Dégradation mécanique de solutions de polymères et ses impacts en récupération assistée d'hydrocarbures

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impacts en récupération assistée d’hydrocarbures

Adeline Dupas

To cite this version:

Adeline Dupas. Dégradation mécanique de solutions de polymères et ses impacts en récupération

assistée d’hydrocarbures. Autre. Université de Bretagne occidentale - Brest, 2012. Français. �NNT :

2012BRES0037�. �tel-00830622�

THÈSE / UNIVERSITÉ DE BRETAGNE OCCIDENTALE

sous le sceau de l’Université européenne de Bretagne pour obtenir le titre de DOCTEUR DE L’UNIVERSITÉ DE BRETAGNE OCCIDENTALE

Mention: "Sciences de l'Ingénieur"

Spécialité: "Sciences et Génie des Matériaux"

École Doctorale SICMA 0373

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présentée par

Adeline Dupas

Préparée à IFP Energies nouvelles et au Laboratoire d'Ingénierie des MATériaux de Bretagne EA 4250

1

Dégradation mécanique de solutions de polymères et ses impacts en récupération assistée d'hydrocarbures

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Thèse soutenue le 12 Décembre 2012 devant le jury composé de :

Lionel CHOPLIN

Professeur des Universités, ENSIC Nancy / Rapporteur

Dominique HOURDET

Professeur des Universités, ESPCI, Paris / Rapporteur

Michel MOAN

Professeur des Universités, LIMATb, Brest / Examinateur

Ahmed ALLAL

Professeur des Universités, IPREM-EPCP / Examinateur

Edith PEUVREL - DISDIER

Chargée de recherche CNRS, CEMEF, Sophia Antipolis / Examinateur

Jean-François ARGILLIER

Expert scientifique, IFPEN, Rueil Malmaison / Examinateur Thierry AUBRY

Professeur des Universités, LIMATb, Brest / Directeur de thèse

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Nomenclature1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1H ₂ Introduction1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1K ₂ Partie 1 : ₂ Matériaux et méthodes1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1L ₂ 1. ₂ Matériaux1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1L ₂ 1.1. ₂ Poly(Oxyde d’Ethylène) (POE)1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1L ₂ 1.2. ₂ Polyacrylamide partiellement hydrolysé (HPAM)1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1HH ₂ 2. ₂ Dispositifs expérimentaux de dégradation mécanique1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1HK ₂ 2.1. ₂ Dispositif de dégradation1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1HK ₂ 2.2. ₂ Rhéomètre à contrainte imposée1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1HL ₂ 3. ₂ Dispositifs expérimentaux de caractérisation des solutions de polymères1!!!!!!!!!!!!!!!!!!!!!!!!!!!!1HM ₂ 3.1. ₂ Viscosimètre!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1HM ₂ 3.2. ₂ Rhéomètre rotatif à contrainte imposée1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1HM ₂ 3.3. ₂ Dispositif microfluidique1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1FG ₂ 3.4. ₂ Chromatographie d'exclusion stérique (SEC) couplée à la diffusion de la lumière (MALLS) et à la viscosimétrie différentielle1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1FK ₂ Partie 2 : ₂ Dégradation mécanique d'une solution diluée de polymères1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1FN ₂ 1. ₂ Dégradation mécanique d'une solution diluée de polymères : étude bibliographique1!!!!!!!!!!!1FN ₂ 1.1. ₂ Description des écoulements élongationnels modèles1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1FN ₂ 1.2. ₂ Dégradation en écoulement stationnaire (QSSF)1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1KG ₂ 1.3. ₂ Dégradation en écoulement transitoire (FTF)1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1KK ₂ 1.4. ₂ Influence du régime d'écoulement sur la dégradation en écoulement transitoire (FTF) et stationnaire (QSSF)1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1KO ₂ 1.5. ₂ Caractérisation expérimentale de la dégradation1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1KP ₂ 1.6. ₂ Effet de la qualité de solvant1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1QH ₂ 1.7. ₂ Effets de la dégradation sur les propriétés rhéologiques1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1QL ₂ 2. ₂ Dégradation mécanique de solutions diluées de poly(oxyde d'éthylène) : étude

expérimentale1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1QM ₂ 2.1. ₂ Influence de la masse molaire sur la dégradation1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1QM ₂ 2.2. ₂ Effet de la qualité de solvant1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1OK ₂ 2.3. ₂ Scénario de scission1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1OP ₂ 2.4. ₂ Conséquences de la dégradation mécanique sur les propriétés rhéologiques1!!!!!!!!!!!!!!!!1OM ₂ 3. ₂ Dégradation mécanique d'une solution diluée de polyacrylamide partiellement hydrolysé : étude expérimentale1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1LF ₂

3.1. ₂ Influence de la masse molaire sur la dégradation1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1LF ₂

3.2. ₂ Conséquences de la dégradation mécanique sur les propriétés rhéologiques1!!!!!!!!!!!!!!!!1LK ₂

