradation of the polymer matrix in the filler vicinity, eventually enabling at high irradiation dose some decohesion mechanisms. The decrease in the ability of the ATHT-matrix interaction to avoid decohesion with increasing irradiation can be evidenced by the results of the tensile test cycles carried out at 80C (see Figure 6). Indeed irradiation leads to a strong decrease in the stress value at which the increase in cycle area occurs. This is evidenced for treated and untreated fillers, though this decrease is more important for treated fillers: it changes from around 5 MPa at 0 kGy down to 3 MPa at 510 kGy. Note however, that the stress level measured at a given strain for E-CR-150ATHT is still higher than that measured for untreated filler, indicating that some strong covalent bonds between the filler and the matrix remain. Thus, all the experimental results clearly show the influence of the filler presence and the influence of the filler matrix interaction in both the degradation kinetic and its consequences on the mechanical properties.

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Figure 5: Large deformation behavior at 80C of: a) E-CR-150ATHU, b) E-CR-150ATHT

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Figure 6: a) Tensile tests at 80C for E-CR-150ATHU-510, b) Evolution of the cycle area with the true stress for E-CR-150ATHU and for E-CR-150ATHT

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3.5. Evaluation of the filler influence on the degradation kinetic

The more rapid degradation of the matrix in presence of filler can be quantitatively estimated from the different experimental results. For E-CR-150ATHU: considering the modulus data, it can be made the assumption that the reinforcement factor is independent on the irradiation dose. Such assumption is reasonable since the filler dispersion, geometry and modulus is likely not modified by irradiation. Taking a reinforcement factor F of 3.11 (which is the theoretical value given by the Christensen and Lo model), the evolution of the elastic modulus Em of the polymer phase can be deduced from the experimental values of the elastic modulus of the composite material E at 80C, (cf. Figure 7 b). It is clearly shown from the deduced curve the more rapid degradation of polymer phase in the filled materials than in the unfilled material. As shown in a previous paper [10], the evolution of the elastic modulus of the matrix during irradiation for E-CR and E-CR150ATHU materials can be fitted above 50 kGy, following the relation:

E fit

E0 1 Fp

13

exp

ASD

With D the irradiation dose, E0 the extrapolated elastic modulus of the matrix at 0 kGy, Fp the soluble fraction, S a parameter significant of the efficiency of the dose in the scission reaction. Note that this equation is only used above 50 kGy since a crosslinking phenomenon occurs below 50 kGy. The additional parameter A is taken equal to one for E-CR; its value in the case of E-CR-150ATHU is deduced from the curve fit. Taking all the other parameters equal to those used for E-CR, a very good fit is obtained with a factor A equal to 1.5 (cf. Figure 7 b), suggesting that the filler presence leads to a degradation kinetic 1.5 times more rapid.

Taking a reinforcement factor of 3.5 (which corresponds to experimental data), the found acceleration of the degradation due to the filler presence would be more important than that estimated with a reinforcement factor of 3.1 and therefore our conclusion would be even reinforced.
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Figure 7: Evolution of the elastic moduli as a function of the irradiation dose: a) for E-NC (experimental data, ()) and the E-NC-150ATHU deduced matrix (), and curve fits (dashed line A=1, bold lines A=2) ; b)for for E-CR (experimental data, ()) and the E-CR-150ATHU deduced matrix, (), and curve fits (dashed line A=1, bold lines A=1.5)

Another estimation of the kinetic acceleration by the filler presence can be deduced from the sol fraction data. To do so, the Charlesbys approach is used [30, 31]. This gives a simple expression relating the sol fraction Fp to the irradiation dose. As shown in a previous paper
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[30], for E-CR material, the relation of Charlesby becomes affine with D, since the major phenomenon occurring after 50 kGy is chain scission:
Fp Fp p0 D qf 1 with u1 q f u1 Mn w 6

In this relation, the proportion of crosslinked monomers is constant and equal to qf. The value of this constant can be estimated from the extrapolated elastic modulus of E-CR at 0 kGy (cf. Figure 7 a). It is found equal to 0.015. Moreover, in this equation, p0D represents the chain scission kinetic. Here it is made the assumption that this kinetic is proportional to the irradiation dose (like Charlesby did in his work). Therefore p0 is a constant. M n and w are respectively the average number molar weight and the molar mass of the polymer unit. As shown in the figure 8 b), the experimental evolution of Fp

Fp versus irradiation dose is

in a good agreement with the relation (6). The value of p0 deduced from the fit is equal to 1.67x10-5 kGy-1. The same approach is used for E-CR-150ATHU material. Again the fit is very satisfactory. It is found a slope value of 1.7x10-3 kGy-1. Taking for qf the same value than for the matrix, it is found a value of p0 equal to 2.58x10-5 kGy-1. This is again 1.5 times the value of p0 found for E-CR, confirming the value of the acceleration factor previously deduced from the modulus data.

Figure 8: Evolution of Fp

Fp versus irradiation dose for E-CR (experimental data (),

linear fit (dashed line) and for E-CR-150ATHU (experimental data (), linear fit (bold line)

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E-NC-150ATHU material: Same approach can be used for uncrosslinked materials. This case is more difficult, since these materials are submitted to an important crosslinking process during irradiation. However the evolution of the modulus of the E-NC-150ATHU matrix taking the same reinforcement factor used for E-CR-150ATHU (3.1) can be estimated. The deduced curve (Figure 7 a)) suggests again that the crosslinking process (before 165 kGy) and the degradation (after 165 kGy) are more rapid in presence of fillers. Again an estimation of this acceleration by the fillers can be quantified. Following [10], the elastic modulus of matrix for these materials (E-NC, E-NC-150ATHU) can be fitted by:

E fit

E0 ' 1 Fp

13

E0 ' 1 Fp

13

1 exp

ACD exp

ASD

With S significant of the scission kinetic and C related to the crosslinking process. A is equal to one for E-NC since it is the reference material. For E-CR-150ATHU, taking the same parameters used for E-NC, except the parameter A as an adjustable parameter, the best fit is obtained with A equal to 2. Thus the acceleration by the filler presence of the chemical processes involved by irradiation is also evidenced in the case of initially uncrosslinked materials and seems to be even more pronounced. To conclude, all experimental results suggest that the introduction of ATH fillers in EPDM matrix increases the efficiency of the irradiation. The acceleration factor is of the order 1.5 for crosslinked materials and even higher for uncrosslinked one. Different articles report ATH degradation under gamma or electronic irradiation [13, 14, 32]. This degradation especially leads to their dehydration and the formation of radicals. These supplementary radicals might be at the origin of the observed accelerated degradation in the composite. Same articles suggest that the supplementary radicals are localized at the filler surface. This points out that the accelerated degradation in composite should preferentially occur in the filler vicinity. The use of filler treatment could have brought supplementary information on this phenomenon. Unfortunately, as discussed previously, the E-CR150ATHT matrix was initially less crosslinked than E-CR. This leads during irradiation to a supplementary crosslinking phenomenon, which hinders the same type of analyses performed with E-CR-150ATHU. This makes any conclusion on the role of the filler surface in the degradation process more difficult. However, if we consider the evolution of the sol fraction of E-CR-150ATHU and of E-CR-150ATHT versus irradiation dose, we can note that both join at high irradiation dose, suggesting that the crosslinling process occurring in E-CR150ATHT at the beginning of irradiation compensates the initial lower crosslink density so that this one reaches the one of E-CR-150ATHU at high dose. Thus, at high irradiation level, the matrix in both materials composite might be similar, which would be in agreement with the evolution of the elastic modulus. Within this assumption, that would mean that the acceleration of the degradation mechanism is similar for both materials. Such conclusion is surprising since the ATH treatment is expected to modify the formation of the supplementary radicals at their surface. This can be possibly explained by a degradation of the filler-matrix covalent bonds induced by filler treatment. However, the swelling results and the mechanical properties at large deformations imply that these interactions are not totally degraded during irradiation. If some questions remain about the mechanisms involved in the acceleration of the degradation kinetic by the fillers, in any case this acceleration has tremendous consequences in the mechanical properties when the materials are tested above their melting temperature
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(60C). The next section is focused on the consequences of the irradiation on the mechanical properties below this temperature, i.e. in the semi-crystalline state.

3.6. Consequences on mechanical properties at 25C It has been reported in a previous study [33] that our unfilled EPDM presents a lamellar microstructure in the undeformed state. In the case of ATH filled EPDM, the Small-Angle XRay Scattering experiments cannot be easily used because of the presence of fillers: indeed the absorption due to the fillers masks the crystallite scattering. However, DSC can be used. Figure 9 presents the DSC curves of the unfilled materials, and of E-CR-150ATHU and ECR-150-ATHT non-irradiated and irradiated at 510 kGy. Conversely to the unfilled material which presents a unique peak centered around 45C, the presence of fillers, treated or not, leads to the presence of a second peak (which is not suppressed by the thermal protocol). This second peak is centered at 50C while the first maximum occurs at 40C. The filler treatment does not have any influence on these curves, which means that the filler surface is not involved in this modification of the thermogram. Moreover, the sol fraction presence in the case of E-CR-150ATHT has also no consequences. This is not surprising since the study of the crystallinity of E-CR and of the same uncrosslinked sample has shown that the crosslink density, within the range studied, has only a small influence on the crystallinity ratio. The modification of the thermogram by the filler presence is attributed to a modification of thermal transfer during the thermal protocol and the DSC measurements. However, these modifications are small. Following the well-known Gibbs-Thomson equation, a variation of a DSC peak position from 40C up to 50C is significant of a decrease in the crystallite size of only 0.4 nm. Moreover, the calculation of the crystallinity ratio from the thermogram gives value equal to 111% for all the non irradiated samples. Thus, it can be concluded that the filler has a negligible impact on the crystalline microstructure of the materials.

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Figure 9: DSC analyses of E-CR, E-CR-150ATHU and of E-CR-150ATHT series at 0kGy and 510 kGy The same figure presents the thermogram of the samples irradiated at 510 kGy. Like for unfilled materials, irradiation leads to an increase in the peak temperatures of about +5C. A peak integration leads also to an increase in crystallinity ratio of about 1%. However, such an increase is within the experimental uncertainty; moreover, as said above, such an increase in the peak temperature means a small increase in crystallite size. Thus, it can be concluded that irradiation only leads to a slight process of chemi-crystallization which does not significantly modify the microstructure of the filled materials. Figure 10 reports the elastic modulus of non irradiated E-CR, E-CR-150ATHU and E-CR150ATHT, deduced from the tensile tests presented in Figures 11 and 12. The semi-crystalline phase induces a strong increase in the elastic modulus and in the stress level at given strain for all the materials. The crystalline microstructure seems to control the strain at break, which is remarkably higher than that measured at 80C for the same materials. As expected, the introduction of 150 phr of ATH leads to an important reinforcement of the material, within a ratio of 3.2. Like at 80C, such a ratio is close to the one predicted by Christensen and Lo model [26, 27]. This suggests that there is no synergistic effect between the fillers and the crystallites in the reinforcement such as the one reported in the case of the semi-crystalline nanocomposites [23, 34]. The filler treatment does not have significant influence on this reinforcement. This was expected since it does not have one at high temperature, and it does not either significantly change the crystalline morphology. As shown in the same figure 12, the case of E-CR-150ATHU, irradiation leads to in to a decrease of ca. 25% of the modulus below 300 kGy, which then stabilizes at high irradiation dose. This decrease is much lower
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than the one found at 80C, indicating that the crystallites attenuate the matrix degradation. With treated fillers, the modulus evolution is within the uncertainties. The modulus stability below 300 kGy might be explained by the supplementary crosslinking phenomenon evidenced by the tensile tests performed at 80C.

Figure 10: Evolution of the elastic modulus at 25C with an increasing irradiation dose for E-CR, E-CR-150ATHU and E-CR-150ATHT

As shown in Figures 11 and 12, whatever the irradiation dose, the introduction of fillers leads to a strong increase in the stress level at intermediate strain, followed by a decrease in stress level at the highest strain (in other words to a decrease in hardening). Thus, the stress at break for E-ATH150U is lower than for E-CR, and the strain at break is roughly unchanged. This can be explained by the decohesion process already evoked in section 3.3., which leads at high strain to a lower stress level. This decohesion process seems to be more pronounced for irradiation dose above 50 kGy like previously observed at 80C. As shown in Figure 11 b), like at 80C, the silane treatment induces an important hardening and a decrease in the strain at break. This hardening is obviously due to the filler-polymer covalent bonds which are mechanically active at large strain. Given the experimental uncertainties, it is difficult to comment in detail the rupture behavior. However, like at 80C, it can be noticed a slight decrease in the strain at break for irradiation dose below 300 kGy followed by a increase in this strain at break for higher irradiation dose, while the stress at break slightly decreases. As explained above, this behavior might be due to a promoted

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decohesion mechanism at larger irradiation dose although the development of this mechanism is limited by the silane treatment.

Figure 11: Large deformation behavior at 25C for a) E-CR-150ATHU (Continuous lines) and for b) E-CR-150ATHT (Continuous lines); dashed lines are for E-CR at 0 kGy and at 510 kGy

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Figure 12: Average strains and stresses at break with error bars for E-CR, E-CR-150ATHU and E-CR-150ATHT for tensile tests at 80C and at 25C

4. Conclusions The addition of micronic fillers such ATH induces a reinforcement of the mechanical properties at small strain predicted by classical model. This reinforcement is similar when these fillers are treated with a coupling agent, but the treatment induces a strong hardening at large strains, below and above the melting temperature. The filler influence on the degradation mechanisms during ageing by gamma irradiation, and on the evolution of mechanical properties is clearly evidenced. Indeed, the presence of an important filler fraction accelerates the degradation. Above the melting temperature, this induces a decrease in the apparent mechanical reinforcement factor with increasing irradiation dose. In addition, with untreated fillers, the degradation promotes decohesion mechanisms which enables larger strains at break than those measured with unfilled materials. The acceleration of the degradation kinetic by the filler might be due to the formation of supplementary radicals at the filler surface; however it is not clear whether the use of the filler treatment attenuates or not this accelerating effect. Thus the mechanisms involved in the acceleration of the degradation are not yet well understood by the authors. Note that part of the filler treatment remains efficient at high dose and seems also to delay but not suppress the occurrence of decohesion mechanisms at large strain. Like already observed in the case of unfilled crosslinked EPDM [10] and silica filled EPDM [35], the consequences of ageing by gamma-irradiation are strongly limited below the melting temperature, because of the presence of crystallites. These crystallites can be seen as supplementary multifunctional crosslinks which are mechanically more active than the
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elastomer crosslinks. Therefore the inactivation of the polymer crosslinks by chain scission mechanism is made less important in the material mechanical response and all the phenomena evidenced above the melting temperature are partially masked in the semi crystalline state. To conclude, this paper highlights that the filler presence has an influence on the degradation mechanism and that the consequences of this degradation on the composite mechanical properties are not straightforward. Thus it seems obvious that it is not possible to understand and deduce the evolution of the mechanical properties of filled composite submitted to irradiation from the sole study of the degradation of the unfilled polymer.

Acknowledgment It is a pleasure to acknowledge the joint research program COPOLA between EDF, NEXANS France, LABORELEC, CEA, INRA and CNRS. We thank Dr. Agns Bogner for obtaining the microscopy images.

