Nanostrength Block Copolymers for Epoxy …

1 Nanostrength Block Copolymers for Epoxy Toughening100 nmPABuPMMAPMMA / EpoxyNanostrength for Epoxy toughening Arkema Overview Nanotechnology Platform at Arkema Nanostrength Nanostrength Block Copolymers for Epoxy Value Drivers Epoxy toughening with Nanostrength Range of properties achievable using Nanostrength How it works Application Specific Properties- Composites and Adhesives2 Arkema 2007 overviewSales by regionEurope (excl. France)39%Sales: bn ($ )Capital employed: 31bn39%France18%North America25%Sales per yearCapital employed: bnCapex: 4%of sales18%Row5%Asia13%2007R&D: 3% of sales15 200employeesIn ,200employees3200520062007R&D accelerates product innovationOverview (2007)3% of sales 1 350 researchersR&D by segment12%Vi lBreakthrough1,350 researchersNear 100 joint projects with universities6 R&D centersPortfolio around 5,700 patents12%12%51%25%Vinyl ProductsPerformanceProductsIndustrial Chemicals2005 Chemicals Recent breakthroughsRecent breakthroughs4 Nanotechnology Platform at ArkemaOur customers :Compounds, Thermosets, Pigments, Engineering resins,Paints, Coatings,Adh iAdhesives.

2 Functionalized Specialty Block CRP* initiator&FlexiBloc CopolymersFlexiBloc CRP* &Reactive Block CopolymerBlock Copolymersmacroinitiator5pyNanotechnolog y Platform at ArkemaBlock Copolymers for Epoxy toughening6 Classical vs. Controlled Free Radical Classical Radical Polymerization Controlled Radical Polymerization No control of termination Living chain ends experience reduced Wide polydispersities Random sequencing fitexperience reduced termination Reduced of monomer unitspolydispersities Block Copolymers possiblepossible7 Complete Control of Block Structure Block copolymersClassicalBlock copolymersClassicalBlock Copolymers Incompatibility between blocks organization at the nanometer scaleRandomcopolymerDiblockcopolymerABA triblockcopolymerABC triblockcopolymerscale8 Nanostrength Triblock Polymers Controlled Radical Polymerization (CRP) ABA, ABPl[(Mthl) thlt]bl(BtlA lt)bl[(M th l)]

3 Thl t ] Functional comonomers can be added (AA, MAA, PEGMA, HEMA,..)Poly[(Methyl)methacrylate] -b-poly(Butyl Acrylate)-b-poly[(Methyl)methacrylate]Po ly[(Styrene] -b- poly(Butyl Acrylate)-b- poly[(Styrene] Anionic polymerization SBM Outstanding control of molecular weight, molecular weight polyStyrene -b- polyButadiene-b- poly[(Methyl)methacrylate]9gggdistributi on, composition, chain architecture, functionalizationBlock Copolymers for Epoxy toughening Structural Adhesives(Automotive, Industrial, Assembly, Wind Energy, Electronics ..) Coating(Solvent, Powder,..) Composites(Aerospace, Sports and Leisure,..)p(p,p,) Epoxy compoundsNanostrength is suited for every application that needs an increase in resistance to crack propagationwhile maintaining Tgand Modulus of the to the unique nanostructuration achievable with Nanostrength , it is possible to achieve identical toughnessto competiti e modifiers (CTBN) b tsing red ced loading10to competitive modifiers (CTBN) but using reduced loading Copolymers for Epoxy TougheningAdvantages of Nanostrength .))

4 toughening with little loss of Tg or Modulus Outstanding toughening at lower loading due to unique modifier morphologies Ease of Processing-additive dissolves in Epoxy resinEase of Processingadditive dissolves in Epoxy resin Nanoscale self-assembled particles allow for toughening adhesive bond coatings3. Composites with small inter-fiber spacingCore-ShellCTBN / ~ m1 ~ 5 m10 ~ 100 nmBlock Copolymers for Epoxy TougheningLow Tg systems: DGEBA + JeffamineTMT403 Low Tg systems: DGEBA + JeffamineTMT403 Loading LevelK1CG1 CTgK1CG1 CTgM53 CTBN0% Superior toughening at equivalent loadings Equivalent toughening at lower loadings12 Block Copolymers for Epoxy TougheningIntermediate Tg systems: DGEBA + DICYI ntermediate Tg systems: DGEBA + DICYL oading LevelK1 CTgK1 CTg0% +- +- +- +- +- +- +- +- (Dicy) is hardener representative of.

5 Adhesives-Adhesives- Sports and Leisure composites-Coatings13-CoatingsA Self-assembling Nanotechnology- Affinity between epoxymonomers and PMMA- Repulsion between epoxymonomers and the middle Block (s) Nanophase separation ofPBuAblocks:DGEBAM-A-M Nanophase separation of PBuAblocks:PABuPMMAPMMA / EPABuPMMA / Epoxy14 PMMAPMMA / EpoxyToughening of Epoxy systems Many mechanisms contribute to Epoxy toughness : Shear yieldingShear yielding Shear yieldingShear yielding Multiple crazing Crack pinning Crack bridgingCrack bridging Crack deflection ..Th iithfl ibili tiToughening is more than flexibilization. Flexibilization lowers the modulus of the material to decrease brittleness (CTBN - flexibilizer) by reacting to the backbone of the Epoxy .