1. ₂ Dégradation mécanique d'une solution semi-diluée : étude bibliographique1!!!!!!!!!!!!!!!!!!!!!!!!1LL ₂ 1.1. ₂ Dégradation en écoulement élongationnel stationnaire (QSSF)1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1LL ₂ 1.2. ₂ Dégradation en écoulement élongationnel transitoire (FTF)1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1LN ₂ 1.3. ₂ Effets de la dégradation sur les propriétés rhéologiques1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1LM ₂ 2. ₂ Dégradation mécanique d'une solution semi-diluée de poly(oxyde d'éthylène) : étude

expérimentale1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1PQ ₂ 2.1. ₂ Influence de la masse molaire sur la dégradation1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1PQ ₂ 2.2. ₂ Scénario de scission1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1PN ₂ 2.3. ₂ Conséquences de la dégradation mécanique sur les propriétés rhéologiques1!!!!!!!!!!!!!!!!1NH ₂ 3. ₂ Dégradation mécanique d'une solution semi-diluée de polyacrylamide partiellement

hydrolysé : étude expérimentale1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1NQ ₂ 3.1. ₂ Influence de la masse molaire sur la dégradation1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1NQ ₂ 3.2. ₂ Conséquences de la dégradation mécanique sur les propriétés rhéologiques1!!!!!!!!!!!!!!!!1NP ₂ 4. ₂ Conclusion1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1MG ₂ Partie 4 : ₂ Impact de la dégradation mécanique sur l’écoulement d’une solution de polymères en milieu poreux1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1MH ₂

1. ₂ Contexte de l’étude1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1MH ₂ 1.1. ₂ Influence de la dégradation mécanique sur l'injectivité des solutions de polymères en milieux poreux1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1MH ₂ 1.2. ₂ Influence de la dégradation mécanique sur la récupération d’hydrocarbures1!!!!!!!!!!!!!!!!1MK ₂ 2. ₂ Démarche expérimentale1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1MO ₂ 2.1. ₂ Solutions étudiées1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1MO ₂ 2.2. ₂ Montage expérimental!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1MO ₂ 2.3. ₂ Milieu poreux1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1ML ₂ 2.4. ₂ Protocole d’injection1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1MN ₂ 3. ₂ Ecoulement d’une solution de polyacrylamide partiellement hydrolysé (HPAM) : résultats expérimentaux1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1MM ₂

3.1. ₂ Propriétés rhéologiques hors milieux poreux1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1MM ₂ 3.2. ₂ Injection de HPAM en milieu poreux granulaire1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1HGG ₂ 4. ₂ Conclusion1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1HGQ ₂ Conclusions et perspectives1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1HGO ₂ Références1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1HGP ₂ Communications1!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!1HHK ₂ 1

1

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1,1%CF5FC1936C%31 η 1,1%CF5FC1B3161F56C5D#1 η

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1 23F1%CF5FCF15D1183F93F11FG^"116$CB31B1%CF5FC8 931"5D9%3F12;KG149F3D1BDF1 31885C93!1 2'59B5DD3116'59CECD31 316143D31B3161B95C31 13D1A5DC5D1 B31 1 B5DD3D1 F1 93F43C%383D1161%CF5FC1CD9CDF 3131153AACC3D1B31EECDF!1215D3D9C5D19CC31 U 1 5993F45DB11615D3D9C5D1149C91B3163663161936C5D1B'EECDF1D'3F146F1%6CB3#13D19CF5D1 B'CD39C5DF186C463F13D931&D3F! 9

1 1C931B$C66F9C5D#1615931 c

r

− 1

η 3D1A5DC5D1B31 9 53D31%3163145675(7B31B$76 D31 B318FF31856C931E6311Q(HG

E!856

111931S A! 1<CE931OT!11

1

[ ] η

c

r

− 1 η

-9:9-;9 -9<9-;9 -9=9-;9

1

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92F9C9427329C4C9C94+951?9B9/C9*0D-)91

1 "331B8931113AA3314591D1B3F145678 93F#163F19F6F1F5D194C6F1BDF1 631631C*B3FF5F1,1

1

27D ,FC9 1

9

!0

9) 27

$9 6; 9!)

$9 Eη η η ηF9 !)

$99 A@9

.5+1H(HG

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1 H1 F#KG1 G#PG1 G#FH1

.5+1F(HG

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1 F1 H#NG1 H#HG1 G#KK1

.5+1Q(HG

1E!856

1 Q1 H#GG1 H#MG1 G#FN1

.5+1P(HG

1E!856

1 P1 G#NG1 F#KG1 G#KN1

.5+1N(HG

1E!856

1 N1 G#QN1 K#OG1 G#KK1

/7C9A9-F638F43C49C494273249C4C49C94+9838C4)9

1 23F1%639F1B31 1

49F3D3F1BDF1631631C*B3FFF185D93D1316'313F1D15D1F56%D1 4591631.5+#131C13F13D159B1%31616C9931255B6371 316! #1HMMF!1+D13AA3#1 1

3F1B'D1 46F1 AC631 31 63F1 CD39C5DF1 45678 93VF56%D1 F5D1 C8459D3F1 5#1 3D1 B'93F1 3983F#1 31 631 8C6C31 5DFC31 D1 5D1 F56%D1 4591 631 45678 931 5DFCB91,1 1 1 3F1 659F1 5849CF1 3D931 G#K1 31 G#Q1 25%366#1HMMG#19189131<933B#1HMPP!116'CD%39F3#1BDF1631F1B'D18%CF1F56%D#1 1 1 431 -931F49C3911H#163F1CD39C5DF145678 93V45678 931D1659F14945DB9D3F1"5%CF#1FGHH!1

[ ] η

1 "3F1 9F6F1 F5D1 5DAC98F1 491 6'B31 B31 61 %CF5FC1 CD9CDF 3#1 1 49C91 B31 61 936C5D1 3(49C83D631B319911*15/CD11*1;BCDE391*1;19B1E3DE1 316! #1FGGL1,1

9 [ ] η = K

M

9 9329*9

5_1 C 131 a1F5D1B3F15DFD3F1936C%3F11D154631F56%D1V145678 931B5DD#11D313849931 B5DD3!1

1 2'3(45FD1a#1ED96383D15849CF13D931G#O131G#N#1B43DB1B31615DA598C5D1B3161&D31 BDF1631F56%D131B5D1B31616C1B1F56%D1%CF**%CF1B145678 931,1a1]1G#O13D1F56%D1θ14591B3F1 43653F1FCFC3F116'1D5D14399!1