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26. CHRISTENSEN RM, LO KH. Journal of the Mechanics and Physics of Solids, 1979; 27:315-330 27. CHRISTENSEN R.M . , Theory of viscoelasticity, Academic Press, New York, 1971. 28. MONTEZIN F, LOPEZ CUESTA JM, CRESPY A, GEORLETTE P. Fire and materials 1997; 21: 245-252 29. DUBNIKOVA IL, BEREZINA SM, ANTONOV AV. Journal of applied polymer science, 2004; 94: 1917-1926 30. CHARLESBY A, PINNER SH. Proceedings of the Royal Society the London, 1959; A249: 367-386 31. CHARLESBY A. Proceedings of the Royal Society the London, 1954; A222: 542-557 32. KOGURE T. Journal of American Ceramic Society, 1999; 82:716-720 33. PLANES E, CHAZEAU L, VIGIER G, CHENAL JM, STUHLDREIER T. Journal of Polymer Science Part B: Polymer Physics in Press

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Article 4: Influence of fillers on mechanical properties of silica filled EPDM during ageing by gamma irradiation
PLANES E., CHAZEAU L., VIGIER G., STULDREIER T.

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Sommaire

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Abstract .............................................................................................................................................. 179 1. 2. Introduction ............................................................................................................................... 179 Experimental.............................................................................................................................. 181 2.1. 2.2. 2.3. Materials .............................................................................................................................. 181 Ageing conditions................................................................................................................ 182 Instruments .......................................................................................................................... 182 IR spectroscopy ........................................................................................................... 182 Swelling meausrements ............................................................................................... 183 Swelling in xylene ................................................................................................... 183 Water uptake............................................................................................................ 183 Tensile tests ................................................................................................................. 184 Differential scanning calorimetry analysis .................................................................. 184

2.3.1. 2.3.2. 2.3.2.1. 2.3.2.2. 2.3.3. 2.3.4. 3.

Results and discussion ............................................................................................................... 186 3.1. 3.2. 3.3. Preliminary characterization of studied materials ............................................................... 186 Oxidation ............................................................................................................................. 187 Degradation kinetic Consequences on mechanical properties at 80C ............................ 187 For E-CR material ....................................................................................................... 187 For E-SiU material ...................................................................................................... 190 For E-SiT material ....................................................................................................... 192

3.3.1. 3.3.2. 3.3.3. 3.4. 4.

Consequences on mechanical properties at 25C ................................................................ 195

Conclusions ................................................................................................................................ 198

Acknowledgments.............................................................................................................................. 199 References .......................................................................................................................................... 200

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Cet article concerne ltude de linfluence des charges silices. Ces charges ont la particularit dtre de taille nanoscopique i.e. davoir une trs grande surface spcifique. Cela a des consquences connues sur le renforcement qui est en gnral bien plus lev que dans le cas des charges microniques. Lobjectif de cet article est dtudier si cela a aussi des consquences sur lvolution des proprits mcaniques lors du vieillissement par irradiation. Comme pour lATH, deux types de charges ont t tudis : lune sans traitement et lautre avec un traitement favorisant les interactions charge-matrice. Une tude la fois des proprits mcaniques ltat amorphe (i.e. 80C) mais aussi ltat semi-cristallin (i.e. 25C) est prsente.

Abstract Silica filled EPDM have been irradiated at room temperature. When the silica has no surface treatment, the matrix degradation is accelerated. Moreover, irradiation leads to a modification of the silica surface and stronger interactions between filler and matrix are formed at high radiation dose. Conversely, in the dose range studied, when using a silica treatment which promotes the formation of filler/matrix covalent bonds, irradiation leads to their mechanical deactivation, either by their direct degradation, or by the degradation of the polymer in their vicinity. Moreover, the treatment of silica enables to delay the acceleration of the degradation to the highest radiation dose studied. This delay might be due to a more difficult diffusion of the supplementary radicals created by the silica, because of the presence of the silane treatment. Thus, the presence of silica fillers as well as their surface treatment influences the impact of irradiation on the mechanical properties of the filled materials. It influences it both chemically, by a modification of the kinetics of the degradation reactions, and physically, through the complex modification of the stress transmitters involved in the mechanical properties of the filler network.

1. Introduction

Some applications of filled elastomer can involve ageing by gamma irradiation. For instance, the elastomers used as cable insulation in nuclear power plants are submitted to irradiation during their lifetime. Several studies have been devoted to the understanding of the consequences of ageing on the mechanical properties of unfilled elastomers [1, 2, 3, 4, 5 ]. However in most applications, elastomers are formulated with fillers. For instance, incorporation of silica fillers in elastomers are well known to improve their mechanical properties, as indicated by the increases in elastic modulus, hardness and wear resistance it enables. However, the use of such fillers can also influence the degradation mechanisms. They can modify the polymer degradation by trapping radicals or degradation by-products which can interact with intermediate chemical species involved in the matrix degradation. They can also be degraded and lead to the formation of supplementary degradation byproducts, which can interact with the matrix degradation process. Moreover, whether fillers are still inert or not during the matrix degradation, this matrix degradation can induce a
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modification of the filler-matrix interaction: this may have consequences in the reinforcement efficiency of the filler, and therefore be involved in the consequences of the degradation in the overall properties of the composite. Very few studied were devoted to the irradiation effect on silica filled rubbers, and they mainly focused on polydimethysiloxane (PDMS) filled silica systems [6, 7, 8, 9, 10]. Indeed, silicone rubbers are known to exhibit a high resistance to various kinds of irradiation. Stevenson et al. [6] have reported that radiation induces crosslinking between the filler and the matrix and have shown its influence on high strain mechanical properties. More precisely, other studies [7, 8, 9, 10] have shown the modifications of PDMS-silica interfaces induced by gamma irradiation: firstly a decrease in filler-matrix interactions at low gamma dose has been evidenced due to the destruction of the hydroxyls species by the paramagnetic species created at the silica surface; then at high gamma dose, a reduction of segmental chain dynamics has been demonstrated, indicating that crosslinking reactions took place either in the polymer phase or either between filler and matrix. To our knowledge no study concerns the ageing of nanoscopic silica filled ethylene propylene diene monomer (EPDM). However, EPDM is often preferred to silicone because of its excellent capability in electric insulation. A previous study about the ageing by gamma irradiation at room temperature in presence of oxygen of unfilled crosslinked EPDM, has shown that the preponderant phenomenon induced by gamma radiation is chain scission [1]. The evolution of the elastic modulus at 80C, that is when this EPDM is in wholly amorphous state, can be easily evaluated from a chain scission simulation, but the rupture behavior at the same temperature is more sensitive to the network architecture, which becomes very irregular during irradiation. At room temperature, the studied EPDM is semi-crystalline. In that case, the arrangement and the proportion of crystallites control the mechanical properties at small deformations [11]. Nevertheless at large strains, the interactions between crystalline entities through tie molecules play a preponderant role. Thus, their degradation induces a smaller hardening phenomenon and a decrease in elongation at break. When introducing silica in EPDM, the created filler-matrix interactions are very different than those found in silica filled PDMS. There are not strong hydrogen bonds between silica and the matrix, such as those observed with PDMS. Therefore, it can be expected that the consequences of ageing under irradiation will be different from those found with silica filled silicone. This motivates the present study, devoted to the consequences of ageing under irradiation on the mechanical properties of a silica filled EPDM. In order to understand the role of the semi-crystalline phase in the polymer matrix, the materials are studied both in the rubbery state (i.e. at 80C) and in the semi-crystalline state (at room temperature). Morever, in most applications, these materials are formulated with a specific coupling agents, such a as bifunctionnal organosilane, which promote the formation of covalent bonds at the filler matrix interface. For this reason, we also present results obtained with a formulation containing such a silane treatment.

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2. Experimental 2.1. Materials

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Figure 1: Reaction of filler-matrix coupling

EPDM elastomer (Nordel IP NDR 3722 P from Dow Chemical Company) is made of 70% ethylene, 29.5% propylene and 0.5% ENB and the crosslinking agent is dicumyl peroxide (Perkadox BC-FF from Akzo Nobel). EPDM is reinforced with silica ULTRASIL VN3 supplied by Degussa. The filler is highly dispersible silica with a specific surface of 175 m2/g, the estimated size of a primary particle is c.a. 15 nm. The filler ratio in the studied materials is constant and equal to 50 phr (50 weight ratios for 100 weight ratios of EPDM, this corresponds to a weight fraction of 33%, and a volume fraction of 17%). The surface treatment chosen to improve the filler-matrix interactions is a vinyltrimethoxysilane Z6300 supplied by Dow Corning. It is made of a reactive foot with three ethoxy groups, which react with the silanol of the silica surface, and an alkyl chains with a vinyl function, which can react with the matrix during crosslinking [12]. The reaction of filler-matrix coupling is illustrated in figure 1. Following the procedure of Ramier et al [13], the optimal quantity of surface treatment, to effectively cover this type of silica surface is estimated to 3 phr. The different formulations are given in table 1. The E-SiU material contains untreated fillers, conversely to E-SiT material, which contains treated fillers. The samples are processed following three steps. The first step is the mixing of the matrix and the incorporation of fillers and crosslinking agent in the polymer. First the matrix is introduced in the internal mixer and mixed for 2 minutes, and then the fillers are introduced. In the case of treated fillers, the organosilane molecules are introduced with 2/3 of the silica, and then the rest of filler is introduced. After 5 minutes of mixing, peroxide is added and mixed for 10 min, at low temperature (80C) to prevent any reaction of the crosslinking system. In order to obtain a better dispersion, the second step is the mixing in an external mixer (cylinders) for 10 min at low temperature (80C). During the last step, the compound is pressed as 1-mm-thick films at 170 C to promote crosslinking reactions. The filler presence induces a sharp increase in
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viscosity of the filler-polymer mix before and during its crosslinking. This is explained by the hydrodynamic effect of the rigid filler phase, but also by the different types of involved interaction, the filler-filler ones, and the filler-matrix ones. Therefore, there is no simple description, and modelling of such reinforcement which would enable to deduce the properties of the matrix, especially its crosslinking density from rheology measurement of the material during curing. Given this difficulty, we used the common industrial method which consists in measuring with a MONSANTO rheometer the curing time needed to obtain 98% of the maximum torque extrapolated at infinite cure time (t98 at 170C). Thus the vulcanisation at 170C is stopped after 10 minutes for the unfilled EPDM and after 5 minutes for silica filled EPDM.

Sample name E-CR E-SiU E-SiT

EPDM 100 100 100

Peroxide 3 3 3

Silica 0 50 50

Surface treatment 0 0 3

Table 1: Formulation of the studied materials (the proportions are expressed in phr: per hundred parts of matrix)

2.2. Ageing conditions E-CR, E-SiU and E-SiT samples (for unfilled EPDM, and EPDM filled with untreated and treated silica respectively) are exposed to -radiation of a 60CO source at a dose rate of 1 kGy/h in an oxygen atmosphere for doses 50, 165, 300, 510 kGy (Arc Nucleart Grenoble France): the water temperature of the pool, where exposures are performed, is about 18C. Afterwards, the samples are stored under vacuum at about 22C. The samples will be named hereafter E-CR-XXX, E-SiU-XXX and E-SiT-XXX with XXX the irradiation dose.

2.3. Instruments 2.3.1. IR spectroscopy In order to evaluate the degree of oxidation of the materials, analyses by IR spectroscopy were performed. Firstly, changes in carbonyl concentration were followed by a Thermo Nicolet Nexus FT-IR spectrophotometer with the Attenuated Total Reflectance (ATR) accessory using 32 scans and a resolution of 4 cm-1. IR spectroscopy in the transmission mode could not be used because the samples are absorbing. Secondly, oxidation (carbonyl) profiles were deduced from IR-microspectroscopy using a Continum microscope coupled to a Nexus Nicolet optical bench (32 scans, resolution of 4 cm-1). A slice of sample of about 40 m was cut by cryo-microtom in the thickness direction. Then IR spectra were measured on this slice every 50 m to have an oxidation profile along the sample thickness. These analysis were conducted in CNEP - Centre National dEvaluation de Photoprotection Clermont Ferrand (France).
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2.3.2. Swelling meausrements 2.3.2.1. Swelling in xylene

Swelling measurement is a useful technique to characterize the network degradation. In the case of unfilled rubber, the swelling restriction is due to crosslinks connecting the polymer chains, which avoid their extension and their diffusion. Because of the filler-rubber interactions, the filler addition is equivalent to the introduction of additional crosslinks, which perturb the polymer swelling. Samples with an initial mass Mi are introduced in xylene for 8 days to achieve the swelling equilibrium; then the materials with a swelled mass Ms are dried under vacuum at 60C during 1 day and finally weighted to obtain the dried mass Md. The swelling ratio Q as well as the sol fraction can be deduced. In the case of the composites, TGA (TGA F3 apparatus from Netzch) enables to estimate the filler weight ratio i in the initial sample and the filler weight ratio d in the dried sample after swelling. Therefore, the swelling ratio Q and the polymer soluble fraction Fp (%) can be evaluated from the following relations: Md polymer M s Q 1 1 xylene M d 1 d

2 1 i Mi At low dose, given the low sol fraction measured for E-SiU and E-SiT materials, the difference found between d and i is within the experimental uncertainties. However, for high irradiation dose, actually for total sol fractions above 20%, it is found that d is clearly lower than i, meaning that the sol fractions contain a significant amount of fillers.
Extensive use has been made of the kinetic theory of rubber elasticity and the Flory-Rhener network theory of swelling to estimate the degree of crosslinking in crosslinked rubbers. The success of these techniques with unfilled elastomers makes highly desirable their extension to the technologically important filler-reinforced rubbers. Unfortunately, the introduction of rigid filler particles into the network leads to some serious theoretical and practical complications. The most basic of these is the inability of the network to undergo deformations which are affine with the sample dimensions. For this reason, we did not use swelling measurements to calculate crosslink densities.

Fp

Mi

Md

2.3.2.2.

Water uptake

Because of the presence of silanol on its surface and of its large specific surface, silica can absorb a significant amount of water. Thus, swelling in water method can provide useful information about the silica surface and eventually the filler-matrix interface. The samples,
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cut as identical parallelepipeds to offer a constant surface to the water, are firstly dried under vacuum for 24 h at 100C to remove the maximum amount of water on the silica surface. After weighting dried samples (Mdried), they are put in distilled water at room temperature for one month and then weighted again (Mswollen). The water uptake Sw (expressed in %) is then calculated from: M swollen M dried Sw 100 3 M dried 2.3.3. Tensile tests Tensile tests are performed on an MTS device equipped with a temperature controlled chamber. Experiments are conducted at 80C and at 25C with a true strain rate 0.01 s -1. An image processing acquisition system (Apollor VideoTraction System) is used to obtain the true stress true strain curve. The samples are dumbbell-shaped with dimensions 20 x 4 x 1 mm3. For one type of samples, three specimens are tested; on figures only one test is reported, but the average stresses and strains at break on the three specimens are given in a separated figure (cf. figure 13). Note that the rupture has not been reached for the E-SiU samples. Besides, the elastic modulus E is calculated as the slope of the linear initial portion of the curve. Tensile test cycles are also performed at 80C. Sample is stretched up to a 0.2 true strain, then relaxed during 5 minutes; then, it is stretched again up to a 0.4 true strain. This experience is repeated with a 0.2 true strain increment until the sample rupture.

