New Material Concepts for Elastomers
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1 for Elastomrs J. G. Mir, R. H. Schustr Dutschs Institut für Kautschuktchnologi.V. Hannovr, Grmany Spring Sminar of th Finnish Rubbr Institut
2 Übrsicht High Prformanc Tchnical Solutions Incrasd Functionality Safty and Comfort in th mobil socity Economic and Ecologic Solutions
3 Foli 3 Targts Matrial Concpts Improvd Prformanc undr Svr Conditions Rducd Failur Rats Prolongd Liftim Improvd Procsss Challngs Aging Rsistant Crosslinking Systms Physically Motivatd Concpts Functional Polymr-Fillr Systms Rubbr Fillr Composits Surfac Tratmnts of Parts
4 Foli 4 Effcts of Rubbr Matrix and Acclrator Structur on Ntwork Proprtis Rubbr NR, BR, SBR S x S S x S S x Chain Ends Acclrator CBS, TBBS, MBS, BzBS DCBS, DBzBS Chain Lngth Microstructur Chmical Constitution S x S S 2 S 2 Entanglmnts Primary Amins Scondary Amins (bulky alkyl radicals) CBS/S NR Crosslink Dnsity (XLD) Crosslink Efficincy Distribution of Crosslink Structurs (XLS) Physical Proprtis of Vulcanizats
5 Foli 5 Improving th Ntwork Structur Nw Crosslink Systms Improvd Rvrsion Rsistanc and Liftim S S (CH ) X S X 26 X common crosslinks x > 4 rvrsion : S x-y S cyclisation, dnm Torqu hybrid crosslinks x < 3 vry stabl at high tmpratur and undr dynamic strss 8 conv. 4 smi v Vulcurn Tim, min. Hat build up Tar rs. Control Control / ovrcurd Vulcurn Systm Vulcurn Systm / ovrcurd Tnsil strngth Hardnss Modulus 00
6 Foli 6 Matrial Concpts Aging Rsistant Crosslinking Systms Physically Motivatd Concpts Functional Polymr-Fillr Systms Rubbr Fillr Composits
7 Foli 7 Prdictions of th Tub modl ( Doi, Edwards 978 ) for monodisprs, linar, multipl ntangld polymrs at small dformations modl tub primitiv chain rfrnc chain M Entanglmnts with nighbouring chains Entanglmnt distanc Dynamic modul BR (93%vinyl );, G' G'' M w = 05000, M w /M n =,03 G'(lastic) ] a [P G N li E+5 u d o M h G''(viscous) E+4c is m 2 a n y E+3d E-6 E-4 E-2Frqunz E+0 [Hz] 2π τrp Frquncy [Hz]
8 Foli 8 Chain Dynamics Chain Architctur E+7 E+6 G' G'' Poly-Butadin Mw Vinyl [%] G,G E+5 GN E+4 τrp Chain cross sction E+3 E-6 E-4 E-2 E+0 E+2 E+4 E+6 Frquncy [Hz] τ rp,b τ rp,d
9 Foli 9 Chain Dynamics: Dmands Thortical Dscription for mdium and high Frquncis Mor Informations concrning th Influnc of Molcular Wight Distribution Bridging Polymr Physics and Polymr Chmistry Taylor Mad Chain Architctur Procssing Viscolastic Proprtis
10 Foli 0 Polymr Ntwork Topology Affin Ntwork Phantom Ntwork Gaussian Statistics Not considrd - Fr Ends - Loops - Trappd Entanglmnts linar Polymr Entanglmnts Entanglmnt spacing Gnralizd Tub Modll (Hinrich t al. 984) (Edwards & Vilgis 988) Trappd Entanglmnts W G T n T n T n G c = + + µ µ= µ µ= µ µ= µ µ= λ λ λ λ ln W G T n T n T n G c = + + µ µ= µ µ= µ µ= µ µ= λ λ λ λ ln G k T l k T R c c B s s B o = = < > υ υ G l k T d s s B o = υ Cross-link modulus: Topological constraint modulus: Trapping factor: T (0<T<)