1 2$3(45FD1 a1 31 61 5DFD31 C 1 5D1 1 B398CDF1 4591 63F1 .5+1 C6CFF1 491 9E93FFC5D1 6CDC93#15883163185D93161<CE931L!1

1

FC9(9A9?83CF 329C49F ,3FC49 9C39 B

C979FC7329C91FA959@2EA95923CF952AF9 2F97C494273249C4C49C94+93748C4)1

1 23F1 9F6F1 B31 61 <CE931 L1 85D93D1 31 63F1 .5+1 C6CFF1 5CFF3D1 1 61 65C1 B31 9911 *1 5/CD11*1;BCDE391*1;19B19;;1,1

9 [ ] η = 3 , 89 × 10

M

^{9 932911}

1 2$3(45FD1 a1 ]1 G#PH1 3F1 3D1 5D1 59B1 %31 61 %6391 CDF9C31 BDF1 631 DB5511 ,1 a1 ]1 G#LP1

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45675(7B31B'76 D3!1

1 :DF1631F1B186DE31A679CD3V+1QGVLG1C6CF1BDF16'B3#161%CF5FC1CD9CDF 3131 631 53AACC3D1 B'EECDF1 5D1 1 B398CDF1 3(49C83D6383D1 4591 31 .5+1 491 61 936C5D1 B'EECDF1S A! 1 0631FT!146111CDFC18CF13D1%CB3D313163F1.5+1C6CFF15CFF3D116165C1B31 9911*15/CD1*1;BCDE391*1;19B19;;1,1

9 [ ] η = 8 , 13 × 10

M

^{9 93295} 1

1 2'3(45FD1a 1 ]1G#QN#149531B3161%639159C31G#O13163153AACC3D1B'EECDF149531B31 H#185D93D13163186DE31E679CD31V1313F1D18%CF1F56%D14591631.5+!1

1

27D ,FC9 Eη η η ηF9 !)

$99 A@9 .5+1H(HG

1E!856

1 H#FG1 G#NL1 .5+1F(HG

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1 G#MG1 G#MQ1 .5+1P(HG

1E!856

1 H#OG1 G#NM1

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1

1 )5F1 BCF45F5DF1 CDFC1 B31 B3(1 F56%DF1 B31 6C1 BCAA93D31 4591 6'B31 B3F1 3AA3F1 B31 BE9BC5D18DC3!1

1 +D15D6FC5D#1BDF1319%C61B31 F3#163F1F56C5DF1B3145675(7B31B'76 D31FC%D3F15D1 149493F131BC3F1,1

1

2273249 ?78C49 2C 578C49

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1 1]1G#LG1E!2

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1]1Q1E!2

1 1]1K1E!2

1 1]1F1E!2

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1 .5+11H#1F#1Q#1P131N(HG

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1

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+1BCFC6631 96DE31A679CD3V+1,1

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1

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1

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1

1

1

1

1.2. Polyacrylamide partiellement hydrolysé (HPAM)

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1

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1 :31491F1F9931C8C3#1631.913F1D145676395673131431B5D1CD39EC91%3163F1 C5DF1 49F3DF1 3D1 F56C5D!1 ;365D1 61 A5931 C5DC31 B1 8C6C3#1 61 5DA598C5D1 B3F1 &D3F1 431 -931 58431 3AA3F1 B'9DE31 6395FC31 1 A5931 C5DC31 63%31 51 C931 1 AC631 A5931 C5DC31S A! 1<CE931NT!1

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1 7D1B3F1A59DCFF39F1B3145679768CB3F149C366383D17B9567FF1C6CFF13D1949C5D1B1

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FF(HG

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1

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1 4613F11D53913163F1.91A59DCF1491;)<1<6539E3915D11C6CFF1FDF1D3149CACC5D1 F44683DC93!1

-F638F4329C494273249C9@19

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1

@19 1

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$9

<25.91KFKF;1 O#N1 F#KG1 H#OG1

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1

1 23F1F56C5DF1B31.91FC%D3F15D1149493F14591BC39161BE9BC5D18DC313D1 9EC831BC6131F38C*BC61,1

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2273249 ?78C49 2C 578C49

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1 .91 9

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2. Dispositifs expérimentaux de dégradation mécanique

1 :3(1C4383DF15D11C6CFF14591BE9B39163F1F56C5DF1B3145678 93F1BC3F1BDF131 9%C61 B31 F31,1 D1 `F7F 831 .4a1 31 D1 958 931 FGGG1 B31 01 4DF983DF!1 23F1 B3(1 BCF45FCCAF1F5D1B9CF1C*B3FF5F!1

2.1. Dispositif de dégradation 2.1.1. Présentation

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1 231 F7F 831 4C66C931 C6CF1 43DBD1 331 F31 1 1 5DF9C1 491 4<.1 +D39EC3F1 D5%3663F1 F365D161D59831.LK1B316'.4!123F1F56C5DF1B3145678 931F5D1CD95BC3F1BDF16319F39%5C9#1D51F1 F91 61 <CE931 M#1 4CF1 4FF3D1 1 9%39F1 D1 4C66C931 F5F1 6$C5D1 B$D31 493FFC5D1 3(3931 BDF1 631 9F39%5C91H!121E8831B3F1493FFC5DF1BCF45DC631%31314493C613F15849CF313D931G#O11FG19!1 2'56383D19149131BCF45FCCA13F158463(31,116'3D931B14C66C93#1615D9C5D1CDBC1D31 A59315845FD3165DEC5DD36631B1(1B31BA598C5D#1DBCF13#1BDF16314C66C93#161F56C5D1 3F1F58CF311D31F566CCC5D13D1CFC66383D!1