2.3.4. Differential scanning calorimetry analysis

All measurements are made with a Perkin-Elmer Diamond calorimeter, with 10-15 mg of material encapsulated in standard aluminum pans. Dry nitrogen is used as the purge gas. The instrument is calibrated with indium using a scanning rate corresponding to the heating rate of the experiments. The crystallization temperature domain of our EPDM is large [11]: from about -50C up to 60C. Indeed, when the polymer is cooled from 80C to -50C, one wide peak can be observed during the heating ramp. If an isothermal treatment of several hours at the temperature Tc is performed during cooling, three melting peaks are obtained during the heating scan: The first one corresponds to the crystallite population, formed during cooling from 80C to Tc. The second one concerns the crystallite population formed during the isothermal treatment at Tc. The third one corresponds to the crystallite population, created during the cooling from Tc to -50C. A test series has been performed to evaluate the optimal crystallization temperature, i.e. the temperature Tc which leads to the highest crystallinity ratio with the fastest crystallization kinetic. The found Tc is 22C and the isothermal treatment to obtain a stable crystallinity ratio is equal to 12h.
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Thus, the thermal treatment applied to all samples is the following: - A heating ramp up to 80C to erase the previous thermal history - And a rapidly cooling down to the optimal crystallization temperature 22C and storage during 12h at this temperature Moreover, in order to not affect the crystallinity by any further treatments around this temperature, in particular the ageing in the pool at 18C, and the post-irradiation at 22C, the samples are annealed by heating ramp at 1C/min up to 38C and maintained at this temperature during 6h. Then they are cooled down to 22C and stored at this same temperature. This treatment enables to get a unique well defined melting peak for unfilled EPDM materials and a double peak for silica filled EPDM. Thus all materials have one or two crystallite populations with melting temperatures above 22C. To study the materials cristallinity after their irradiation, they are cooled from room temperature down to 50C at the cooling rate of 10C/min and heated up to 100C at 10C/min. The cooling from room temperature to -50C is necessary to avoid that DSC peak overshoot overlaps the melting peaks. But this cooling induces the formation of an additional melting peak, which can be observed between -40C and 20C. That is why the crystallinity ratio Xc is defined from enthalpy Hf of the melting peaks between 22C and 60C. Hf Xc 4 1 Hf0 where the weight ratio of fillers and Hf0 is taken equal to 290 J/g [14], i.e. the value for perfect polyethylene crystal, since it is assumed that only polyethylene segments can crystallize.

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As reported in figure 2, the swelling ratio Q of E-SiU is higher (4.2) than the matrix one (3.7). As indicated in the experimental part, the polymer matrix of the composite may be slightly less crosslinked than the unfilled EPDM because of the choice of the curing time. This is in agreement with the sol fraction Fp values: E-SiU contains a soluble fraction of about 3.2%, conversely to the unfilled sample, although this result must be considered with caution because of the experimental uncertainties. Note that this soluble fraction could also be due to occluded polymer in the complex filler structure. The modulus increase provided by the incorporation of silica is visible in figure 5: the elastic modulus at 80C of E-SiU is about 4.5 times higher than the modulus of the unfilled matrix. This is much higher than the reinforcement predicted by the Christensen and Lo model [15]. This model has shown its validity for micron size filler [16] and predicts a reinforcement of a factor 1.6 for 20%vol. of filler. This discrepancy between theory and experiments is generally explained by the formation of a strong filler network [17]. The efficiency of the silica surface treatment in E-SiT is first evidenced by the water uptake measurements (cf. Figure 4): Sw is more important for E-SiU than for E-SiT. Nevertheless, the soluble fraction of E-SiT is higher than the one found for E-SiU. Thus, the E-SiT polymer phase is certainly slightly less crosslinked than that of E-SiU. The reasonable explanation is that a part of the peroxide has been used in the filler/matrix coupling reactions. Despite this, the swelling ratio of E-SiT is smaller (2.8) than the one E-CR. This is not surprising, indeed, in the case of nanocomposites such as the studied materials, in which nanoscopic fillers likely form a percolating reinforcing structure [17], filler-matrix covalent bonds become important in the material response at larger strains, in particular for strain level such as that involved in the swelling measurements, or for strains at which hardening appears in stress-strain curve, that is when the filler structure is stretched (cf. Figure 6a and 6b). Conversely, at small deformations (i.e. in the deformation range of the shear modulus measurement), the nature of the polymer-filler bonds, the fact that they are covalent or physical, is not a key parameter, presumably because they are in any case strong enough to transfer the stress at the filler-matrix interface. Thus, the elastic modulus at 80C of E-SiT is slightly smaller than the one of E-SiU (cf. Figure 5). Note that this lower modulus can be attributed to the slightly less crosslinked matrix, or to a less reinforcing filler structure [18]: the filler treatment may lead to a decrease in the filler-filler interactions by promoting the filler-matrix ones; consequently, the filler network is less efficient to reinforce the composite. The rupture behaviour cannot be discussed for the E-SiU samples, since they systematically break in the clamps. The authors have no explanation for this peculiar behaviour. However, it can be observed that E-SiT breaks earlier and not in the clamps. The silane treatment seemingly leads to a more brittle behaviour of this material. The same phenomenon was observed in the study of treated and untreated ATH filled EPDM [2]. This might be attributed to the absence of decohesion mechanism which might delay sample rupture by decreasing the local matrix stretching.

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3.2. Oxidation

After radio-oxidation of EPDM, IR spectroscopy shows an increase in absorbance in the hydroxyl absorption region (3800-3000 cm-1) [2] corresponding to the formation of alcohols, acids and hydroperoxides. The formation of carbonyl can be evidenced by an absorption maximum at 1713 cm-1 accompanied by several shoulders around 1785, 1755, 1740, and 1695 cm-1[2]. In the case of silica filled EPDM, the same oxidation products are created. For all materials (unfilled and filled), an increase in hydroxyl and carbonyl absorption regions can be observed with an increasing irradiation dose, but it is not possible to quantify these products by ATR and thus to compare the oxidation level of the different elastomers. Indeed, the IR beam depth penetration and the number of reflections can be influenced by the presence of fillers. However, the use of IR - microspectroscopy on the sample thickness obtained by microtomy can provide the oxidation product spatial distribution within the thickness. The variations in absorbance at 1713 cm-1 are chosen for this characterisation. For E-CR-510 and E-SiU-510, i.e. at the maximal irradiation dose, the oxidation profiles are nearly flat; this indicates that in the irradiation conditions of this study, the oxidation processes can be considered homogeneous within the thickness.

3.3. Degradation kinetic Consequences on mechanical properties at 80C

3.3.1. For E-CR material

The consequences of irradiation on unfilled E-CR are reported in reference 1. At the beginning of irradiation (below 50 kGy), no change of the swelling ratio (cf. Figure 2), a slight increase in the soluble fraction (cf. Figure 3) and in the elastic modulus measured at 80C, i.e. above the melting temperature, (cf. Figure 5) indicates that this material is submitted to concomitant crosslinking / chain scissions processes. Then at higher irradiation dose, the increases in the swelling ratio (cf. Figure 2) and in the soluble fraction (cf. Figure 3) indicate that chain scissions become the preponderant occurring phenomenon. The evolution of the sol fraction can be correctly described using the Charlesby approach which enables to calculate the chain scission kinetic. The consequences of the degradation process on the mechanical properties are recalled on figures 5, 6, 7: the modulus at 80C decreases as well as the stress level of the tensile curves, and the ultimate properties deteriorate.

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Figure 2: Swelling ratio Q, as a function of radiation dose, dashed lines are guide for the eyes

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Figure 3: Polymer sol fractions Fp, as a function of radiation dose, dashed lines are guide for the eyes

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Figure 4: Water uptake Sw as a function of radiation dose

3.3.2. For E-SiU material

Between 0 kGy and 50 kGy, E-SiU does not show any significant evolution of the swelling ratio (cf. Figure 2), of the sol fraction (Fp) (cf. Figure 3) and of the elastic modulus at 80C (cf. Figure 5). Thus, at 50 kGy, there is not a modulus maximum like in the case of the E-CR. Given the assumed crosslink density lower in this material than in E-CR, and the crosslinking process induced by radiation, as evidenced by the modulus increase in the case of E-CR, it can be assumed that the matrix in the filled sample has been submitted to the same competing mechanisms of crosslinking and scissions. Within this assumption, the absence of modulus maximum at 50 kGy might be due to its shift at a lower irradiation dose. Then, at irradiation doses above 50 kGy and up to 300 kGy, the swelling ratio rapidly increases (cf. Figure 2), as well as the polymer soluble fraction Fp (cf. Figure 3). Chain scissions take place, but as indicated by the larger extracted polymer ratio Fp of the filled rubber (at 165 kGy, 25% against 6% for E-CR), this phenomenon is much more important than in the case of unfilled material. The same amount of sol fraction is found in E-SiU at 165 kGy as in E-CR material at 510 kGy This sol fraction variation is correlated with the decreases in the elastic modulus at 80C (cf. Figure 5) and in the stress levels measured in tensile test at 80C (cf. Figure 6). In addition, a modification of the silica surface is evidenced by the water uptake measurements, which show a strong decrease of Sw between 0 and 165
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kGy (cf. Figure 4), indicating that the silica surface becomes less hydrophilic, i.e. that the silanol initially on its surface are degraded. These results strongly suggest that the fillers promote supplementary reaction in the filler vicinity. This is supported by literature. Indeed, it has been reported that the irradiation of silica involves the formation of numerous radicals in the bulk [19, 7, 9]. They may tend to recombine or diffuse to the surface, making the surface reactive, and accelerating degradation reactions, in the filler-surface vicinity. At doses above 165 kGy, both modulus and soluble fraction tend to stabilize. Moreover, the stability of Sw, which is the same for both E-SiU and E-SiT, suggests that the silica surface hydrophilia is not significantly modified anymore. However, the swelling ratio goes through a maximum at 300 kGy to decrease at 510 kGy. This indicates that an additional mechanism of crosslinking occurs and counterbalances the chain scission process. Such phenomenon was not observed in the case of the unfilled polymer. As shown in the material stress-strain curves of E-SiU at 510kGy (cf. figure 6), the formation of these supplementary crosslinks leads to an increase in hardening. Thus, there are two sequences in the modification of the silica surface under irradiation: first, it is made more hydrophobic, and then it reacts with the polymer matrix in its vicinity to form covalent bonds. To confirm the strengthening of the filler-matrix interaction, non-irradiated and irradiated E-SiU samples have been submitted to cycle tensile tests at 80C (cf. Figure 7). The area delimited by two successive tests, which is significant of the energy damage, is plotted as function of stress in figure 7 b). Unexpectedly, E-SiU-510 does not show a delay of the stress at which the energy increase when comparing E-SiU-0 and E-SiU-510. This means that the bonds which are assumed to be formed during irradiation are not numerous enough to lead to a significant modification of the damage behaviour.

Figure 5: Elastic moduli at 80C, as a function of radiation dose, dashed lines are guide for the eyes
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3.3.3. For E-SiT material

In the case of E-SiT, between 0 and 50 kGy, a slight crosslink phenomenon is noticeable as evidenced by a modulus increase and the swelling ratio decrease. This can be due to some additional filler-matrix coupling reactions formed by some residual silane treatment, which has not been covalently bonded to the matrix. This can also be due to crosslinking reactions in the matrix provided by some residual peroxide, since it has been shown that the polymer phase in this material is slightly less crosslinked. As shown in the figure 6, the consequences of this crosslinking on the stress-strain curves are a more important hardening and an earlier rupture in addition to an increase in modulus. Above 50 kGy and up to 300 kGy, the swelling ratio (cf. Figure 2) and the soluble fraction (cf. Figure 3) also increase with the radiation dose, but these increases are much less important than for E-SiU; actually they are comparable to those measured for E-CR. Thus, the polymer degradation is seemingly similar to that of E-CR. There is no indication of a more rapid scission mechanism such as that found in the case of E-SiU. However one can note between 300 kGy and 500 kGy that the swelling ratio and the sol fraction rapidly increases and reaches the values found for E-SiU. Thus, the fastest scission mechanism seems to be delayed by the silane treatment and to occur at larger radiation dose. Such interpretation is supported by the evolution of the mechanical properties with the radiation dose. The stress-strain curves show a delayed decrease of the stress level at a given strain when compared with the stress-strain curves of E-SiU: the decrease becomes significantly visible from 300 kGy and it accelerates between 300Gy and 500 kGy. Eventually, after ageing at 500kGy, the materials with treated and untreated silica have very similar stress-strain curves at 80C; moreover, given their same swelling ratio, it can be deduced that both materials have about the same number of covalent bonds at the filler-matrix interface. As shown previously by cyclic test, this number was not strong enough to change the damage behaviour of E-SiU. E-SiT samples have also been submitted to the same cyclic tensile tests at 80C (cf. Figure 7). The non irradiated E-SiT shows an increase in the energy for a higher stress than E-SiU: this evidences the strongest filler-matrix interface in E-SiT, which breaks at higher stress than E-SIU. The cycle performed on E-SIT irradiated at 510 kGy leads to an energy curve similar to the one of E-SIU510, with an increase in energy which begins at the same stress as E-SiU-510. This confirms that a large number of initially mechanically active covalent bonds at the filler-matrix interface have been deactivated by chain scissions in the interface vicinity. In addition, the modulus value lower for E-SiT than for E-SiU might suggests that, especially at 510kGy, all things equal, i.e. the matrix crosslink density, and the filler-matrix interaction, the filler structure in E-SiT is actually less reinforcing than the one in E-SIU; this would be not surprising since the use of a filler treatment is known to impact the filler dispersion in the matrix. To conclude, all the experimental results show that silica filled materials are largely modified under irradiation. They even suggest that the polymer matrix in the composites is more rapidly degraded than the polymer matrix. Our assumption is that silica fillers promote the formation of supplementary radicals which accelerate the polymer degradation. In addition, when it is not treated, degradation mechanisms induce a modification of the silica surface. Once this one is hydrophobised at the same level as the treated filler, some covalent bonds between the matrix and the filler are formed. The already existing strong bonds between filler
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and the matrix in the case of the material filled with treated silica seem to inhibit such process. For such materials, the acceleration of degradation seems to be delayed to larger radiation dose. This could be due to a diffusion of the supplementary radicals created by the silica, slowed down by the silane treatment.

Figure 6: Large deformation behavior at 80C of a) E-SiU (no rupture is observed) and of b) E-SiT (cf. figure 10)

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Figure 7: a) Cycles at 80C for E-SiU-510 and E-SiT-510; b) Evolution of the cycle area versus true stress for E-SiU and E-SiT at 0 kGy and at 510 kGy

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3.4. Consequences on mechanical properties at 25C

It has been reported in a previous study [7] that the unfilled EPDM presents a lamellar microstructure in the undeformed state. In the case of silica filled EPDM, the Small-Angle XRay Scattering experiments cannot be used because of the fillers absorb X-ray. The cristallinity ratio deduced from DSC measurements prior to irradiation is quasi-equal for the three materials E-CR, E-SiU, and E-SiT. However, their thermograms present significant differences (cf. Figure 8) : two peaks are measured for the filled samples and only one for the unfilled material at 0 kGy; moreover, E-SiU sample presents a first peak enlarged towards lower temperature and E-SiT has a first peak which is centered at temperature 5C below that of the peak temperature of E-CR. However, these differences represent only small variations of the crystallite thickness (when the melting peak is shifted from 45C to 55C the lamellar thickness deduced from the Gibbs Thomson equation only changes from 2.7 up to 2.9 nm). They could be explained by a reduced mobility around the fillers, which is obviously lower for treated fillers.