6 Nanostrength (and hll) itidlhil t h iPearson (1993)HYd Ki lh A J J M tS i 27 2763 (1992)core shells) maintain modulus while , Y., and Kinloch, , J. Mater. Sci., 27, 2763 (1992). toughening of Epoxy systemsThe most efficient mechanisms to toughen are system & condition dependant: Low Tg systems, high T or low speed testing conditions: Shear yieldingMatrix network has enoughMatrix network has enough mobility to activate plasticity High Tg systemsHigh Tg systems, low T or high speed testing conditions:: Multiple crazing Crack bridging CkiiMatrix network too cross-linked to activate plasticity Crack pinning Crack deflectionpyR A Pearson"An overview of organic toughening agents for Epoxy resins"ERFDS pring 2000 Pearson, An overview of organic toughening agents for Epoxy resins, ERFD Spring 2000 Conference, April 16-18, 2000, San Antonio, TX toughening of Epoxy systems Existing tougheners have specific toughening mechanisms: Liquid reactive rubbers shear yieldingqyg Thermoplastics crack bridging, pinning & deflection Acrylic Block Copolymers : all mechanisms Shear Yielding (cavitation of the rubber phase) Nanoscale modifiers lead to high density of shear band Acrylic Block Copolymers .

7 All mechanisms Nanoscale modifiers lead to high density of shear band formation Unique morphologies lead to better toughening Crack Bridging Crack Pinning (strong matrix adhesion)17 Crack DeflectionToughening of Epoxy systemsCavitation of nanodomains 18 toughening of Epoxy systemsModifier morphology in cured Epoxy dependent on: Crosslinking/Resin chemistry Block copolymer ChemistryM51, M52, M53: PMMA- Block -PBuA- Block -PMMADGEBA + MDEADEGBA + Jeffamine19 DGEBA + M-DEADEGBA + Jeffamine T403 toughening of Epoxy systemsBlock copolymer Chemistry dictates Modifier Morphology MAM exp15 m DGEBA + DDS5 mRef+10% MAM exp1+10% MAM exp2+10% MAM M22 NMAM exp23 mM22N2 mDevelopment of functionalized grades to further improve nanostructuration with alltypes of Epoxy systems: M22N or M52N:PMMA/DMAblockPBuAblockPMMA/DMA20M22 N or M52N.

8 PMMA/DMA- Block -PBuA- Block -PMMA/DMAT oughening of Epoxy systemsModifier Morphology dictates PropertiesDGEBA J ffiT403 Low Tg systemsLow Tg systemsDGEBA + Jeffamine T403M22N givesM53 gives M22N gives excellent nanostructuration for perfect spider web agglomeration for superior thiptransparencytougheningNe a t Epox of Epoxy systemsPlastic Deformation of the samples with Block copolymersDGEBA + Jeffamine T403 Low Tg systemsLow Tg systems250200250150e (N)Neat100 Forc10% M5310% (mm) toughening of Epoxy systemsBalance of properties:SiDGEBA+ Jeffamine T403 Fluidity at 80 CSuperior toughening with some viscosity penalty with 10%DGEBA+ Jeffamine at 40 CTgpenalty with 10% M53 or at 40 CTg NeatEquivalent viscosity and toughening , E GIC 10% CTBN10% M53gg,improved Tg and modulus at of the loadingKIC 23 Block Copolymers for Epoxy TougheningLoading LevelK1 CTgK1 CTgM52 NCTBN Intermediate Tg systems: DGEBA + DICYI ntermediate Tg systems: DGEBA + DICY0% +- +- +- +- +- +- + + gives worm-like micelle Nanospherical micelles for K1C= for excellent tougheningpperfect transparency (exp.)

9 Grade) toughening of Epoxy systemsFluidity at 40 CNeatCTBN 10%Balance of properties:SuperiorCTBN 10%M52N 10%M52N 5%Superior toughening and Tg at equivalent loadingFluidity at 80 CTg loadingEquivalent qtoughening and viscosity with enhanced Tg at E KIC of the loading25 Nanostrength for Epoxy Toughening160 C cureKIC ( )T ( C) greater advantages with Nanostrength in more toughenable DICY cured systems lower cure M52N CTBN higher Epoxy Equivalent Weight (EEW)resin DGEBA/DICY study done with Ray Pearson Lehigh UniversityNeat10%M52 Nstudy done with Ray Pearson, Lehigh CTBN X 810% CTBN EEWT oughening of Epoxy systemsImpact TestingDGEBA + Dicyandiamide (DICY)High Speed Impact More than 2X (J)improvement in impact energy (CEAST Fractovis dart drop)

10 With Block Awith Block Copolymers . 10-30% improvement in peak force at a tM52N- 10%CTBN-10%27 toughening of Epoxy compositesHigh Tg systemsHigh Tg systemsRTM6 DGEBA+M-DEA10 Fluidity at 100 CLoading LevelK1CG1 CTg0% + at 120 CTg NeatLoading LevelK1CG1 CTg0% toughening and good maintenance of TgE KICM51, M52: Lower MW MAM 28meets RTM specs for viscosityToughening of Epoxy adhesives2530a)NeatNanostrength-10%CTBN- 10%1520 Strength (MPaCTBN 10%510 Lap Shear S0 DICYJ effamine D230 DETAS tudy done by Rescoll laboratories No detrimental effect on adhesion in DICY and polyetheramine (Jeffamine D230) cured epoxies while maintaining Tg and improving fracture toughness Significant improvement in lap shear strength in diethylene triamine (DETA)29 Significant improvement in lap shear strength in diethylene triamine (DETA) cured epoxiesToughening of Epoxy systemsDissolution of Block Copolymers in Epoxy Block Copolymers Dissolution time in low Mw Epoxy resinwill dissolve in Epoxy resin.