1 "5DA59883D113131495DCF316193588DBC5D1.LK#1459131493FFC5D1446C3#1 631BC1%568C31 W 13F1B398CD149183F931B3F1%5683F15663F13D1A5DC5D1B1384F!11

1

1

1 21 5DDCFFD31 B31 61 %C3FF31 8573DD31 BDF1 631 4C66C93#1 BBC31 B31 61 83F931 B1 BC#1 439831B31B398CD391631D58931B3137D56BF131,1

9 η

ρ UD

= Re

99 9329>9

%31,11

ρ 1 ,1 8FF31 %568C31 B31 61 F56C5D1 B31 45678 93!1 21 D59831 .1 LK1 5DFCB 931 61 8FF31

%568C31B$D31F56C5D1B3145678 931E631136631B316$3111]1H1GGG1E!2

#1 7 1,1%C3FF318573DD31BDF16314C66C93#1

: 1,1BC8 931CD39D31B14C66C93#1 η 1,1%CF5FC1B7D8C31B3161F56C5D!1

1 21 9DFCC5D1 3D931 631 9EC831 68CDC931 31 963D1 5993F45DB1 1 D1 D58931 B31 37D56BF1 5849CF1 3D931 F1GGG1 31 Q1GGG1 4591 D31 5DBC31 76CDB9C31 )E73D1 31 CF#1 HMMH#1 37D56BF#1 HNNK#1 37D56BF#1 HNMO!1 1 49C91 B31 31 ]1 Q1 GGG#1 631 9EC831 963D1 3F1 C3D1 6C!1 :DF1 1 D5931 B3#1 D5F1 5DFCB9395DF1 '1 49C91 B'D1 D58931 B31 37D56BF1 9CC31 B31 6'59B931 B31 F1GGG#1 6'56383D1D'3F146F168CDC9313131B3F13AA3F1CD39C36F1449CFF3D!1

1

1

FC9'9A92D43, C9C98F3292F 7489M)9

1 1 1

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2.1.2. Grandeurs caractéristiques

1 21F566CCC5D18DC3116366313F1F58CF3161F56C5D1BDF1631`F7F 831.4a1F'3(49C831 BCAA93883D1F365D16319EC831B'56383D!1

1 +D156383D168CDC93#16165C1B31.5CF3C6631439831B31B398CD391631(1B31CFC66383D1161 495C1B14C66C93 γ 1

4591D1BC1%568C31 W 1,1

9

4 R

Q

w

π

γ 1 ≈

9 9329(9

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1 :'49 F1 6'C5D1 B31 "5EF/3661 HMPF#1 1 6'3D931 B1 4C66C93#1 631 (1 B'65DEC5D1 8573D1 F'3(49C83158831FC1,1"5EF/366#1HMPF

9

w c

w

θ γ

ε γ 1 1

1 = ∝

2 tan

9 932989

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1 "31(1B'65DEC5D13F1B5D1495459C5DD361161%C3FF318573DD31 7 1,1

9 R

U Q

= π

9 9329I9

1 21%C3FF31 7 1F391C6CF31459199CF3916'CD3DFC1B316'56383D168CDC93!1 1

1 +D1 56383D1 963D#1 61 E9DB391 CD8C31 ED96383D1 C6CF31 4591 99CF391 6'CD3DFC1B316'56383D13F161%C3FF31B31A9CC5D1 7U 13(49C83116'CB31B3161%C3FF318573DD31 71 ,1

9 2

*

f

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9 9329'9

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58831E9DB391CD8C3199CFC31B316'56383D!1

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C9*N0

9) 27

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2.2. Rhéomètre à contrainte imposée

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1

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1

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1

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1

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1

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1

1 23F1E589C3F1"5331F5D1F366383D1C6CF3F14591BC39163158459383D19565EC31 B31 A6CB3F1 431 51 8573DD383D1 %CF3(!1 +663F1 F5D1 3D1 ED961 5DFC3F1 B31 B3(1 76CDB93F1 5(C(,16$D185C631975D1 1316$931AC(31975D1 !11

1 231D58931B3137D56BF1314591331E589C31314591D1A6CB31D3/5DC3D1B31%CF5FC1 η 131 B318FF31%568C31113F1BACDC#14591D31%C3FF31DE6C931 Ω #1491,1

9 9 932909

1

1 .591B31AC63F1%639F1B3137D56BF#16$56383D13F168CDC93!1*B361B$D31%63919CC31 B1 D58931 B31 37D56BF#1 6'56383D1 B3%C3D1 CDF631 F5F1 6'3AA31 B3F1 5D9CC5DF1 CD39C3663F1 CDFC6C1B3107659*"533#1%31449CC5D1B319563(159C3F15D995CAF1S A! 1<CE931HFT!1 1

1 11

FC9*9A9$9782 83FC9-2C33C9$9M437389C9/D72F5-2C33C)1

1

1 "31D58931B3137D56BF19CC31F'5C3D158831FC1=D123391 316! #1HMLK1,1

9

5 , 0

3 , 41

Re 1

2 4 3

5 6

= −

c b

b

c

R R

R 9 93299

1

1 ;C16$5D15DCD311E83D391631D58931B3137D56BF#163F19563(1B9CF146F11F31833D1 1 5FC66391 49C5BC383D#1 BC8CDD1 3D5931 46F1 61 F789C31 B31 6'56383D!1 +D1 5DCDD1 1

η

− ρ

= Ω R ( R R )