Figure 8: DSC analyses of E-CR, E-SiU and E-SiT samples at 0 and 510 kGy

Irradiation leads to a shift of the peaks of about +5C. This corresponds to a slight crystallite growth which can be explained by a slight chemi-crystallisation. This is confirmed by the
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progressive increase in the cristallinity ratio from 10.5% to 11.5%. However, if chemicrystallisation occurred, this phenomenon remains limited.

Figure 9: Large deformation behavior at 25C of a) E-SiU (no rupture is observed) and of b) E-SiT

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Figure 10: Average stresses and strains at break for E-SiT and E-CR at 80C and at 25C

Figures 9 a), 9 b) and 10 present tensile tests at 25C of E-SiU and E-SiT. The tensile test curves of E-CR and E-CR-510 are plotted on the same curves. As shown on these figures, the mechanical properties at 80C and at 25C are very different because of the presence of crystallites at room temperature. The deduced moduli are reported on figure 11. Unaged filled samples have the same modulus which is, like at 80C, much higher than that of the unfilled sample: the slightly higher ratio of the filled sample modulus by the modulus of the unfilled sample (around 6 at 25C against 4.5 at 80C) suggests that the reinforcement is due to a mixed crystallite silica network. This idea is supported by the size of silica fillers (around 15 nm) which is in the same range as the crystallite size. Moreover, as expected when measuring modulus, and as recalled above, the covalent bonds between the filler and the matrix in the ESiT sample have as much significant influence on the modulus value as the physical interactions between fillers and matrix in the E-SiU material. The modulus slightly increases in the beginning of irradiation, due to the small chemicrystallisation phenomenon. Thus, like observed in the study of the effect of irradiation on ECR [7], the crystallite presence strongly decreases the impact of the degradation on the mechanical properties in the semi-crystalline state. This holds true for strain below 0.4 since the tensile curves obtained at the different irradiation doses for E-SiU and E-SiT are nearly superimposed (Figure 11). At larger strain, the degradation of the amorphous phase, already evidenced at 80C, obviously decreases the stress transfer between crystallites during the matrix deformation, leading to a decrease in the hardening phenomenon.

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Figure 11: Evolution of the elastic modulus at 25C with an increasing irradiation dose

The creation of filler-matrix bonds in the E-SiU samples by high irradiation dose has a limited impact on the hardening process of the corresponding tensile curve at 25C. As assumed above, this means that these bonds are in small numbers. Besides, even if E-SiU and E-SiT have similar stress-strain curves at 80C, all the E-SiT curves obtained at 25C show a much more important hardening than the tensile curves obtained with the E-SiU samples. Whatever the irradiation dose, the stress level measured for E-SiT is much higher than the one measured with E-SiU (a ratio of about 2 is observed for a true strain equal to 1). Thus, the crystallites presence partly masks at large strain the desactivation, evidenced in the rubbery state, of the filler-matrix covalent bonds by the polymer degradation 4. Conclusions The incorporation of nanoscopic fillers in EPDM induces the formation of a filler network with a larger reinforcement efficiency than when the fillers are micron size. The materials with treated fillers have an elastic modulus close to the one of EPDM filled with untreated fillers. But in the amorphous state like in the semi-crystalline state, they show an more important hardening with a faster rupture. At 25C, the reinforcement measured for both materials is higher than the one found at 80C, which indicates the formation of a mixed crystallite silica network. These materials have been irradiated at room temperature:

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Without treatment, the polymer phase degradation is accelerated. Our explanations is the formation of supplementary radicals induced by the silica irradiation. But at the highest irradiation dose studied, a particular mechanism can be observed: due to the modification of the silica surface, stronger interactions between filler and matrix are formed. Conversely, the silica treatment seems to inhibit the formation of supplementary covalent bonds between the filler and the polymer. In addition, irradiation, leads to a mechanical deactivation of the initially present covalent bonds at the interface, either by their direct degradation, or by the degradation of the polymer in their vicinity. Moreover, the treatment of silica enables to delay such acceleration of the degradation to the highest radiation dose studied. This delay might be due to a more difficult diffusion of the supplementary radicals created by the silica, because of the presence of the silane treatment. As a consequence, both filled rubbers (with and without silane treatment) have similar mechanical behavior at 80C at 510 kGy. At room temperature, i.e. in the semi crystalline state, their properties are mainly controlled by the crystallites. This semicrystalline phase is not deeply modified. In addition, at room temperature, conversely to the filler-matrix covalent bonds created by the silane treatment, the ones created by gamma irradiation in the composite with untreated silica have a much lower impact on the mechanical properties. To conclude, the different experimental results clearly show that the presence of silica fillers as well as their surface treatment influences the impact of irradiation on the mechanical properties of the filled materials. They influence it both chemically, by a modification of the kinetics of the degradation reactions, and physically, through the complex modification by irradiation of the stress transmitters involved in the mechanical properties of the filler network.

Acknowledgments

It is a pleasure to acknowledge the joint research program COPOLA between EDF, NEXANS France, LABORELEC, CEA, INRA and CNRS.

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References

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1. PLANES E, CHAZEAU L, VIGIER G, FOURNIER J. Polymer, 2009; 50: 4028-4038 2. RIVATON A, CAMBON S, GARDETTE JL. Nuclear Instruments and Methods in Physics Research B 2005; 227: 343-356 3. RIVATON A, CAMBON S, GARDETTE JL. Nuclear Instruments and Methods in Physics Research B 2005; 227: 357-368 4. CELETTE N, STEVENSON I, DAVENAS J, DAVID L, VIGIER G. Nuclear Instruments and Methods in Physics Research B 2001; 185: 305-310 5. CELETTE N, STEVENSON I, DAVID L, VIGIER G, SEYTRE G. Polymer International 2004; 53: 495-505 6. STEVENSON I, DAVID L, GAUTHIER C, ARAMBOURG L, DAVENAS J, VIGIER G. Polymer, 2001; 42: 9287-9292 7. CHIEN A, MAXWELL R, CHAMBERS D, BALAZS B, LEMAY J. Radiation Physics and Chemistry, 2000; 59: 493-500 8. PATEL M, MORRELL PA, MURPHY JJ, SKINNER A, MAXWELL RS, Polymer Degradation and Stability, 2006; 91: 406-413 9. MAXWELL RS and BALAZS B, Journal of Chemical Physics, 2002; 116(23): 10492-10502 10. MAXWELL RS, COHENOUR R, SUNG W, SOLYOM D, PATEL M. Polymer Degradation and Stability, 2003; 80: 443-450 11. PLANES E, CHAZEAU L, VIGIER G, JM CHENAL, T STUHLDREIER. Accepted in Journal of Polymer Science: Part B: Polymer Physics 12. PAL PK and DE SK. Polymer, 1984; 25: 855-862 13. RAMIER J, CHAZEAU L, GAUTHIER C, GUY L, BOUCHEREAU MN. Journal of Polymer Science: Part B: Polymer Physics, 2006; 44: 143-152 14. BANDRUP J, IMMERGUT E, GRULKE E, editors. Polymer Handbook. New-York: Wiley Interscience Publication; 1999 15. CHRISTENSEN RM and LO KH. Journal of the Mechanics and Physics of Solids, 1979; 27:315-330 16. PLANES E, CHAZEAU L, VIGIER G, FOURNIER J, STEVENSON-ROYAUD I. Submitted to Polymer Degradation and Stability 17. CHAZEAU L, GAUTHIER C, VIGIER G, CAVAILLE J.Y. Handbook of "organicinorganic hybrid materials and nanocomposites, Pt2" Dr. H.S. Nalwa ed., American Scientific Publishers, 2004 18. RAMIER J, GAUTHIER C, CHAZEAU L, STELANDRE L, GUY L. Journal of Applied Polymer Science: Part B: Polymer Physics, 2007; 45: 286-298 19. CATALDO F, CAPITANI D, PROIETTI N, RAGNI P. Radiation Physics and Chemistry, 2008; 77: 267-272

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Annexe 3 : Observations microscopiques de profils de fractures

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Afin dtudier lvolution des interactions charge-matrice lors de lirradiation 25C, des profils de cryofractures dlastomres chargs ont t observs en microscopie environnementale (ESEM). Lutilisation de cet appareil permet dviter la mtallisation des chantillons.

1. Observation des matriaux E-150ATHU et E-150ATHT

Matriau E-150ATHU-0 (non vieilli)

Matriau E-150ATHT-0 (non vieilli)

Lobservation des images montrent une bonne rpartition des charges, que celles-ci soient traites ou non. La taille des charges correspond celle obtenue par granulomtrie laser. Pour le matriau non vieilli, la fracture froid conduit la formation de trous certainement crs par le dpart des charges, montrant ainsi de faibles interactions charge-matrice.

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Matriau E-150ATHU-510 (irradi temprature ambiante 510 kGy)

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Lorsque ce matriau avec les charges non traites est irradi, les trous forms par le dpart des charges ne sont plus visibles et les interfaces charge-matrice apparaissent beaucoup plus diffuses. De plus, leffet de tartinage observ traduit une forte dgradation du matriau. Matriau E-150ATHT-510 (irradi temprature ambiante 510 kGy)

Pour le matriau avec les charges traites, leffet de lirradiation nest pas vident. Les images suggrent peut tre une dgradation moins importante du fait dun contraste plus net entre charges et matrice.

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2. Observation des matriaux E-SiU et E-SiT

Lobservation des EPDM chargs silice est moins aise du fait de la taille nanoscopique des charges. On voit des agrgats de lordre de 60 nm rpartis de faon homogne dans le matriau et qui forment une structure complexe. Le traitement des charges ne modifie pas sensiblement la dispersion des charges du moins cette chelle dobservation. Matriau E-SiU-0 (non vieilli)

Les effets de lirradiation sont impossibles commenter comme le montrent les images cidessous. Matriau E-SiU-510 (irradi temprature ambiante 510 kGy)

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Matriau E-SiT-510 (irradi temprature ambiante 510 kGy)

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Pour conclure, les observations ESEM ne sont pas concluantes pour observer les effets de lirradiation mais ont nanmoins permis de vrifier la bonne dispersion des charges.

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Article 5: Role of temperature during ageing by gamma irradiation of filled EPDM Consequences on mechanical properties
PLANES E., CHAZEAU L., VIGIER G.

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Sommaire Abstract ................................................................................................................................. 209 1. Introduction ................................................................................................................... 209 2.1. 2.2. 2.3. Materials .................................................................................................................. 210 Ageing conditions .................................................................................................... 211 Experiments ............................................................................................................. 211 IR spectroscopy ................................................................................................ 211 Swelling in xylene ............................................................................................ 212 Tensile tests ...................................................................................................... 213

2.3.1. 2.3.2. 2.3.3. 3. 3.1. 3.2.

Results and Discussion .................................................................................................. 213 Homogeneity of the degradation process ................................................................ 213 For unfilled EPDM .................................................................................................. 214 Thermal ageing at 80C.................................................................................... 214 Irradiation at 25C ............................................................................................ 216 Irradiation at 80C ............................................................................................ 217 Thermal ageing at 80C.................................................................................... 220 Irradiation at 25C ............................................................................................ 222 Irradiation at 80C ............................................................................................ 223 Thermal ageing at 80C.................................................................................... 224 Irradiation at 25C ............................................................................................ 226 Irradiation at 80C ............................................................................................ 226

3.2.1. 3.2.2. 3.2.3. 3.3. 3.3.1. 3.3.2. 3.3.3. 3.4. 3.4.1. 3.4.2. 3.4.3.

Consequences of the different ageing conditions on the E-ATHU rubber .............. 220

Consequences of the different ageing conditions on the E-SiU rubber ................... 224

4. Conclusions .................................................................................................................... 228 Acknowledgments................................................................................................................. 228 References ............................................................................................................................. 229

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LEPDM tudi prcdemment a t irradi temprature ambiante, or cette temprature, il est semi-cristallin. Les cristallites pouvant perturber les mcanismes doxydation, il savre intressant dtudier lirradiation de ce matriau 80C, i.e. lorsquil est ltat amorphe. Nanmoins il ne faut pas ngliger le seul effet de la temprature, puisquil a t montr dans la littrature quune augmentation de celle-ci peut acclrer les cintiques de dgradation sous irradiation. Bien entendu des formulations charges (ATH et silice) sont galement tudis dans les mmes conditions. De plus, titre de comparaison, une campagne de vieillissement thermique 80C est galement mene pour isoler leffet seul de la temprature.

Abstract The consequences of the combined effect of irradiation and temperature on the mechanical properties of an EPDM, unfilled or filled with ATH or silica fillers are studied. It is evidenced that an increase in the temperature of irradiation has very strong consequences: all the mechanisms occurring during irradiation at 25C are largely accelerated at 80C. This is mainly due to the thermal activation of the chemical reactions occurring during irradiation.. This conclusion is true whether the materials are filled or unfilled and whatever the filler size (micronic for ATH and nanoscopic for silica). Moreover the acceleration of the degradation induced by the filler presence previously obersved at 25C is less pronounced during irradiation at 80C. In addition, in the case of silica filled EPDM, the creation of strong fillermatrix bonds, already reported for irradiation at 25C, are also thermally activated and therefore enables to this material to keep its integrity at high irradiation dose.