11 Foli Advantags of th Tub Modl 4 uniaxial xp. fit pur shar xp. simulation quibiaxial xp. simulation 4 uniaxial xp. fit pur shar xp. simulation quibiaxial xp. simulation 3 NR (unfilld) 3 NR (unfilld) non-affin tub modl (G=0.43 MPa, G=0.2 MPa c n/t=68) strain 0 Moony-Rivlin (C=0.25 MPa, C=0.05 MPa) (Klüppl, 2002) strain Succssful application for Filld Elastomrs with Gc, G und T
12 Foli 2 Physically motivatd Matrial Laws Implmnting Basic Concpts Us of charactristic Matrial Paramtrs Prdictions of Matrial Proprtis Finit Elmnt Programs [MPa] ng. strss σ o E-SBR / 60 phr N339 (prstrain 200 %) Edwards-Vilgis upturn invrs Langvin upturn strain ε Rducd Effort in Dvlopmnt Incrasd Product Quality Consistnt Prdictions through physically motivatd Matrial Laws
13 Matrial Concpts Foli 3 Aging Rsistant Crosslinking Systms Physically Motivatd Concpts Functional Polymr-Fillr Systms Rubbr Fillr Composits
14 Foli 4 Chain Architctur Mw MWD Microstr. Branch. Functional Mtallocn Catalysis (980) variabl variabl variabl ys ys Anionic Polymrization (960) varibal narrow variabl no ys Coordination Polymrization (955) varibl broad rstrictd ys no Fr-Radical Polymrization (928) high broad rstrictd ys ys
15 Foli 5 Chain-Functionalization Mtalocn Catalysis Anionic Polymrization X X Sn X Y X Fr-Radical Polymrization X X X X X X X Functionalisation through polymranalogous Ractions X
16 Foli 6 Functionalizd Polymrs Intractions with Functional Fillrs O H OH H O... Si(OR) 3 O Si O Si Silica tan Dlta 0,8 0,7 0,6 0,5 0,4 VSL ,07 % OH 0,53 % OH,0 % OH 0,3 0,2 COOH CN COOH 0, (Bayr AG) Tmpratur [ ] Improvd Traction through Functionalization
17 Foli 7 Surfac Activity Modifications (Exampl: Silica) Si Si-C3 Si-C8 HO OH Si O Si OH OH OH Si OH Si O HO OH HO OH Si O OH OR Si Si O O OH Si Si O HO OH HO OH Si O OH OR Si Si O O OH Si Si O HO OH G' / MPa G' / MPa Si Si-C3 Si-C8 0 0, 0 00,2 0,8 0,4 Silica / BR Φ = 0,20 Si-C8 Amplitud / % Si Si-C3 Silica / BR Φ = 0,20 0,0 0, 0 00 Amplitud / % Rolling Rsistanc G'' max [MPa] G'' (Tg) Traction BRSi75 2 BRSi208 3 BRSi203 4 BRSi208-/3 5 BRSi 40 0,00 0,05 0,0 0,5 0,20 0,25 0,30 Volum Fraction Incrasd Traction and rducd Rolling Rsistanc
18 Foli 8 tan δ A B dynamic Amplitud [%] Polymrs Spctral Dimnsions Rolling Rsistanc (drum) A B ABS wt (Bton) Rolling Rsistanc Wt grip
19 Foli 9 Fractal Natur of Fillr-Aggrgats (Grspachr, 989) U ~ A ( α u =,30...,50) } M ~ R ( α m = 2,3... 2,6) Fillr-Ntwork afractal Objct Fillr-Ntwork Fillr-Clustr ar flxibl Objcts (Fridlandr, 998) Glpoint φ Rubbr-Fillr Intraction
20 Foli 20 Polymr-Fillr Intractions control Gl Point Variabl Loading (E-SBR, N330) Microdisprsion 5 LOG (Volum Rsistivity) [ Ω cm] Ep δ [J/cm 3/2 ] 8 7 SBR (35) SBR (23,5) SBR (8) NR S n Insulating Prcolation Conducting 6 EPDM Φ c CB [phr] Carbon Black Loading [phr] Elctrical Prcolation Point (Ep) By improving Polymr-Fillr Intractions th Prcolation Thrshold is shiftd towards highr Fillr Loadings
