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Nanostrength Block Copolymers for Epoxy Toughening

Nanostrength Block Copolymers for Epoxy Toughening

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05/11/2014

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Nanostrength
Block Copolymers for Epoxy Toughening
 
 Robert Barsotti, Arkema Inc., 900 1st Avenue, King of Prussia, PA, 19406, USA
Abstract
 Due to their high strength, excellent high temperatureproperties and good adhesion to many surfaces, epoxiesare extremely valuable engineering materials incomposite, adhesive, coating, and electronic applications.Epoxies, however, suffer from a very low toughness.Arkema’s controlled radical and anionic polymerizationtechnology has been used to synthesize block copolymersadditives, which provide excellent toughening to epoxieswithout sacrificing modulus or glass transitiontemperature. By incorporating functionality into the epoxymiscible block of the polymer, nanostructuration of thesepolymer additives are achieved in a wide range of epoxysystems, resulting in excellent thermal and mechanicalproperties.
Introduction
 
Due to their high strength, excellent hightemperature properties and good adhesion to manysurfaces, epoxies are extremely valuable engineeringmaterials in composite, adhesive, coating, and electronicapplications. Epoxies, however suffer from a very lowtoughness. One approach to improve the toughness of epoxies is via flexibilization. Monofunctional or highMW difunctional epoxy molecules can react directly intothe epoxy matrix, lowering its crosslink density. Thisimproves the toughness of the material but does so bysacrificing strength and lowering the glass transitiontemperature of the network. Similarly, reactive rubbermodifiers, such as carboxy-terminated butadieneacrylonitrile (CTBN), can react into the surroundingepoxy matrix. Again toughness is increased but with thesacrifice of strength and thermal properties.
1
A second approach to toughening is the inclusion of softerphase material which does not react into the matrix, eithercore-shell particles, typically with a PMMA shellsurrounding a low T
g
rubber core
2
or thermoplasticspheres such as polysulfone (PSU). In core shells, uponan impact event or an approaching crack tip front, stress isconcentrated in the low T
g
rubber core, causing cavitationof the core. This cavitation then causes subsequent plasticdeformation of the surrounding matrix (often referred to asshear banding), absorbing energy from the impact or crack front and thus toughening the epoxy. The difficulty withthe use of core shells in epoxies relates to the problems of achieving a uniform dispersion; the highly cross-linkedrubber cores do not allow for their dissolution in epoxyresins. (Core shells are typically used to toughenthermoplastics where extremely high shear and hightemperatures aid dispersion during extrusion.)Thermoplastic spheres suffer from having a much highermodulus. Thus, they are not effective as stressconcentrators and cannot easily cavitate. They can onlytoughen the epoxy by physical mechanism such as crack pinning or crack deflection, less efficient mechanisms thanthe previously described cavitation and shear bandformation mechanism. Due to this poor efficiency, theyare often used at high concentrations, where they can havea detrimental effect on properties critical to processingsuch as viscosity.In order to overcome the deficiencies associated with theaforementioned types of epoxy toughening agents,controlled radical polymerization and anionicpolymerization has been used to design acrylic block copolymers under the trade name of Nanostrength
 
block copolymers. The structure of these block copolymers canbe tuned to give excellent toughening to a wide range of epoxy systems without sacrificing strength or thermalproperties.
Block Copolymers – A Self AssemblingTechnology
 
One family of block copolymers useful in epoxies aretriblock polymers consisting of polymethylmethacrylate-b-polybutylacrylate-b-polymethylmethacrylate (MAM)family. The PMMA blocks give compatibility to epoxyresin, while the PBuA blocks provide an immisicible softrubber phase for toughening. The MAM products (e.g.M51, M52 and M53) can easily be dissolved in a typicaldiglycidyl ether of bisphenol A (DGEBA) resin with theapplication of heat and a low amount of shear. Whendissolved in DGEBA resin, the MAM block copolymerself-assemble into nanostructures. The PMMA block willassociate with the epoxy resin, forming an effective shellsurrounding an immiscible PBuA core. (Figure 1) TheBates group has shown using non-acrylic block copolymers polymers that the size and shape of the self-assembled structures can be varied from sphericalmicelles to worm-like micelles to vesicles by increasingthe ratio of epoxy immiscible block to epoxy miscibleblock.
3
 A second family of block copolymer useful for tougheningof epoxies are styrene-b-butadiene-b-polymethylmethacrylate (SBM, such as grades E21 andE41) block copolymers. These polymers, made by
 