1. Introduction Rubber composites are sometimes used in environments, for instance, in nuclear power plants, where they may be exposed to high-energy radiation and heat. It is well known that irradiation and heat, depending on their level, can lead to the degradation of these materials and therefore shorten their lifetime. However the effect of the combination of both on the degradation of elastomers has only been the topic of very few studies, which have, for instance, measured the evolution during ageing of ultimate elongation [1, 2], of the dynamic viscosity [3], or of the concentration in oxidation products [4]. All these works evidenced that the rate of increase in carbonyl concentration and the rate of decrease in ultimate elongation of ethylene-propylene elastomer (EPR) submitted to the combination of heat and radiation are much higher than the sum of the rates obtained for each ageing condition. This synergistic effect can be generally attributed to different factors. Temperature increase can lead to a larger mobility of the polymer chains and the chemical reactions involved in polymer degradation are thermally activated. Particularly, a temperature increase promotes the decomposition of hydroperoxydes created by irradiation, which enables the formation of additional radicals. Taking into account this decomposition, Colin et al. [5] have developed a kinetic model to predict the lifetime of unstabilized and unfilled polyethylene exposed to gamma-irradiation and temperature in air, which is in good agreement with the experimental results collected in the literature.
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Besides, in the case of semi-crystalline material, the dependence on temperature of their crystallinity must also be taken into account to explain this synergy. Due to the weak permeability of oxygen in crystallites [6, 7], such materials, when they are irradiated above their melting temperature, are likely more sensitive to radiations than when they are irradiated in their semi-crystalline state. For instance, the study of the irradiation of an EPDM at room temperature and at 80C [8] has highlighted substantial differences between ageing conditions, because 80C is above the melting temperature of a substantial fraction of small crystallites. Moreover, a return below the melting temperature after irradiation above the melting temperature can promote a reorganization of the semi-crystalline microstructure of the material and explain the preservation of its mechanical properties [9]. The crystallization of the chain cut during ageing can even lead to supplementary crystallization called chemicrystallization, which can even improve the material mechanical properties. Thus, many complex phenomena are involved in an ageing combining heat and irradiation of semi-crystalline polymers. Moreover these phenomena are very dependent on the initial studied material, in particular its crystallinity, its melting temperature, and its chemical nature To our knowledge, literature is limited on this topic, especially about the consequences of ageing on the mechanical properties. Thus the purpose of this paper is to study the consequences of the combined effect of irradiation and temperature on the mechanical properties of an unfilled EPDM. As the studied semi-crystalline EPDM (with 1015% of crystallinity ratio) has a large melting temperature domain, between 20C and 60C, the chosen irradiation temperature is 80C i.e. above the melting temperature of its crystallites. The consequences of this ageing process will be compared to those obtained after irradiation at 25C [10, 11, 12, 13].Moreover for most of EPDM applications, fillers are introduced to improve their properties. In previous studies [10, 6, 12, 13], EPDM rubbers with and without fillers (ATH or silica) have been aged by gamma irradiation at room temperature under oxygen atmosphere. It was found that even if the polymer phase is degraded by the same degradation mechanisms, the filler presence induces particular phenomenon. In the case of silica filled EPDM, an acceleration of the degradation kinetic has been evidenced as well as a modification of the silica surface, and crosslinking reactions between filler and matrix at high irradiation dose. It was also noticed an acceleration of the degradation process in ATH filled EPDM by the presence of ATH. This leads to a peculiar evolution of the mechanical properties of this material compared to the one found with unfilled EPDM: a more rapid decrease in the elastic modulus and an increase in the strain at break attributed to filler-matrix decohesion mechanisms promoted by the polymer degradation in the close vicinity of the filler surface. In this paper, the same materials, silica filled EPDM and ATH filled EPDM, are studied after ageing under gamma irradiation at 80C in oxygen atmosphere. In addition, for a better comprehension of the degradation mechanisms, a thermal-oxidation campaign at 80C is also performed. The consequences of the three ageing methods - thermal ageing at 80C, irradiation at 25C and irradiation at 80C - on the mechanical properties - are then compared. 2. Experimental 2.1. Materials The EPDM elastomer (Nordel IP NDR 3722 P from Dow Chemical Company) is made of 70% ethylene, 29.5% propylene and 0.5% ENB (Ethyl Norbonene) and the crosslinking agent is the dicumyl peroxide (Perkadox BC-FF from Akzo Nobel). EPDM is reinforced with ATH
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[12]3 (Apyral 40 CD from NABALTEC) or silica [13]4 (ULTRASIL VN3 from DEGUSSA). The filler ratio in the ATH filled EPDM studied is equal to 150 phr (150 weight ratios for 100 weight ratios of EPDM, this corresponds to a weight fraction of 60%, and a volume fraction of 35%) and the filler ratio in silica filled EPDM is equal to 50 phr (i.e. 33 wt% and of 17 vol%). The different formulations are given in Table 1. The samples are processed as follows: the matrix is introduced in the internal mixer and mixed for 2 minutes, then the fillers are introduced. After 5 minutes of mixing, peroxide is added: the mixing is then performed for 10 min, at low temperature (80C). Then a mixing is performed in an external mixer (cylinders) for 10 min still at 80C. Then, the compound is pressed as 1-mm-thick films, at 170 C to promote crosslinking reaction. The curing time (t98 at 170C) is previously estimated from torque measurement performed with a MOSANTO analyser; it is the time needed to obtain 98% of the maximum torque ; it is chosen equal to 10 min for unfilled EPDM and ATH filled EPDM, and to 5 minutes for silica filled EPDM. In the previous study [13], it has been shown that the polymer phase of this composite is slightly less crosslinked than the unfilled material. EPDM Peroxide ATH Silica E-CR 100 3 0 0 E-150ATHU 100 3 150 0 E-SiU 100 3 0 50 Table 1: Formulations of the different materials (the proportions are expressed in phr: per hundred parts of matrix) 2.2. Ageing conditions E-CR, E-ATHU and E-SiU samples (for unfilled EPDM, EPDM filled with ATH and silica respectively) are exposed to -radiation of a 60CO source at a dose rate of 1 kGy/h in an oxygen atmosphere: At room temperature (the water temperature of the pool was around 18C) for doses 50, 165, 300, 510 kGy. At this temperature, these materials are semi-crystalline with a cristallinity ratio of ca. 11% [11, 12, 13]. At 80C for doses 50, 165 kGy and 300 kGy. At this temperature, the materials are above their melting temperature; therefore, they are totally amorphous. At 300 kGy, ECR and E-150ATHU samples have flown. Conversely, E-SiU materials have kept their integrity. But unfortunately, they were polluted by the other degraded materials. This prevented their analysis for doses above 165kGy.

For comparison, all the samples have been also thermally aged at 80C in ventilated oven during 50h, 165h and 300h. Afterwards, all samples were stored under vacuum at about 22C. The samples will be named hereafter E-CR-YYYY-XXXX, E-SiU-YYYY-XXXX and E-ATHU-YYYY-XXXX; YYYY represents the ageing conditions: IR25 for irradiation at 25C, IR80 for irradiation at 80C and T80 for thermal ageing at 80C, XXXX is the irradiation dose or the ageing time.

2.3. Experiments 2.3.1. IR spectroscopy


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Analyses by IR spectroscopy are performed in order to evaluate the oxidation of the materials. Firstly, changes in carbonyl concentration were followed by a Thermo Nicolet Nexus FT-IR spectrophotometer with the technique Attenuated Total Reflectance (ATR) accessory using 32 scans and a resolution of 4 cm-1. IR spectroscopy in the transmission mode could not be used because the samples are absorbing. Secondly, oxidation (carbonyl) profiles were deduced from IR-microspectroscopy using a Continum microscope coupled to a Nexus Nicolet optical bench (32 scans, resolution of 4 cm-1). A slice of sample, of about 40 m, was cut by cryo-microtomy in the thickness direction. Then IR spectra were measured on this slice every 50 m to have an oxidation profile along the sample thickness. These analysis were conducted in CNEP - Centre National dEvaluation de Photoprotection Clermont Ferrand (France). 2.3.2. Swelling in xylene

Swelling measurement is a useful technique to characterize the network degradation. In the case of unfilled rubber, the swelling restriction is due to crosslinks connecting the polymer chains, which avoid their extension and their diffusion. Because of the filler-rubber interactions, the addition of fillers is equivalent to the introduction of additional crosslinks, which perturb the polymer swelling. Samples with an initial mass Mi are introduced in xylene for 8 days to achieve the swelling equilibrium, and then the materials with a swelled mass M s are dried under vacuum at 60C during 1 day and finally weighted to obtain the dried mass Md. In the case of the composites, TGA (TGA F3 apparatus from Netzch) enables to estimate the filler weight ratio i in the initial sample and the filler weight ratio d in the dried sample after swelling. Therefore, the swelling ratio Q and the polymer soluble fraction Fp (%) can be evaluated from the following relations: Ms Md polymer Q 1 1 xylene M d 1 d

2 1 i Mi For E-ATHU samples, for the irradiation doses tested, d and i are found equal, suggesting that the sol fractions do not contains fillers. For E-SiU materials, at low dose, given the low sol fraction measured for this material, the difference found between d and i is within the experimental uncertainties. However, at high irradiation dose, actually for total sol fractions above 20%, it is found that d is clearly lower than i, meaning that the sol fractions contain a significant amount of fillers.
Extensive use has been made of the kinetic theory of rubber elasticity and the Flory-Rhener network theory of swelling to estimate the degree of crosslinking in crosslinked rubbers. The success of these techniques with unfilled elastomers makes highly desirable their extension to the technologically important filler-reinforced rubbers. Unfortunately, the introduction of rigid filler particles into the network leads to some serious theoretical and practical complications. The most basic of these is the inability of the network to undergo deformations which are affine with the sample dimensions. For this reason, we did not use swelling measurements to calculate crosslink densities.

Fp

Mi

Md

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2.3.3. Tensile tests

Tensile tests are performed on an MTS device equipped with a temperature controlled chamber. Experiments are conducted at 80C with a true strain rate 0.01 s-1. 80C is above the materials melting temperature. An image processing acquisition system (Apollor VideoTraction System) is used to obtain the true stress true strain curve. The samples are dumbbell-shaped with dimensions 20 x 4 x 1 mm3. For one type of samples, three specimens are tested; on figures only one test is reported, but the average stresses and strains at break calculated from the three tests are given in a separated table. Note that the rupture has not been reached for the E-SiU samples. Besides, the elastic modulus E is calculated as the slope of the linear initial portion of the curve. 3. Results and Discussion 3.1. Homogeneity of the degradation process

Figure 1: Oxidation profile by micro-FTIR spectroscopy for the materials E-CR, E-ATHU and E-SiU aged at 80C during 300h and -irradiated at room temperature at 510 kGy and at 80C at 165 kGy. (Absorbance at 1713 cm-1 is normalized to the absorbance measured on the sample surface)
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After radio-oxidation or thermal ageing of EPDM, an increase in absorbance in the hydroxyl absorption region (3800-3000 cm-1) was observed [14] corresponding to the formation of alcohols, acids and hydroperoxides. The formation of carbonyl band can be evidenced by an absorption maximum at 1713 cm-1 accompanied by several shoulders around 1785, 1755, 1740, and 1695 cm-1[14]. The measurements by IR spectroscopy (ATR) have shown that in the case of filled EPDM, the same oxidation products are created. For all materials (unfilled and filled), an increase in hydroxyl and carbonyl absorption regions can be observed with an increasing irradiation dose, but it is not possible to quantify these products by ATR and thus to compare the oxidation level of the different elastomers. Indeed, the IR depth penetration and the number of reflections can be influenced by the presence of fillers. Moreover, scattering phenomena can occur. However, the use of IR - microspectroscopy on sample slice can provide the oxidation product distribution within the sample thickness. The variations in absorbance at 1713 cm-1 are chosen for this characterisation. Figure 1 presents the oxidation profiles of E-CR, E-SiU and E-ATHU irradiated at room temperature at 510 kGy, irradiated at 80C at 165 kGy, and aged at 80C during 300h. The oxidation profiles are flat for thermal ageing at 80C, indicating an homogeneous oxidation within the sample thickness. For E-CR and E-ATHU sample, the profile is kept quasi-flat whatever the irradiation conditions. In the case of silica filled EPDM, the oxidation profile is slightly more heterogeneous than that observed for others materials, but this heterogeneity level can be considered relatively low : actually the variation is below 15 %. 3.2. For unfilled EPDM 3.2.1. Thermal ageing at 80C

Time (h)

Thermal ageing at 80C 03 03 03 03

Dose (kGy)

0 50 165 300

0 50 165 300 510

Fp after Irradiation at 25C 03 33 63 93 21 3

Fp after Irradiation at 80C 03 83 29 3 100 3

Table 2: Evolution of the polymer soluble fraction Fp (%) for E-CR rubber, for each ageing condition

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Figure 2: a) Swelling ratio Q versus irradiation dose or time for E-CR for the three ageing methods (lines are guide for the eyes) b) elastic modulus measured at 80C versus irradiation dose or time for E-CR for the three ageing methods (lines are guide for the eyes) Figure 2 presents the evolution of the elastic modulus measured at 80C and of the swelling ratio Q of E-CR submitted to thermal ageing at 80C, as a function of the ageing time. The swelling ratio Q decreases with an increasing time whereas the elastic modulus decreases. As reported in Table 2, no evolution of the polymer soluble fraction Fp is evidenced. All these results indicate that E-CR is submitted to a crosslinking phenomenon. This is in agreement
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with the evolution of the large strain behaviour at 80C (cf. Figures 3 and 4): an increase in the stress level at a given strain is observed as well as a decrease in the strain at break. Thus chain scission does not occur at this temperature for time below 300h. This is in agreement with Kelidj which found that the induction period for a classical unstabilized and unfilled PE aged at 80C is around 300h [7]. Note that in this study, this induction period is evaluated by the measurement of oxidation products concentration estimated by IR spectroscopy and not like in our case by mechanical measurements. Note also that in our case, peroxide added in the formulation is largely in excess compared to the ENB proportion (0.5 %) and the exposition of the material at 80C can promote the decomposition of residual peroxide (still present after material processing) and additional crosslinking reactions.

3.2.2. Irradiation at 25C

Figure 3: Large strain behavior observed at 80C of E-CR for each ageing method.

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Figure 4: Average strains and stresses at break of E-CR rubber deduced from tensile tests performed at 80C, for each ageing condition.

Consequences of irradiation at 25C have already been discussed in a previous paper [10]. Between 0 and 50 kGy, a competition between crosslinking and chain scissions takes place. Then, after 50 kGy, chain scissions become the main degradation process. This leads to a decrease in the elastic modulus and in the strain at break with an increasing irradiation. Moreover, the network architecture of the material becomes very irregular. After degradation, the network contains more and more weakened zones, which deteriorate the material ultimate properties. Given the distributed character of these chain lengths, the elongation at break is likely controlled by the shortest chains which percolate through all samples whereas the increase in the average length of the active chains control the material modulus. 3.2.3. Irradiation at 80C

The evolutions of swelling ratio and of the elastic modulus at 80C during irradiation at 80C are compared to data obtained for irradiation at 25C in figure 2. For irradiation at 80C, like in the case of irradiation at 25C, an increase in the irradiation dose leads to an increase in the swelling ratio corresponding to a decrease in the elastic modulus measured at 80C (cf. Figure 2). Thus, in both irradiation conditions, the preponderant phenomenon occurring in the studied material is chain scissions. The only difference is that the degradation is much faster in the case of irradiation at 80C, so that conversely to E-CR-IR25-510, E-CR-IR80-300 is totally soluble, i.e. totally degraded. Several explanations to these results can be given. During irradiation at 80C, E-CR is above its melting temperature and is therefore totally amorphous. As the major part of degradation is assumed to take place in the amorphous region of semi-crystalline materials, E-CR may be more sensitive to radiation, when its crystalline phase is molten. However, given the low crystallinity ratio of the studied EPDM around 11%, it can be considered that this is not the key explanation of our results. The radio-oxidation and the radio-thermo-oxidation of polyethylene have been studied by Kelidj et al. [7, 15]. The complete radio-oxidation mechanism proposed by Kelidj et al. [14] is the following: (IR) PH + h P (II) P + O2 PO2 (III) PO2 + PH POOH + P (VI.0) PO2 + PO2 [PO OP]cage + O2
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(VI.1) [PO OP]cage POOP (VI.2) [PO OP]cage P=O + P-OH (VI.3) [PO OP]cage 2P + 21S + 21 P=O + 2(1-1) P-OH where 1 is the yield of carbonyl buil-up in the non-terminating process and S the scission products. All these reactions are thermally activated, which means that a temperature increase should accelerate the degradation process. Moreoever, during thermal ageing, hydroperoxydes can be decomposed by an unimolecular and bimolecular mechanism, to induce the formation of radical species, following the reactions [7, 15]: (Iu) POOH P (Ib) 2 POOH P + PO2 Consequently, when the material is irradiated at high temperature, these two additional initiation reactions must be added to the radio oxidation mechanisms. Thus, heat during irradiation leads to a much faster increase in radical concentration and therefore also accelerates the degradation mechanisms. The evolution of the mechanical properties during irradiation at 80C is similar to the one observed with irradiation at room temperature (see figures 3 and 4). During ageing under irradiation at 80C a decrease in the strain at break and in the elastic modulus with the irradiation dose is observed. However the modulus decrease is much faster than when irradiation is performed at 25C. Moreover, the decrease in elongation at break is faster than the decrease in modulus, so that E-CR-IR80-165 has a much lower strain at break than E-CRIR25-510 in spite of their close modulus. Since it has been previously shown that the thermal ageing at 80C induces a crosslinking phenomenon, it seems reasonable to think that such crosslinking also occurs during irradiation at 80C. This process is of course less important than the scission mechanism. If one considers that the chain scissions induced by irradiation are independent on the crosslinking mechanism, then they occur at 80C on a material effectively more crosslinked than the material kept at 25C. This explains the lower elongation at break of the materials irradiated at 80C.