Re

E83D39161%C3FF31B3195C5D#15D1AC1439B93116$56383D1531F789C31315D15C3D1659F1D1 56383D1CD39C36!1

1 21 45FFCC6C1 5AA3931 491 31 958 931 31 331 E589C31 B'C845F391 D1 56383D1 D5D*

68CDC931118CF311495AC1BDF1331 F314591BC39161BE9BC5D18DC31B31F56C5DF1B31 45678 93F13D19EC831CD39C36!11

1 .6FC39F1 E589C3F1 "5331 5D1 1 C6CF3F#1 B5D1 63F1 99CFC3F1 F5D1 B5DD3F1 1 0631 L!1 231 5C(1 B31 61 E589C31 B43DB1 B31 61 %CF5FC1 B1 A6CB31 1 3F391,1 4591 63F1 F56C5DF1 BC63F#1 '3F1 61 E589C31 B5631 3D93A39#1 46F1 F3DFC63#1 C1 1 1 C6CF3#1 31 4591 63F1 F56C5DF1 F38C*BC63F1B3145678 93F#161E589C3143C176CDB931FC846313D93A39111C6CF3!1

1

782 83FC9 6

9! $9 6

9! $9

6C

676789B9F3F9 C97H8329'9

O4624389 N 9!6$9

"53311

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"53311 43C176CDB931 FC846313D93A391

HQ1 HO#HL1 HQG1 KQ1

/7C9(9A9-F638F43C49C4982 83FC493748C4&92 FC9C96CD27496F3C96C

9C394624389B9C949 844CF92F92F9C49CC349CF3C749!19C90009)

$)1

1

1 23F1 3AA3F1 CD39C36F1 5F39%F1 659F1 B31 31 56383D1 F5D1 BF1 1 6'CDFC6C1 B31 076591 \1

"533#13143%3D1-93199CFF1491631D58931B31076591A75D1 316! #1FGGH1,1

2 2 3

η ρ R

Ta Ω e

= 1 1 1 9329*9

%31 1,1975D1B176CDB93185C63131 3 #14CFF391B316'3D93A391,1 3]1 * ! 1

231 D58931 B31 076591 9CC3#1 0 1 ]1 HPHF#1 8931 631 F3C61 1 49C91 B1 B361 6'CDFC6C1 F31 B%3654431 A75D1 31 6! #1 FGGH!1 .591 0 1 b1 0 #1 63F1 3AA3F1 CD39C36F1 D31 F5D1 B5D1 46F1 DE6CE363F1 B3%D163F13AA3F1%CF3(!1

1

1 2'CD3DFC1B316'56383D168CDC93151963D1C845F3116$CB31B1958 93115D9CD31 C845F31FGGG1F39199CF31491D31%C3FF3#158831BDF1631F1B1F7F 831.4149F3D1C*

B3FFF,161%C3FF316CDC931F9163176CDB931CD9C391 71 ]1c ! !1 1

1

1

1

1

3. Dispositifs expérimentaux de caractérisation des solutions de polymères

1 ACD1B$%639163F15DF3D3F1B3161BE9BC5D18DC31F9163F149549CF19565EC3F1 3161F9931B3F189585663F1BC3F#146FC39F1BCF45FCCAF#1B9CF1C*49 F#15D11384657F!11

3.1. Viscosimètre

1 .59163F183F93F1B31%CF5FC11AC631(1B31CFC66383D#1D5F1%5DF1C6CF1D1%CF5FC8 931 25/1;391KGd1"5D9%3F!121E589C31C6CF313F1D31E589C31"5331B'3D93A391OGG1e8!121 E8831B31%CF5FC145%D1-93183F931F$3DB1B31O(HG

11HGG1.!F14591B3F1(1B31CFC66383D1 66D1 B31 G#GF1 1 HFG1 F

!1 "31 4493C61 1 1 C6CF1 4591 CB3DCAC391 63F1 9EC83F1 B31 5D3D9C5D1 B3F1 F56C5DF1B3145678 931CDFC1314591B398CD39161%CF5FC1CD9CDF 313163153AACC3D1B31EECDF1 B3F145678 93F1BCF!1

3.2. Rhéomètre rotatif à contrainte imposée

1 231 958 931 1 FGGG#1 9C %383D1 49F3D1 3D1 H!F!F1 58831 5C61 B31 BE9BC5D#1 3F1 E6383D1C6CF1BDF1331 F314591584939163F195E9883F1B3F1F56C5DF1B3145678 93F1%D1 3149 F1F566CCC5D18DC3!1"3F183F93F15D1196CF3F13D1E589C31?D3*46D19349F3D31 F9161<CE931HK!1.59163F1F56C5DF1BC63F#1D31E589C31?D3*46D1B31L181B31BC8 93131B$DE631 E6311H^OM111C6CF3#1DBCF131459163F1F56C5DF1F38C*BC63F#1D31E589C31?D3*46D1B31 Q181B31BC8 93131B$DE631H^OM11149A9314591EED3913D1F3DFCC6C!1

1

1

FC919A9782 83FC9-PC9Q97)9

1

1 49 F1 4FFE31 BDF1 631 958 931 95CA1 51 631 F7F 831 .4#1 61 %CF5FC1 D3/5DC3DD31 3D1 CFC66383D1 B3F1 F56C5DF1 B31 45678 93F1 1 1 83F931 31 584931 1 36631 B31 61 F56C5D1 CDCC63!1 )5F15DFCB95DF1'C61711BE9BC5D1659F316143931B31%CF5FC13F1F49C393151E6311HG1X!1