21 Foli 2 Dynamics of Fillr Ntworks (Rinforcmnt) (Low Strain; γ 0) Gl Point Φ G ' 0 G ' a P N B - ( ξ ) ξ 3+df,B G ' 0 d f,b =fractal dimnsion of CCA clustr backbon (d f,b =,3) d f = G ' P Φ fractal dimnsion of CCA clustrs (d f =,8) a ξ 3 3+df,B 3 - d f G ' P = G ' P Φ 3,5 Scaling law is not affctd by Particl Siz Chmical Natur Aggrgation is strongly influncd by Fillr-Matrix Intractions
22 Fillr Ntwork and Enrgy Dissipation Foli 22 γγ /2 β τ G' ( γ ) = (G' o - G' ) [ + ( / ) ] - + G' a b Systm γ /2 β CB N ,52 EBR 7 0,59 Thortical Dscriptions of non-catastrophic nrgy-dissipation ar dmandd
23 Foli 23 Surfac Activity of Fillrs: Roughnss al Dimnsions (Hss, 978) Surfac Fractal Dimnsions Furnac Blacks D S 2.60 Graphitizd Blacks D 2.33 S Surfac Roughnss is not controlling th rinforcing fficincy of Furnac Blacks (Goritz, 996)
24 Enrgtic Surfac Structur of CB Foli 24
25 Foli 25 Controlling Contrary Intractions Rubbr - Fillr Fillr - Fillr mdium nrgtic sits (Typ II) high nrgtic sits (Typ III and IV) Good Disprsion much Bound-Rubbr Hystrsis: high at T ~ 0 C low at T ~ 60 C Poor Disprsion lss Bound-Rubbr Hystrsis: low at T ~ 0 C high at T ~ 60 C
26 Foli 26 Surfac Activity Modifications (Exampl: Furnac Blacks) Disprsion Modification Traction Plasma Tratmnt Rolling Rsistanc Procss Modifications "Nanostructurd Blacks" Incrasd Traction and rducd Rolling Rsistanc
27 Foli 27 Functional Polymr Fillr Systms Rducing Fillr-Fillr Intractions Improving Fillr-Polymr Intractions to improv Fillr Disprsion to rduc Hystrsis to incras Abrasion and War Rsistanc to prolong Lif tim undr svr srvic conditions
28 Foli 28 Matrial Concpts Aging Rsistant Crosslinking Systms Physically Motivatd Concpts Functional Polymr-Fillr Systms Rubbr Fillr Composits
29 Foli 29 Rubbr Fillr Composits Polymrization in watr Latx (rubbr mulsion) SEM 0,5 mm Co-prcipitation prcipitant Solid/ liquid sparation procss watr Drying Furnac procss Fluffy (CB suspnsion) SEM
30 Stratgis for Rubbr Mixing Foli 30 g Powdr Rubbr /Spcial Mastrbatchs Continuous Mixing Twin Scrw Extrudr Batch Mixing Intrnal Mixr
31 Foli 3 Powdr Rubbr vs Bal Rubbr Bal Mixs 94 % B-M7 B-M5 Powr [ kw] P-M2 B-M Tim [Sc] 99,2 % Powdr Rubbr Mixs 500 P-M0 300 P-M2 00 0,
32 Foli 32 Powdr Rubbr + Chmicals Softnr Dgassing Advantags of Continuous Mixing Dgassing Rotor spd (rpm) Enrgy input (kwh/kg) 0,444 0,53 Output tmp. ( C) Rsidnc tim (s) Configuration I Advantags stady powr supply no batch to batch vatiations littl oprator attndanc rducd nrgy costs high mixing fficincy Suprior Quality G (kpa) 00 Bal Rubbr (Intrnal Mixr) Powdr Rubbr (Extrudr) 500 Conf.I Conf.I , 0 00 log Strain [%]
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