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Figure 5: Fp

Fp versus irradiation dose: for E-CR (experimental data after irradiation at

25C () and 80C (), and linear fit (dashed line)) and for E-ATHU (experimental data after irradiation at 25C () and 80C (), and linear fit (bold line)). The fastest degradation observed when irradiation is performed at 80C can be quantitatively estimated from the sol fraction data. To do so, the Charlesbys approach is used [16, 17]. It gives a simple expression relating the sol fraction Fp to the irradiation dose. As shown in previous paper [10], during irradiation at 25C of E-CR rubber, this expression is affine for an radiation dose D above 50 kGy, since the main occurring process is chain scissions: Gs wD 1 Fp Fp with u1 M n w 7 qf q f u1 In this relation, the proportion of crosslinked monomer qf is constant. This value can be estimated from the extrapolated elastic modulus of E-CR at 0 kGy. It is found equal to 0.015. Moreover, GswD represents the chain scission kinetic with Gs the chain scission yield. Here it is made the assumption that this kinetic is proportional to the irradiation dose (like Charlesby did in his work). M n and w are respectively the average number molar weight and the molar mass of the polymer unit. As shown in figure 5, the experimental evolution of Fp
Fp

versus irradiation dose is in good agreement with relation (7). The value of Gs deduced from the fit is equal to 5.2x10-7 mol/J. The same approach is used for irradiation at 80C, assuming that the crosslinking phenomenon observed during thermal ageing at 80C is negligible compared to the phenomenon of chain scission occuring during irradiation at 80C. This assumption is reasonable since the modulus evolution of E-CR-T80 shows an increase of a
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factor of ca. 15% whereas the modulus decrease is of about 80%. This assumption is also confirmed by the fact that the fit is again very satisfactory (see Figure 5). Taking the same value of qf used for irradiation at 25C, It is found a value of Gs around to 3x10-6 mol/J. This is ca. 6 times the value of Gs found for irradiation at 25C. Note that an account for the qf evolution (i.e. a slight increase of this parameter induced by a crosslinking phenomenon), would lead to a factor even higher. Thus, the thermal activation of the degradation mechanisms and the decomposition of hydroperoxydes induced by gamma radiation is very important.

3.3. Consequences of the different ageing conditions on the E-ATHU rubber 3.3.1. Thermal ageing at 80C

The influence of ageing on the degradation kinetic of E-ATHU is now explored. The thermal ageing at 80C is firstly considered. The swelling ratio Q (cf. Figure 6) and the soluble fraction Fp (cf. Table 3) of E-ATHU are stable up to 300h, whereas the elastic modulus is stable up to 165 kGy and then slightly decreases. Thus the crosslinking phenomenon observed for the unfilled matrix is not noticeable for E-ATHU. Moreover the large strain behavior at 80C (cf. Figures 8 and 9) shows an increase in the strain at break with an increasing ageing time. Therefore, either the crosslinking phenomenon observed for the unfilled matrix is not activated and a slight degradation process has taken place, or this crosslinking phenomenon effectively occurs, but this process is concomitant with chain scission mechanism, which is more important than in the case of E-CR. The inactivation of the crosslinking reactions may be explained by adsorption of residual peroxide on ATH surface. On the other hand, thermal ageing at 80C might lead to release free water from the filler which might promote the matrix degradation mechanisms. This is supported by the strain at break increase of E-ATHU with the time of thermal ageing, which suggests the occurrence of chain scission mechanism inducing filler-matrix decohesion. Time (h) 0 50 165 300 Thermal ageing at 80C 03 03 03 03 Dose (kGy) 0 50 165 300 510 Irradiation at 25C 03 03 43 12 3 27 3 Irradiation at 80C 03 03 26 3 100 3

Table 3: Evolution of the soluble fraction of polymer Fp (%) for E-ATHU rubber for the three ageing conditions

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Figure 6: Swelling ratio Q versus time or irradiation dose for E-CR and E-ATHU for each ageing condition

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Figure 7: Elastic modulus measured at 80C versus irradiation dose or time for E-150ATHU and E-CR, for each ageing methods 3.3.2. Irradiation at 25C As evidenced in a previous study [11], the degradation kinetic during gamma-irradiation at 25C of ATH filled EPDM is activated by the filler presence. Our assumption is that the presence of an important proportion of fillers induces the formation of supplementary radicals. In addition, this particular phenomenon has consequences on the evolutions of the mechanical properties, since it induces filler-matrix decohesion and cavitation processes during tensile tests performed at 80C.

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Figure 8: Large strain behavior observed at 80C of E-ATHU after each ageing method.

Figure 9: Average strains and stresses at break of E-ATHU rubber deduced from tensile tests performed at 80C, after each ageing condition.

3.3.3. Irradiation at 80C Like during irradiation at 25C, E-ATHU is mainly submitted to chain scissions during irradiation at 80C. This is evidenced by an increase in swelling ratio Q (cf. Figure 6) and in soluble fraction Fp (cf. Table 3), as well as a decrease in the elastic modulus at 80C with increasing irradiation dose (cf. Figure 7). The ratio of the elastic modulus measured at 80C of E-150ATHU on the elastic modulus (at 80C) of E-CR decreases from 3.5 to 2.4 (cf. Figure 7) from 0 to 510 kGy [10], whereas this ratio decreases from 3.5 to 1.8 from 0 to 165
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kGy for irradiation at 80C. Considering that there is no reason for a modification of the reinforcement factor by the fillers (since the microstructure and the filler mechanical properties are constant during irradiation), this suggests that the introduction of fillers induces a more rapid polymer degradation by irradiation and that this degradation is more important when the irradiation is performed at 80C. The same approach used for E-CR material is applied to E-ATHU material to estimate the activation of the degradation by the increase in temperature of irradiation. As shown in a previous study [9], the crosslinking degree of the polymer phase in the initial E-ATHU material is similar to the one of E-CR rubber. Assuming again that qf is constant and equal 0.015 and that chain scissions are the predominant events occuring after 50 kGy (cf. Figure 5), Gs is found equal to 3.7x10-6 mol/J. As the experimental values are less numerous (4 for irradiation at 25C and 3 for irradiation at 80C with an extrapolation after 50 kGy), it is more difficult to estimate the chain scission yield Gs for irradiation at 80C. But it seems that this is 1-1.25 times the value estimated for E-CR submitted to the same ageing conditions and 5-6 times the value estimated for E-ATHU aged by irradiation at 25C. Thus, the influence of an important proportion of ATH fillers on the degradation kinetic seems to be less pronounced during irradiation at 80C than that observed for irradiation at room temperature. The consequences of ageing by irradiation at 80C on the large strain behavior measured at 80C are presented in figures 8 and 9. From 0 to 50 kGy, the curve evolution is similar to the one observed for irradiation performed at 25C: a decrease in stress level at given strain and an increase in the strain at break are observed. But after 50 kGy, the strain at break strongly decreases. This behavior is still coherent with the facts observed for irradiation at 25C: the ATH presence enables a larger strain at break in irradiated filled EPDM compared to unfilled EPDM.

3.4. Consequences of the different ageing conditions on the E-SiU rubber 3.4.1. Thermal ageing at 80C

The evolution of the swelling ratio Q of E-SiU samples as a function of time is presented in figure 10. The extracted ratios are given in table 4. Thermal ageing at 80C leads to a decrease in the swelling ratio Q with ageing time. Thus crosslinking takes place during thermo-oxidation at 80C like in the case of the unfilled polymer. But the Q decrease for the silica filled material is more important since it leads to the same value at high dose although it begins from a higher value in the unaged state (Indeed, for processing reason, E-SiU is initially slightly less crosslinked than E-CR [13]). This suggests that the crosslinking process is more important in E-SiU, probably because the material is initially farther from its maximum possible crosslinking density. This important crosslinking process is confirmed by the evolution of the elastic modulus at 80C (cf. Figure 11) and by the tensile tests at 80C (cf. Figure 12), which show a significant increase in modulus and in the stress levels with ageing time.

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Dose (kGy) Thermal ageing at 80C 0 0 0 Irradiation at 25C 3.2 3 3.2 3 25.3 3 33.8 3 35.6 3 Irradiation at 80C 3.2 3 17 3 30.1 3

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0 50 165 300 510

Table 4: Polymer sol fraction Fp of E-SiU as a function of irradiation dose after ageing at 25C and after ageing at 80C.

Figure 10: Swelling ratio Q versus time or irradiation dose for E-CR and E-SiU, for the three ageing conditions

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Figure 11: Elastic modulus measured at 80C versus irradiation dose or time for E-SiU and E-CR 3.4.2. Irradiation at 25C

As reported in reference [13], because the polymer phase of this composite is less crosslinked, irradiation at 25C, leads also to a slight crosslinking phenomenon at the beginning of irradiation. However, after 50 kGy, the main occurring process is chain scission. This process is promoted by silica. But the consequences of such acceleration of chain scission are less dramatic than in the case of ATH filled EPDM since the silica filler network remains mechanically efficient (the E-SiU-510-80 is still high and around 8 MPa). Note that the presence of the filler network prevents any use of the Christensen and Lo model, since the fillers cannot be seen as individual particles. Moreover, the degradation of silica under gamma irradiation [18, 19] promotes the formation of filler-matrix interactions whose the presence is evidenced at high irradiation doses (above 300 kGy), by a decrease in the swelling ratio (cf; Figure 10), and a stabilization of the sol fraction (cf. table 4). 3.4.3. Irradiation at 80C

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Figure 12: Large strain behavior observed at 80C of E-SiU after ageing, for the three methods ageing (rupture is not observed) Swelling ratio and polymer sol fraction Fp of the E-SiU samples irradiated at 80C are presented in figure 10 and Table 3 respectively. The stability of the swelling ratio Q and the increase in Fp between 0 and 50 kGy indicate that chain scissions and crosslinking are in competition. As for irradiation at room temperature, the crosslinking can be explained by the less important crosslinking of the polymer phase of E-SiU. But this process seems to be more important at 80C than at 25C. In fact, the samples E-SiU-IR25-50 and E-SiU-IR80-50 have the same swelling ratio, whereas the E-SiU-IR80-50 material has a much larger Fp value than that measured for the sample irradiated at 25C. Thus, the crosslinking process taking place during irradiation at 80C seems to be more important than that observed during irradiation at 25C. Again this result evidences the synergistic effect between the temperature and the irradiation, which accelerates all degradation mechanism i.e. both crosslinking and chain scissions. The consequences are that E-SiU-IR80-50 has the same tensile properties than the unaged sample (cf. Figure 11). After 50 kGy, E-SiU is submitted to a major chain scission phenomenon, since an increase in the swelling ratio Q and in the polymer extracted ratio Fp is observed for irradiation at 80C (Figure 9 and Table 4). As the extracted polymer ratio Fp is more important for E-SiU samples than the ones of E-CR samples, the polymer phase of the composite is more degraded than the unfilled material. Despite this, the Q value of E-SiUIR80-165 lower than that of E-SiU-IR25510 indicates the formation of filler-matrix interactions as evidenced for irradiation at 25C at the highest dose, i.e. at 510 kGy.
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Concerning the mechanical properties, the elastic modulus at 80C of E-SiU rubber irradiated at 80C decreases from 14 MPa down to 6 MPa, i.e. down to a modulus value lower than the one of E-SiU-510. Thus at low strains the higher degradation of polymer phase is visible and is in agreement with the sol fraction results. However the large strain behavior at 80C (Figure 7) shows a very strong hardening. Therefore the filler network limits the material degradation, this network being reinforced by the formation of strong filler-matrix bonds. This has for consequences that conversely to E-CR and E-ATHU irradiated at 80C, the silica filled rubber keeps its integrity at 300 kGy. 4. Conclusions

An increase in the temperature of irradiation has very strong consequences. All the mechanisms occurring during irradiation at 25C are largely accelerated at 80C. Thus the unfilled material shows much faster chain scission process, and therefore a much faster decrease in its mechanical properties. The melting of the material crystallites cannot explain such acceleration which is actually mainly due to the thermal activation of the chemical reactions occurring during irradiation and to the decomposition of hydroperoxides. This conclusion can be identical in the case of filled materials, whatever the filler size (micronic for ATH and nanoscopic for silica). Moreover, the acceleration of the degradation by the filler presence is less pronounced than that observed for irradiation at 25C. In addition in the case of silica filled EPDM, the creation of strong filler-matrix bonds, already reported for irradiation at 25C, are also thermally activated and therefore enables to this material to keep its integrity at high irradiation dose.

Acknowledgments It is a pleasure to acknowledge the joint research program COPOLA between EDF, NEXANS France, LABORELEC, CEA, INRA and CNRS for its financial support and in particular Nexans France.