"31 9C 931 439831 B31 B398CD391 3(49C83D6383D#1 4591 31 F56C5D1 B31 45678 93F1 BC3#1

36131F5C1631BCF45FCCA1B31BE9BC5D1C6CF13136131F5C16319EC831B'56383D15DFCB9#1

61%C3FF3199CFC31B1F3C61B31BE9BC5D1 7

1 'C61A1C845F3914591BE9B39161F56C5D!1461

5D%C3D1B3194436391S A! 149E943F1F!H131F!FT131 7

11D31BACDCC5D1BCAA93D31F365D1631BCF45FCCA1

B31BE9BC5D1C6CF!1

3.3. Dispositif microfluidique

1 ACD1 B31 99CF391 63F1 49549CF1 3D1 65DEC5D1 B3F1 F56C5DF1 B31 45678 93F1 BC3F#1 D5F1

%5DF1 C6CF1 D1 BCF45FCCA1 9589C31 8C95A6CBC31 B%365441 491 61 F5C1 89CCD31 35;3DF31C158839C6CF31B3F1C4383DF14436F1=5"d1=CF5FC83391DB135833915D*

*"C4!1

1 "3F1C4383DF158493DD3D1D31458431Z145FF31F39CDE31[143983D1B$C845F391D1BC1

%568C3119%39F1BCAA93D3F1E589C3F1B$56383DF144363F143F!1"3F143F1F5D1A9C3F1 3D1 .793(1 31 85D3F1 F91 D31 F31 FC6C5D31 935%3931 B$591 31 5D3DD1 63F1 439F1 B31 493FFC5D!1

"D1 B31 3F1 439F1 5%931 D31 F9A31 9931 B31 NGG(NGG1 e8f!1 "31 F5D1 B3F1 439F1 1 8389D3F1 B5D1 61 BA63C5D1 F31 9BC1 3D1 %9CC5DF1 B31 4C1 639C3!1 :3F1 BC6F1 F91 6391 3D565EC31F5D1B5DDF14916311319EB1FGGK!123F189C(1C6CFF1459163F143F1=5"d1 439833D1 B31 493DDCF391 6391 C6CFC5D1 9#1 5D9C9383D1 (1 BCF45FCCAF1 8C95A6CBC3F1 3D1 6F58 93F14567BC876FC65(D3#163F1D(1D31F$6 93D14F!1

1 2$3DF38631 B1 BCF45FCCA1 3F1 FF39%C1 491 D1 5&C391 B31 5D9?631 31 4C651 491 D1 495E98831 2=C3/!17D314551B1F7F 8313F149F3D31161<CE931HQ!1

1

FC959A9OC9#C4C 7C9942439 6F27C)9

1 21 F5C1 35;3DF31 1 B%365441 B3F1 43F1 1 D61 B95C1 31 D31 431 B31 5D9C5D1 31 3(4DFC5D1743956C3F!1.591D5931B3#1D5F1%5DF1C6CF161431B315D9C5D1313(4DFC5D1 743956C3F1BC31`43165DEC5DD3663a1S A! 1<CE931HOT1B5D163F1BC83DFC5DF1F5D163F1FC%D3F1,1 1

F22CF9 9!R $9

9

! $9

%9

! $9 -9

! $9

?9

! $9

693C79C9 E!N$9C96SN9

E

9

!R $9

E

9

!R $9 N

9

!R $9 N

9

!R $9

HPL1 H!H1 G!N1 G!N1 K!FMO1 1]1

QGG1LGN1e8

1 K1FGG1 QKK1 HFO!F1 MFO!F1 /7C989A9? C4249C9796C987232C77C9+O64-T)9

1

1 1

FC9>9A96CF84C33294638 3C9#C96C9B9623F6329C39CN4293DCF27C4)9

1

1 2$56383D165DEC5DD361BDF16143135;3DF313F1B31743146DC93#1$3F**BC9313#1659F1 B31 6$C9383D#1 6'4CFF391 B 1 B31 6'DC665D1 93F31 5DFD31 659F1 31 F1 69E391 /( 1 %9C31 .C43#1 FGGP!1.59161431C6CF3#1 /( 1FC1D3165C1743956C31,1

9 9 93291 1

%31 15DFD131E611 6

!1

1 21 BA598C5D1 65DEC5DD36631 8573DD31 B31 3D17#1 ε #1 1 3D931 B31 61 5D9C5D#1 1 4591 3(493FFC5D1,1

9 9 93295 1

%31 /

169E39116$3D93131 /

,169E3918CDC881B31615D9C5D!11

1 .91C6639F#14591D1BC1 W 1B5DD#1631(1B$65DEC5D18573D1 1F'3(49C83158831FC1,11

9 9 9329> 1

1 :DF1 631 BCF45FCCA1 C6CF#1 61 5D9C5D1 743956C31 3F1 FC%C31 B'D31 3(4DFC5D1 C1 6C1 3F1 F789C3!1 23F1 4393F1 B31 9E31 BDF1 3F1 B3(1 49C3F1 F5D1 CB3DC3F1 31 F5D1 83F93F1 491 B3F1 439F1FCF1B3149131B$931B3161E589C3!1

1 23F1 4393F1 B31 9E31 49383D1 65DEC5DD36631 F5D1 663F1 1 49C91 B3F1 4393F1 B31 9E31 3D931 63F1 439F1 .F1 31 .K1 B5D1 5D1 939D31 61 5D9CC5D1 3D1 CFC66383D1 BDF1 331 9EC5D1 9CCD637#1FGGM1,1

9 ∆ P

= P 2 − P 3 − ∆ P

^{9 9329(} 1

1 23F14393F1B319E313D1CFC66383D13D93163F1439F1.F131.K1F5D1B398CD3F1149C91B3F1 4393F1B319E313D93163F1439F1.H131.F1,1

9

( ^{1 2} )

2 1

3 2

23

P P

x x

x P

x −

−

= −

∆

9 93298 1

1 1 1

x ) c x (

w =

w ) ln( w

1

=

ε

ε 1 7 8

A 9 B

C −

= ε

0

1

w

1 w

1

dl

1 Q

1 23F14393F1B319E313D165DEC5D1F$9C%3D1659F1,1

9

( ^{1 2} )