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References 1. GILLEN KT, CLOUGH RL. Polymer Degradation and Stability 1989;24:137-168 2. ITO M. Nuclear Instruments and Methods in Physics Research B 2005;236:229-234 3. ITO M. Radiation Physics and Chemistry 1977; 18:653-660 4. ITO M. Nuclear Instruments and Methods in Physics Research B 2007;265:227-231 5. COLIN X, MONCHY-LEROY C, AUDOUIN L, VERDU J. Nuclear Instruments and Methods in Physics Research B 2007;265:251-255. 6. EDIN S. Polymer 2005;45:6353-6359 7. KHELIDJ N, COLIN X, AUDOUIN L, MONCHY-LEROY C, PRUNIER V. Polymer Degradation and Stability 2006;91:1593-1597 8. ASSINK RA, CELINA M, GILLEN KT, CLOUGH RL, ALAM TM. Polymer Degradation and Stability 2001;73:355-362 9. BATEJA, S.K. Journal of Applied of Polymer Science 1983;28:861-872 10. PLANES E, CHAZEAU L, VIGIER G, FOURNIER J. Polymer 2009;50 : 4028-4038 11. PLANES E, CHAZEAU L, VIGIER G, CHENAL JM, STUHLDREIER T. Accepted in Journal of Polymer Science Part B : Polymer Physics 12. PLANES E, CHAZEAU L, VIGIER G, STEVENSON-ROYAUD I, FOURNIER J. Submitted to Polymer Degradation and Stability. 13. PLANES E, CHAZEAU L, VIGIER G, STUHLDREIER T. Submitted to Polymer Degradation and Stability. 14. RIVATON A, CAMBON S, GARDETTE JL. Nuclear Instruments and Methods in Physics Research B 2005;227:343-356 15. KHELIDJ N, COLIN X, AUDOUIN L, MONCHY-LEROY C, PRUNIER V. Nuclear Instruments and Methods in Physics Research B 2005; 236:88-94. 16. CHARLESBY A, PINNER SH. Proceedings of the Royal Society of London 1959;A249:367-386 17. CHARLESBY A, PINNER SH. Proceedings of the Royal Society of London 1954;A222:542-557 18. PATEL M, MORRELL PR, MURPHY JJ, SKINNER A, MAXWELL RS. Polymer Degradation and Stability 2006;91:406-413. 19. CATALDO F, CAPITANI D, PROIETTI N, RAGNI P. Radiation and Physics and Chemistry 2008;77:267-272

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Annexe 4 : Consquences du vieillissement par irradiation 80 C sur les proprits mcaniques temprature ambiante des EPDM non chargs

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Aprs leur retour temprature ambiante des analyses DSC ont t menes sur les matriaux E-CR irradis 80C. Les analyses DSC correspondantes compares celles obtenues pour les chantillons irradis 25C sont prsentes dans la figure 1. Aprs irradiation 80C, un seul pic de fusion est conserv au contraire de lirradiation 25C. En effet dans ce dernier cas, il avait t mis en vidence lapparition dune deuxime population. Ceci peut tre du soit au vieillissement par irradiation gamma, soit la monte en temprature effectue dans lappareil de DSC conduisant un processus de fusion-cristallisation-fusion. Lirradiation 80C a lieu au dessus de la temprature de fusion des cristallites, donc tout le matriau est affect par la dgradation. De plus, le matriau aprs recristallisation est totalement rorganis. Daprs les analyses DSC, la distribution de tailles des cristallites slargit au cours de lirradiation. Nanmoins, la position des pics de fusion tant la mme pour les trois matriaux E-CR-0, E-CRIR80-50 et E-CR-IR80-165, la taille des cristallites dans les trois chantillons est donc similaire daprs la formule de Gibbs-Thomson. Ainsi la microstructure de tous les chantillons tudis semble tre voisine. Lvolution des taux de cristallinit en fonction de la dose dirradiation est prsente sur la figure 2; titre de comparaison lvolution obtenue pour lirradiation 25C est reporte. Comme plusieurs tudes lavaient montr1-2-3, le retour temprature ambiante aprs un vieillissement une temprature au dessus de la temprature de fusion des cristallites permet une rorganisation de matriau : en effet les chanes coupes lors de lirradiation peuvent ventuellement recristallises. Comme il tait attendu, ce processus est beaucoup plus important dans le cas de lirradiation 80C quavec lirradiation 25C.

45C

E-CR-IR25-510

E-CR-IR25-300

E-CR-IR25-165

E-CR-IR25-50

E-CR-0

E-CR-IR80-50

E-CR-IR80-165

20

30

40

50

60

70

80

90

100

Temperature (C)

Figure 1 : Analyses DSC des matriaux Epdm-CR irradis 25C et 80C.

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15

14

Irradiation at 25C Irradiation at 80C

Crystallinity ratio (%)

13

12

11

10

100

200

300

400

500

600

Dose (kGy)

Figure 2 : Evolution du taux de cristallinit au cours de lirradiation 25C et 80C pour le matriau E-CR.
Elastic modulus at 25C Irradiation at 25C Irradiation at 80C Soluble fraction Irradiation at 25C Irradiation at 80C

8,0

25

7,5

20

Elastic modulus at 25C (MPa)

7,0 15 6,5 10 6,0 5

Soluble fraction (%)

5,5

5,0 0 100 200 300 400 500

0 600

Dose (kGy)

Figure 3 : Evolution du module lastique 25C au cours de lirradiation 25C et 80C pour le matriau E-CR. Ci-dessus est prsente lvolution du module lastique 25C au cours de lirradiation 25C et 80C. Ltude des proprits mcaniques temprature ambiante des matriaux EPDM avait montr le rle prpondrant des cristallites4 : leffet de renforcement par le rseau de cristallites est manifeste. Cest une raison pour laquelle le module lastique 25C volue peu pendant lirradiation 25C. En ce qui concerne lirradiation 80C, une forte augmentation du module est observe entre 0 et 50 kGy. Le matriau E-CR-IR80-50 a un module voisin de lE-NC (Epdm non rticul)4, ce qui parat en accord avec les rsultats tablis prcdemment4, puisque ces deux matriaux ont des taux de cristallinit voisins. En
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effet il a t montr que larrangement et la proportion de cristallites contrle le comportement mcanique faible dformations et que pour les doses dirradiation tudies, le degr de rticulation ainsi que la fraction soluble navait quune influence secondaire. Par contre llastomre E-CR-IR80-165 a un taux de cristallinit beaucoup plus lev que le matriau non rticul (E-NC). Ceci pourrait sexpliquer par le fait que lirradiation peut induire un nombre suffisant de coupures sur les squences propylne permettant une cristallisation plus facile des bouts de chanes thylnes rsiduels. Le module lastique 25C de ce matriau E-CR-IR80-165 devient quivalent celui du matriau non vieilli E-CR-0. Ceci peut sans doute sexpliquer par le fait que celui-ci possde une forte fraction soluble (14 %) mcaniquement peu rigide, qui contribuent diminuer le module lastique. Leffet de renfort par les cristallites a donc ses limites quand la dgradation devient trop importante.

22 20 18
E-CR-2min

E-CR-IR80-50

16

True stress (MPa)

E-CR-0

14 12 10 8 6 4 2 0 0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4 1,6 1,8
E-CR-IR25-165 E-CR-IR25-510 E-CR-IR80-165

True strain

Figure 4 : Comportement mcanique aux grandes dformations temprature ambiante pour le matriau E-CR. Lvolution du comportement mcanique aux grandes dformations au cours de lirradiation 25C et 80C est prsente dans la figure 4. Lvolution observe pour lirradiation 80C est trs similaire celle observe lors du vieillissement par irradiation 25C. Prcdemment, il avait t expliqu que pour les plus grandes dformations, les interactions entre cristallites et la phase amorphe via les molcules liens et la prsence dune importante fraction soluble semblait jouer un rle important, il semblait tout de mme que la diminution de la proportion de molcules lien soit un paramtre discriminant. Le phnomne de cristallisation des chanes coupes par irradiation amliore lgrement le comportement la rupture de 0 50 kGy. Compar lE-CR2min (EPDM avec un taux de rticulation plus faible que lE-CR-0 (cf. article 1 et 2)) et lE-CR, la prsence de fraction soluble et la dgradation dune partie des molcules liens dans lE-CR irradi 50 kGy 80C semblent tre compens par un taux de cristallinit plus lev. Mme si le taux de cristallinit est lev 165 kGy, la prsence dune forte proportion de fraction soluble et la dgradation importante des molcules liens sont responsables dune forte diminution de lallongement la rupture entre 50 kGy et 165 kGy. Ainsi le phnomne de cristallisation des chanes coupes par irradiation semble limiter voir amliorer les proprits mcaniques du matriau faibles doses dirradiation. Mais plus
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hautes doses dirradiation, celui-ci nest plus assez efficace compar limportante fraction soluble prsente dans le matriau et limportante dgradation des molcules liens : les proprits mcaniques sen trouvent donc largement affectes.

Ainsi lors de lirradiation 80C, le retour temprature ambiante permet une rorganisation du matriau. Le phnomne de cristallisation lors de la descente en temprature assist par les coupures de chanes ayant lieu lors de lirradiation est relativement important. Ce processus se droule plus facilement lorsque le matriau est soumis un recuit aprs vieillissement. De plus les chantillons ont des tailles de cristallites voisines : seul le taux de cristallinit volue. Mme si les conditions de vieillissement sont diffrentes, les comportements mcaniques temprature ambiante montre une volution similaire celle observe pour lirradiation 25C. De fait, aux faibles dformations, peu importe le degr de rticulation et pour des fractions solubles relativement raisonnables, les proprits mcaniques sont gres par larrangement et la proportion de phase cristalline. Lorsque la fraction soluble devient importante (E-CR-IR80-165), une diminution du module est nanmoins observe. Aux grandes dformations, la dgradation des molcules liens combine la prsence de fraction soluble lors de lirradiation conduit une dgradation du comportement la rupture. Le processus de cristallisation explicit plus haut compense cette dgradation jusqu une certaine dose.

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Conclusions et Perspectives

Conclusions et Perspectives
Conclusions

Nous nous sommes efforcs au cours de ce travail dtablir la relation entre les mcanismes de dgradation occasionns par le vieillissement par irradiation et les consquences sur les proprits mcaniques des lastomres chargs. Nous nous sommes intresss plus particulirement tudier linfluence des charges.

Le polymre tudi dans cette tude est un EPDM qui a t rticul au peroxyde. A temprature ambiante, il est lgrement semi-cristallin ( 10%). A partir de la caractrisation de la microstructure cristalline de cet lastomre, il a t mis en vidence que celui-ci est constitu de deux phases (article 2): lune semi-cristalline avec un taux de cristallinit denviron 20% et lautre essentiellement amorphe. La zone semi-cristalline est continue dans tout le film et contrle ainsi les proprits mcaniques. Aux faibles dformations, larrangement et la proportion de cristallites, peu dpendants du degr de rticulation contrlent les proprits mcaniques. Au cours de la dformation, la microstrcuture semicristalline devient fibrillaire conduisant des allongements la rupture beaucoup plus levs que ceux observs 80C. Dans le cas dapplications industrielles, ce type dlastomre est gnralement charg. Dans cette thse, il est propos dtudier linfluence de deux types de charge : lune de taille micronique, les trihydrates daluminium (ATH) et lautre nanoscopique, la silice. Pour ces deux types de charges, des formulations avec des agents de couplage ont t tudies. Laddition de charges ATH conduit un renforcement qui peut tre prdit par un modle classique. Ce renforcement est identique dans le cas des charges traites. Dautre part, le comportement la rupture de ces matriaux est classique, puisqu une rupture beaucoup plus prcoce que celle dtermine pour llastomre non charg est observe. En outre, lajout dun agent de traitement conduit un durcissement plus important, qui peut sexpliquer par une augmentation de la multifonctionnalit des charges, si celles-ci sont assimiles des nuds de rticulation. A temprature ambiante, les proprits mcaniques sont sensiblement amliores du fait de la prsence des cristallites (article 3). En revanche, lincorporation de silice nanoscopique conduit la formation dun rseau connexe de charges et le renforcement observ est beaucoup plus lev que celui prdit par les modles classiques. Ce renforcement est dailleurs plus important ltat semi-cristallin (i.e. 25C) qu ltat amorphe (i.e. 80C) suggrant la formation dun rseau mixte chargecristallite. A ces deux tats, linfluence du traitement des charges se manifeste par un durcissement plus lev et une rupture beaucoup plus prcoce par rapport au cas des charges non traits. Dailleurs pour ces derniers, la rupture des chantillons na pas pu tre observe pour les deux tempratures tudies (25C et 80C). Compares la matrice, les dformations la rupture observes pour ces lastomres chargs sont ou seraient, suivant le type de charges, beaucoup plus leves que celles du matriau non charg (article 4). Ce phnomne est classiquement observ dans le cas des charges nanoscopiques.

Ces matriaux ont t ensuite irradis temprature ambiante (articles 1 4), soit ltat semi-cristallin et 80C (article 5), donc ltat amorphe. Dans les deux cas, les matriaux rticuls ont t soumis un phnomne majoritaire de scissions de chanes. Dans
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Conclusions et Perspectives
le cas de lirradiation temprature ambiante, il a mme t montr que cette cintique de dgradation est similaire celle observe pour le polythylne en tenant compte de la cristallinit des matriaux. En effet comme la morphologie cristalline ne semble pas tre trs modifie lors de lirradiation (article 2), ce qui peut tre explique par la faible permabilit des cristallites loxygne, la phase amorphe semble plus sensible la dgradation. A 80C, cette cintique de dgradation est acclre. Cet effet est gnralement attribu dune part lactivation thermique des ractions chimiques induites par irradiation et dautre part linstabilit thermique des hydroperoxydes cres par lirradiation. Nanmoins ltat semicristallin du matriau doit tre galement pris en compte. En effet, du fait de la plus grande sensibilit de la phase amorphe, un matriau irradi dans cet tat devrait subir une dgradation plus importante. Malheureusement, cette tude na pas permis de conclure sur le rle respectif de la temprature et de la modification de la cristallinit par la temprature. Une autre campagne dessais une temprature diffrente ou une tude de lirradiation ltat semicristallin et ltat amorphe pour un autre EPDM dune cristallinit diffrente serait ncessaire. Dans le cas des lastomres non rticuls, un phnomne de rticulation non ngligeable a t mis en vidence. Pour les deux conditions dirradiation tudies, en prsence de charges, il a tout dabord t montr que la diffusion de loxygne pour les paisseurs tudies na pas t perturbe puisque les lastomres chargs montrent des profils doxydation relativement homognes. Dans le cas des charges ATH, en comparaison de lEPDM non charg rticul, une dgradation plus rapide de la phase polymre a t mise en vidence. Pour les charges traites, les consquences de ce mcanisme sont plus limites. Pour les charges silice, faibles doses dirradiation, les deux matriaux sont soumis un phnomne de rticulation. Du fait de la difficult valuer le temps de cuisson, la rticulation de la phase polymre peut se poursuivre au dbut de lirradiation. Dans le cas des matriaux avec des charges traites, les ractions de couplage charge-matrice peuvent galement continuer. A hautes doses dirradiation, ces matriaux subissent un phnomne majoritaire de coupures de chanes, mais un effet diffrent est noter en prsence de lagent de couplage. Sans agent de traitement, la dgradation de la phase polymre est beaucoup plus importante que celle observe pour la matrice. Ceci peut tre expliqu soit par la sous rticulation initiale de la phase polymre dans ce composite soit par lintensification des mcanismes de dgradation due la haute densit lectronique de la silice. De plus, un mcanisme particulier de dgradation a t mis en vidence : la surface de la silice devient moins hydrophile au cours du vieillissement, ce qui peut induire la formation dinteractions charges-matrice. La campagne dirradiation 80C a dailleurs montr que ce mcanisme est thermiquement activ. Dans le cas de charges traites, ce mcanisme est inhib, ce qui a pour consquence dobtenir 510 kGy des comportements mcaniques trs proches pour ces deux matriaux chargs.

Une fois les mcanismes de dgradation bien identifis pour tous les matriaux tudis, nous nous sommes intresss aux consquences du vieillissement par irradiation sur les proprits mcaniques. Tout dabord, nous avons tudi les proprits de ces lastomres ltat amorphe, i.e. 80C. Pour lEPDM non charg rticul, les consquences sur les proprits mcaniques sont une diminution du module lastique et de lallongement la rupture avec une disparition du durcissement. Cette diminution simultane est contradictoire avec celle classiquement observe pour les lastomres : une diminution du degr de rticulation est gnralement accompagne dune augmentation de lallongement la rupture. Cependant, durant le
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Conclusions et Perspectives
vieillissement, des dfauts comme la formation de chanes pendantes, de chanes libres et dhtrognits de rseau sont crs, alors que la masse moyenne entre nuds augmente. Un modle de coupures de chanes du rseau lastomre avec des nuds ttrafonctionnels a ainsi t dvelopp pour valuer la modification de larchitecture du rseau. Les rsultats de la simulation montrent que le module de cisaillement de ces matriaux irradis peut tre facilement dduit partir dune estimation de la masse molaire moyenne entre nuds et en tenant compte de la fraction soluble. De plus lvolution des distributions de longueur des chanes actives prdites par le modle est relativement cohrente avec les distributions dtermines exprimentalement par thermoporosimtrie. Une confrontation entre le modle et lexprience suggre que le comportement la rupture est directement li la densit initiale de rticulation (aussi longtemps que le mcanisme de dgradation na pas totalement dtruit les chanes les plus courtes) et la fraction soluble, puisque cette dernire est la manifestation de zones lastiquement inactives dans le matriau. Pour les EPDM chargs ATH, une diminution du ratio du module du composite sur celui de la matrice lors de lirradiation ( 80C comme 25C) est observe, ce qui semble confirmer lhypothse dune dgradation plus importante de la phase polymre. Ceci est galement en accord avec lintensification du phnomne de dcohsion charge-matrice avec une dose dirradiation croissante permettant une augmentation de lallongement la rupture de ces matriaux. Pour les lastomres chargs silice sans agent de couplage, les interactions charges-matrice cres par irradiation se manifestent par un durcissement plus lev. Afin dtudier lvolution des proprits mcaniques temprature ambiante durant le vieillissement, une tude de la microstructure cristalline de tous ces matriaux a t ncessaire. Pour lEPDM charg, lors de lirradiation temprature ambiante, le taux de cristallinit reste relativement stable durant le vieillissement. De plus, la morphologie cristalline semble tre peu modifie par lirradiation, cela reste vrai en prsence de charges. Comme faibles dformations, les proprits mcaniques de lEPDM sont contrles par la proportion et larrangement des cristallites, tous les matriaux irradis ont sensiblement le mme comportement mcanique. En revanche, aux plus grandes dformations, les interactions entre les cristallites formes par les molcules liens ainsi que la prsence de fraction soluble, jouent un rle important, ce qui explique un durcissement plus faible et une diminution de lallongement la rupture avec une dose dirradiation croissante. Pour lirradiation 80C, le retour temprature ambiante permet une rorganisation du matriau. Ainsi pour lEPDM non charg, un phnomne de chimie-cristallisation a t mis en vidence, ce qui permet de compenser la dgradation voire amliorer les proprits mcaniques, de mme lorsque les fractions solubles sont relativement limites. Dans le cas des lastomres chargs, les consquences de lirradiation temprature ambiante sur les proprits mcaniques 25C sont beaucoup plus limites du fait de la prsence des cristallites. En effet celles-ci peuvent tre assimiles des nuds de rticulation multifonctionnels qui sajoutent leffet des nuds chimiques. Dans le cas des charges silice, contrairement au couplage charge-matrice obtenu par le traitement silane, les interactions charge-matrice cres par irradiation ont un faible effet mcanique cette temprature.

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Conclusions et Perspectives
Perspectives

En termes de perspectives, bon nombre de points restent approfondir. En ce qui concerne les mcanismes de dgradation, il existe dans la littrature quelques modles cintiques relatant le vieillissement de certains polymres sous certaines conditions. Par ailleurs, notre travail a permis de mettre au point un modle de coupures de chanes dun rseau lastomre tridimensionnel en considrant les chanes msoscopiques comme des jonctions entre nuds de rticulation. Lun des avantages de ce modle est quil peut sappliquer dautres matriaux. Il serait ncessaire dtablir une relation entre ces deux types de modlisation. Dautre part la prise en compte du phnomne de rticulation observ dans le cas des EPDM non rticul sest rvle difficile et relativement couteux en termes dhypothses. Une de ces hypothses est que la rticulation seffectue de manire statistique dans la chane. Or le cas de lEPDM est plus complexe du fait de la multiplicit des sites de rticulation. Dautre part, une hypothse implicite de ce modle est que la phase cristalline temprature ambiante ninflue pas sur le mcanisme de scissions de chanes. Celle-ci semble tre relativement vrifie dans notre cas du fait de la faible cristallinit de nos matriaux. Mais pour un polymre plus cristallin, quelles vont tre les consquences dun tel mcanisme de coupures de chanes ? De plus, pour expliquer la fragilisation du polythylne lors de son vieillissement, Fayolle et al.1 ont mis lhypothse dune plus grande ractivit des molcules liens. Cependant, ce phnomne na pas encore t mis en vidence. Pour notre matriau, il semble que ce soit le cas, si lon considre que ces molcules liens font intervenir essentiellement des squences propylne, elles-mmes plus sensibles la dgradation. Cela reste confirmer. Des tudes sur lvolution de la morphologie cristalline des polythylnes lors de lirradiation pourraient permettre de faire un lien avec notre travail. De une tude de lirradiation de matriaux analogues ayant des taux de cristallinit et des taux de molcules liens variables pourrait tre intressante sachant que ces deux paramtres sont trs dpendants lun de lautre.

Dans le cas des EPDM chargs silice, la dgradation de la phase polymre est plus importante que celle observe pour la matrice, mais ceci peut tre expliqu de deux faons. Lidal serait dtudier un matriau similaire mais avec un degr de rticulation de la phase polymre quivalent celui de la matrice afin de dterminer si cette dgradation supplmentaire est due ou non la prsence de la silice. Ltude de lirradiation des PDMS chargs silice a suscit de nombreuses tudes qui ont permis de mettre en vidence dune part la dgradation de la silice sous irradiation et dautre part la formation de liaisons chargematrice. Pour nos matriaux, des phnomnes analogues ont lieu. De plus, la prsence dun agent de couplage semble inhiber ces mcanismes. Des tudes supplmentaires seraient ncessaires pour conforter ces rsultats et dterminer la nature de ces interactions : pourquoi sont-elles bien visibles ltat amorphe alors que leur effet est si ngligeable ltat semi cristallin ? Comment lagent de couplage annule ce mcanisme : sagit-il dun agent de protection ? Dans ce cas, quel est ce mcanisme ? Des ractions de couplages charge-matrice se poursuivent-elles pendant lirradiation ? Dans le cadre de COPOLA, une collaboration avec le LRP (Thiais) (Equipe Franoise LAUPRETRE Cdric LORTHIOIR) devrait permettre dapporter des lments nouveaux partir danalyses RMN de ces mmes matriaux. A limage des tudes faites par Patel et Maxwell, des analyses EPR et mmes dilectriques pourraient se rvler tre intressantes.
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Conclusions et Perspectives
Pour les EPDM chargs ATH, malheureusement la littrature sest rvle bien pauvre sur leffet de lirradiation sur cette charge. Ce qui a t effectu pour la silice serait ncessaire pour cette charge pour mieux comprendre linfluence des charges sur les mcanismes de dgradation occasionns par lirradiation. En effet, la mise en vidence dune zone plus dgrade au voisinage des charges lors de lirradiation de ces matriaux reste incomprise. Ceci pourra tre ventuellement approfondi par les travaux du LRP et les analyses proposes prcdemment pourraient tre galement une solution.

Pour les deux charges, une quantit deau non ngligeable est prsente leur surface. Dune part, linfluence de cette eau rsiduelle est peu connue sur les mcanismes de dgradation. Dautre part, lors dun vieillissement en temprature, quel est leffet de son ventuelle dgradation ?

Une autre perspective importante mais plus ambitieuse est la modlisation du comportement mcanique des lastomres au cours de lirradiation. ltat amorphe, pour llastomre non charg, partir de limportante base de donnes exprimentale, et par le biais dun modle de coupures statistique, dune part lvolution du module lastique au cours du vieillissement a pu tre simule, dautre part larchitecture du rseau lastomre a pu tre relativement bien caractrise. Ainsi ltape supplmentaire serait de comprendre comment se comporte ce rseau sous dformation et par consquent de vrifier si la prsence de zones faibles est lorigine dune rupture plus prcoce du rseau. Lintrt dtudier le vieillissement dlastomres chargs est de modliser des matriaux avec une dispersion de charges identiques lors du vieillissement avec comme seuls paramtres variables la dgradation de la matrice et lventuelle modification des interactions chargecharge et/ou charge-matrice. Il existe actuellement plusieurs approches pour la modlisation des lastomres chargs. Une approche classique est semi-physique : les modles proposs utilisent une description physique du rseau lastomre et complexifie son comportement par lintroduction dun rseau fictif reprsentant linfluence des charges (Arruda Boyce2, Kluppel3). Une autre approche appele micromcanique vite lutilisation de ces rseaux fictifs par le recours la technique de lhomognisation. Mme si celle-ci permet une description fidle du rseau de charges, les cas prsents se limitent aux faibles taux de charges (Ponte Castaneda4). Dans le cas des lastomres ATH (toujours ltat amorphe), comme le rseau de charges est faible, la description du matriau pourra tre simplifie. Dans un premier temps, une modlisation par lments finis utilisant la fois une loi de comportement classique pour la matrice et des conditions aux limites spcifiques, ces deux paramtres pouvant voluer au cours du vieillissement, pourrait tre dveloppe. Il sagirait ensuite de lier lvolution de ces paramtres avec celles des donnes exprimentales. De plus partir des zones de concentration de contraintes dfinies par la modlisation il serait ncessaire de vrifier les mcanismes de dcohsion charge-matrice, responsables de la rupture des matriaux, et mme de les quantifier au cours du vieillissement. Au dpart la modlisation pourrait se limiter une charge noye dans une phase polymre, puis ltude dun composite pourrait tre ralise, en effet dans le cas dimportante fractions volumiques de charges, la description du matriau pourrait tre plus complexe. Dans un second temps, on pourrait ventuellement comparer
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Conclusions et Perspectives
cette modlisation avec des modles autocohrents 2+1 phases ayant eux recours lhomognisation. Dans le cas des charges nanoscopiques, le comportement mcanique des lastomres chargs reste trs difficile modliser. Il nexiste pas ce jour de modles permettant une description complte, en effet la description du rseau de charges pose toujours un problme. Ainsi pour les EPDM chargs silice, une modlisation discrte pourrait tre labore. Lchelle de description choisie serait msoscopique, i.e. lchelle des nuds de rticulation, et les charges seraient dcrites comme des nuds de rticulation multifonctionnels avec des liens diffrents entre elles, i.e. interaction charge-charge et la phase polymre, i.e. interactions charge-matrice. Toute la gamme de sollicitation pourrait tre teste en allant jusqu la rupture, pour cela un critre de rupture de liens devrait tre dfini. La cintique de dgradation serait intgre par une modification directe de ces liens. Une approche avec les modles semiphysique pourrait ventuellement tre aborde. Le dernier point resterait la prise en compte de la rupture dans cette modlisation, qui devrait ncessairement tablir un lien entre le critre de rupture macroscopique et la microstructure du matriau modlis. Ceci constituerait un progrs incontestable dans le domaine. Le dernier objectif de cette modlisation mcanique serait lintgration de la phase cristalline. Comme les charges, une modlisation discrte pourrait tre dveloppe en dcrivant les cristallites comme des nuds de rticulation multifonctionnels avec des liens avec la matrice susceptibles dvoluer au cours du vieillissement. Ce type de description pourrait convenir pour les faibles dformations. Ensuite, cette description atteint ses limites lorsque la morphologie cristalline devient fibrillaire. En effet, il nexiste ce jour aucun modle prenant en compte lvolution de la microstructure dun polymre au cours de sa dformation. Ainsi la prise en compte la fois des cristallites et des charges lve un vritable dfit, surtout dans le cas des lastomres chargs silice, puisque un rseau mixte charge-cristallite est form.

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Rfrences
FAYOLLE B et al., Mechanism of degradation induced embrittlement in polyethylene, Polymer Degradation and Stability, 2007. 92: p.231 BERSTROM J.S. and BOYCE M.C., Mechanics of materials, 2000 32: 11 627-644, , Voir aussi : www. Polymerfem.com 3 KLUPPEL M., SCUSTER R.H., HEINRICH G., Structure and properties of reinforcing fractal filler networks in elastomers, Rubb. Chem. Technol., 1997 70: 243 4 PONTE CASTANEDA P., TIBERIO J., Journal of mechanical physics solids, 2000 48 : 6-7 1389-1411
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FOLIO ADMINISTRATIF THESE SOUTENUE DEVANT L'INSTITUT NATIONAL DES SCIENCES APPLIQUEES DE LYON
NOM : PLANS
(avec prcision du nom de jeune fille, le cas chant) Prnoms : Emilie TITRE : Influence des charges sur lvolution des proprits mcaniques des EPDM chargs lors de leur vieillissement par irradiation DATE de SOUTENANCE : 12/11/2008

NATURE : Doctorat Ecole doctorale : Matriaux

Numro d'ordre : 2008-ISAL-0089

Spcialit : Microstructure et comportement mcanique et macroscopique des matriaux - Gnie des Matriaux Cote B.I.U. - Lyon : T 50/210/19 / et bis CLASSE :

RESUME : La dtermination de la dure de vie des matriaux est un enjeu industriel important, notamment dans le cas des matriaux base polymre utiliss dans les installations nuclaires. Notre travail a ainsi port sur ltude du vieillissement par irradiation dlastomres chargs et lidentification du rle des charges dans les mcanismes de vieillissement. La matrice tudie est un Ethylene Propylene Diene Monomere (EPDM), polymre semi-cristallin avec une temprature de fusion Tf autour de 60C. Les charges utilises sont des silices nanoscopiques ou des trihydrates daluminium microniques (ATH), traites ou non afin de mieux comprendre le rle des interfaces chargesmatrice lors du vieillissement. Les matriaux ont t caractriss en termes physico-chimique, microstructural et mcanique (au dessous et au dessus de Tf ) en fonction de la dose dirradiation laquelle ils ont t soumis (jusqu 500 kGy). Quels que soient les matriaux irradis, le phnomne de scission de chanes est majoritaire lors du vieillissement. Un modle de coupures de chanes statistiques dans un rseau bidimensionnel a t labor et a mis en vidence, outre le rle des nuds de rticulations, toute limportance des dfauts crs sur les proprits mcaniques en rupture. En ce qui concerne les matriaux chargs, la prsence de charges semble acclrer la dgradation. De plus, la dgradation au voisinage des charges ATH a pour consquence un important phnomne de dcohsions charges-matrice lors dessais mcaniques aux grandes dformations. Cela se manifeste au dessus de T f par un trs fort accroissement de lallongement la rupture. Le traitement des ATH par agent de couplage attenue cet effet. De mme, le traitement de la silice semble retarder lacclration de la dgradation. Dans le cas des charges silice non traites, des ractions de rticulation par lintermdiaire de dfauts cres la surface des charges semblent avoir lieu haute dose. Enfin, pour tous les matriaux tudis, les consquences du vieillissement sur les proprits mcaniques temprature ambiante sont fortement limites par la prsence des cristallites. On notera aussi que la gamme de temprature de fusion tant large, le comportement mcanique des matriaux tudis, et son volution sous irradiation reste trs dpendant de la temprature. Enfin, pour complter cette tude, une campagne dirradiation ralise 80C (temprature suprieure la temprature de fusion des cristallites) a montr une trs forte activation thermique de la dgradation sous irradiation. MOTS-CLES : vieillissement lastomres chargs proprits mcaniques Laboratoire (s) de recherche : MATEIS Directeur de thse: Grard VIGIER et Laurent CHAZEAU

Prsident de jury : Emmanuel BALANZAT Composition du jury : Emmanuel BALANZAT, Jacques VERDU, Franoise LAUPRETRE, Marie-France VALLAT, Jrme FOURNIER, Grard VIGIER, Laurent CHAZEAU