2 1

3 3 2

2 P P

x x

x P x

P

P

−

−

− −

−

=

∆

9 9329I 1

1 23F1 4393F1 B31 9E31 3D1 65DEC5D1 43%3D1 -931 FFC1 B398CD3F1 1 49C91 B31 61 4CFFD31 BCFFC431659F1B316'3(3DFC5D1B1A6CB3119%39F1615D9C5D14CF16'3(4DFC5D1,1

D ^Γ

ν

ν d D

ext

: . 9 9329' 1

%31,11

1 11Γ

1,13DF391B3F15D9CD3F13D165DEC5D1

1 11:

1,13DF391B3F1(1B31BA598C5D13D165DEC5D1 1

1 ;C1 6'5D1 F445F31 31 631 (1 B31 BA598C5D1 3D1 65DEC5D1 3F1 5DFD1 BDF1 61 5D9C5D1 V1 3(4DFC5D#1 659F1 C61 3D1 3F1 B31 8-831 4591 61 5D9CD31 3D1 65DEC5D#1 31 5D1 431 CDFC1 B398CD391 6'3(493FFC5D1B31614CFFD31BCFFC431491DC1B31%56831,1

yy yy xx xx ext

ext

D = τ γ 1 + τ γ 1

Γ : 9 9329*0 1

1

1 23F14393F1B319E3F1B3F11615D9CC5D165DEC5DD36631F5D1659F1B5DD3F1491,11 )

(

ext

Q

P ν τ γ τ γ 1

1 +

=

∆ 9 9 9329* 1

5_9ν13F9D1%5683199CFC39! ν 9]1N#LM188

1BDF1D5931F#131 W 1631BC!1 1

.591D156383D146DC931B31(1B'65DEC5D15DFD1 ε 1 # 9 5D15C3D1,1

yy

xx

γ

γ

ε 1 = 1 = − 1 9 9 9329**9

3 9 ν τ τ ε

1 ) (

ext

Q

P = −

∆ 9 9 9329*19

%311τ

1*1τ

1,14938C 931BCAA93D31B3F15D9CD3F1D59863F1,1 ( τ

− τ

) = η

ε 1 ⁾⁹ 5_9 η

93F161%CF5FC165DEC5DD3663!11

1 CDFC163F14393F1B319E31B3F11615D9CC5D165DEC5DD366315D145913(493FFC5D16CDBCDE#1 HMNN#1.C431319CCD637#1FGGM1,1

9

η

ε 1

Q P = v

∆ 9 9 9329*59

1

1 44365DF1 491 C6639F1 3#1 4591 D1 A6CB31 D3/5DC3D1 B31 %CF5FC1 3D1 CFC66383D1 η

#1 61

%CF5FC13D165DEC5D146D31145913(493FFC5D10955D#1HMGL1,10955D#1HMGL1

9 η

= 4 η

^{9 9329*>9}

1

3.4. Chromatographie d'exclusion stérique (SEC) couplée à la diffusion de la lumière (MALLS) et à la viscosimétrie différentielle

1 23F1 F56C5DF1 B31 45678 93F1 5D1 1 FFC1 99CF3F1 491 9585E94C31 B$3(6FC5D1 F9C31 ;+"1 54631 1 95CF1 B339F1 ,1 61 BCAAFC5D1 B31 61 68C 931 86C*DE631 51 96C1 DE631 2CE1;39CDE 1922;#1D1%CF5FC8 931BCAA93DC361:=#1D1B33919A9589C314:!1

"3313DC313F1FFC14436319C4631B3C5D131D1B3F1B339F1445931B3F1CDA598C5DF1 BCAA93D3F131584683DC93F!11

1 231 B3391 1 BCAAFC5D1 B31 68C 931 A59DC1 D31 83F931 BC9331 B31 61 8FF31 856C931 31 F449C83161D3FFC1B316C939161565DD3!11

1 215D3D9C5D13F183F93116'CB31B1B33919A9589C3!11

1 231%CF5FC8 931BCAA93DC36183F93161%CF5FC1CD9CDF 3131439831B31B398CD39161C663#1 615DA598C5D13161F9931B3F185663F198CACC5D#1E9EC5D!11

1 21 9C4631 B3C5D1 5AA931 B5D1 61 45FFCC6C1 B31 A59DC91 53F1 3F1 E9DB39F1 3D1 D31 F3631 3(49C3D3!1

1 23F13(49C3D3F143983D16199CFC5D1B3F1F56C5DF1B3145678 93F15D1196CF3F1%31 6$C4383D1 B1 6595C931 .5678 93F1 6C545678 93F1 ;9A31 7DC%39FC1 B31 53D1 B5D1 D1 B3F1BCF45FCCAF16315DFCD13F149F3D19C %383D1C*B3FF5F!1

3.4.1. Chromatographie par exclusion stérique F6C9

1 21 9585E94C31 491 3(6FC5D1 F9C31 3F1 D31 3DC31 B31 F49C5D1 B3F1 89585663F1 F31 F91 61 C6631 B3F1 &D3F1 %56831 7B95B7D8C31,1 63F1 85663F1 63F1 46F1 43C3F1F5D1933D3F1659F13163F1E95FF3F163D146F194CB383D!1214F31FC5DDC9313F1D1E361 B3145678 9319C614593(1CD6F1BDF161565DD3!11

-23249CN8F C37C49

1 7D31 F56C5D1 B31 659931 B31 F5BC81 )"61 G#H1 856!2

1 1 1 C6CF31 58831 6D1 49 F1 AC69C5D1F91D1AC6931B31G#H1e819C66C4593!1

1 231 F56%D1 3F1 3DFC31 BE31 1 6'CB31 B1 F7F 831 :A7*FG;1 B31 ;C8B31 BE3391 4CF1 611D1BC1B31G#O182!8CD

1458431;C8B312"*HGC1S A! 1<CE931HLT!1

1 HGG1e21B'DC665D14966383D1AC691F91D1AC6931B31G#F1e81F5D1CD3F1 %C 16'CD3391

58C31;42*FG!1231A9C5DD383D11196CF13D1C6CFD1D3149*565DD315.C1;6*A1

FC%C31B31B3(1565DD3F13D1F9C315.C1;61NGQ131NGL1W#158831C66F91F9161<CE931HL!1

1

FC9(A92638 9C97963F2 32F3C9F9CN67429438FC96278C9N983C63CF49129C39?6M)9

3.4.2. Couplage avec la diffusion de la lumière statique aux petits angles (MALLS)

F6C9

1 7D31F56C5D1BC631F58CF311D1975DD383D1BCAAF316168C 931BDF153F163F1BC93C5DF1B31 6'3F43!12'CD3DFC1B316168C 931BCAAF3149161F56C5D1B43DB1B316'DE631B'5F39%C5D 1 !1 1 23F1B5DD3F15D119C3F14916185B31B31EC881HMQN13D1C6CFD16'C5D1,1

!U &9'5I$9 1 2 ...)

) ( , (

1

2

+

+

= A c

M c q p R Kc

θ w

99 9 1 9329*(9

1 5_1615DFD3 9

2 4

0 2 0

4

7 8 A 9 B

= C

dc dn N K n

λ

π 9 9 9 9329*89

31631944591B31763CE

0

) ,

( r

I r R = I θ ⋅

θ

9 9 9329*I9

9

1 %31D

1,1CDBC31B319A9C5D1B1F56%D#1 1 3

1,165DE391B$5DB31B1ACF31CDCB3D#1 1 ) 1,1D58931B$%5EB95#1

1 1,15D3D9C5D13D145678 93#11

1 dc

dn ,1CD983D1B$CDBC31B319A9C5D1B145678 93#1

1 9

1,18FF318566C9318573DD313D145CBF1B145678 93#1 1 4θ#91 ,1CD3DFC168CD3F31BCAAF3#1

1 4

,1 CD3DFC1B1ACF31CDCB3D#1 1 1,1%3391B31BCAAFC5D#1

1 4# 1,1A391B31A5983#1 1 91 ,1BCFD31B'5F39%C5D#1

1 θ : 1DE631B'5F39%C5D1B1ACF31BCAAF1 1

,1F35DB153AACC3D1B1%C9C36!1

1

1 "331 C5D1 5DBC1 1 9391 B3F1 BCE9883F1 4436F1 BCE9883F1 B31 EC881 ,1 2 )

(sin

kc R f

Kc = θ +

θ

19349F3DF1F9161<CE931HP!1

1

FC98A9?F C9C9U 9!U &9'5I$)1

1 7D31B56313(9456C5D#115D3D9C5D131DE631 θ 1D6F#1439831B5D1B31B398CD391 9

1 31

!1231975D1B31EC9C5D1B3F1&D3F18958566C93F1431659F1F'3D1BBC93!1

-23249CN8F C37C499

1 23F1 83F93F1 B31 BCAAFC5D1 B31 61 68C 931 5D1 1 96CF3F1 %31 D1 F43958 931 :2)1 +5;1

27103D565E71C41B$D31F59316F391AF1KG1821

1]1LMG1D8131B$D31366631CO1B31

OG1e2!11

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!1

1

3.4.3. Couplage avec la viscosimétrie différentielle

1 231%CF5FC8 931439831B3183F939161%CF5FC1CD9CDF 31B3F1F56C5DF1B3145678 93F131B5D1 631975D17B95B7D8C31B3F1&D3F151 3DCF145678 93F149F3D3F1BDF161F56C5D!1 4613F1 FFC1 C6CF1459153DC91B3F1CDA598C5DF1F916'1B31F9931B3161F56C5D1B3145678 93F1F9153161 BCF9CC5D1B318FF31856C93!17D1B3F1B339F163F146F1C6CFF13F1631BCF45FCCA119314C66C93F1 3D145D1B3123F5D3!1.591331B3#1631B3391C6CF13F1631=CF5F9144127103D565E71 4D!!9

1 23F1 439F1 B31 493FFC5D1 83F93D1 61 BCAA93D31 B31 493FFC5D1 FC31 1 8C6C31 B1 45D1 31 61 5993C5D1B31493FFC5D14.13D9316'3D9313161F59C3!17D19F39%5C91B31F56%D1FC1%D16314C66C931

"Q1 %56831 B31 B6C1 439831 B31 F'FF9391 31 61 4F31 85C631 9%39F31 631 4C66C931 659F31 61 F56C5D11D67F3919%39F316314C66C931"K1S A! 1<CE931HNT!11

1

1

FC9I9A96CF84C33294638 3C9H94624 ,3FC98FC3C7)1

1 23F183F93F1B3161BCAA93D31B31493FFC5D1 :. 131B31615993C5D1B31493FFC5D1 4. 1439833D1B31 B398CD391 63F1 %CF5FCF1 F4CAC3F1 31 B'3D1 BBC931 61 %CF5FC1 CD9CDF 31 31 631 975D1 7B95B7D8C31B3F1&D3F145678 93F!11

1 21%CF5FC1F4CAC31F'5C3D1149C91B3161936C5D1,1

9 IP DP

DP

sp

2

4

0 0

= −

= − η

η η η

9 9 9329*' 1