anioinic polymerization, are particularly beneficial inapplications where low temperature impact resistance isneeded.The structuration present in the final cured epoxy usingblock copolymers depends on the chemical nature of thecrosslinker (hardener) and the chemical composition of the block copolymer.
4
Less polar crosslinking agents suchas M-DEA (methylene-diethylaniline) have goodcompatibility with PMMA so the exact structurationpresent in the uncured DGEBA resin remains in the curedepoxy. With more polar crosslinking agents, thecompatibility with PMMA is not as favorable. Uponaddition of the hardener, the MW of the epoxy moleculesbegins to increase, making the enthalpic contribution tofree energy more important than the entropic contribution.Unless good chemical compatibility is maintained, microor macro aggregation of the block copolymer can occur.In order to increase the compatibility of block copolymerswith more polar hardeners, MAM grades have beendeveloped which incorporate dimethylacrylamide (DMA)into the PMMA blocks. (e.g. M52N) DMA has a higher
χ
 parameter (22.7 (J/cm
3
)
½
) which increases thecompatibility of the miscible block with more polarcuratives such as diaminododecylsulfonate (DDS) (
χ
=23.5(J/cm
3
)
½
)
4
The DMA allows for better chemicalcompatibility and thus allows for nanostructuration, in theform of either spherical micelles or worm-like micelles, toremain in the cured epoxy.
Block Copolymers in Epoxy
Block copolymers allow for unique property sets to beachieved in epoxy systems, opening the door for newepoxy applications. Due to their non-reactive backbone,block copolymers can provide increases in tougheningwithout sacrificing T
g
or modulus. Due tonanostructuration, block copolymers
 
provides superiortoughening as compared to reactive rubber flexibilizers orcore shell toughening agents. In fact block copolymerscan be used at significantly lower use levels thancompetitive products to reach the same toughening levels.Additional advantages of block copolymers include theability to dissolve these polymers in epoxy resin (no needfor time consuming and inconsistent dispersion). Thesmall size of the self-assembled structures allows for itsuse in composites with small inter-fiber spacing or thinbond line adhesives.DGEBA epoxies were studied with several differenthardeners, M-DEA, polyetheramine (PA), dicyandiamide(DICY) and diaminodiphenylsulfone (DDS). The curedepoxy bars were evaluated for toughening by testing theK
1C
, (ASTM D5045-99) or the ability for the epoxy tostop crack growth. The T
g
of the epoxy was measured bydynamic mechanical analysis. The properties of block copolymer modified epoxies were compared to neat epoxysystems and those modified with CTBN. Tapping ModeAtomic Force Microscopy (TM-AFM) phase imaging wasused to observe the morphology of the modifiers in thecured epoxy.In the DICY cured DGEBA epoxy systems, block copolymers
 
with dimethylacrylamide (M52N) showssubstantial improvements in toughening as compared toequivalent loadings of micron sized reactive rubbertoughening agents (grade CTBN X13, with 74%butadiene) . (See Table 1) These polymers also showbetter T
g
retention than CTBN. Furthermore, equivalentlevels of toughening can be achieved using only 5%loading of M52N vs. 10% CTBN. At this loading ratio,the block copolymers have even larger advantages in T
g
 (with additional advantages in modulus and viscosity).When an identical formulation was cured at lowertemperatures, the advantage of M52N over CTBN becameeven greater (10% loading results in a K
1C
of 2.40 MPA*m
1/2
and a T
g
of 118
°
C with 10% M52N, while 10%CTBN gives a K
1C
of 1.88 MPA* m
1/2
and a T
g
of 112
°
C).Table 1. Comparison of toughening with block copolymers and CTBN in a DICY cured DGEBA epoxy.(K
1c
in MPA* m
1/2
;
 
T
g
in
°
C
 
)
 M52N CTBN X13
Loading Level K
1C
T
g
K
1C
T
g
 
0%
0.88 148.1 0.88 148.1
2.50%
 
1.32 146.4 1.03 TBD
5.00%
1.64 144.2 1.32 139.1
10.00%
1.82 135.4 1.62 129.2Figure 1. (Top) Schematic of MAM block copolymersproducts self-assembling in epoxy resin. (Bottom) TEMimages of self assembled nanostructures in epoxy resin.
DGEBA
200 nm100 nm
Butyl Acrylate,PMMA,PMMA/Epoxy
 
 It is interesting to look at the structure/propertyrelationship for block copolymers in epoxy. In the DICYsystem, a traditional MAM with no DMA (such as M53)at 10% loading undergoes micro-macrophase separation,resulting in a poor K
1C
(1.35 MPA* m
1/2
). M52N whichforms worm-like micelles in this system showsoutstanding toughening (K
1C
=1.82 MPA* m
1/2
with 10%loading). These worm-like micelles are very asymmetric,10-50 nm in width but several hundred nm in length. Anexperimental grade with even better compatibility to theepoxy matrix gives spherical micelles and a good but notoutstanding toughening (K
1C
=1.54 MPA* m
1/2
with 10%loading). (Figure 2)Figure 2. AFM Tapping modes images of 10% loading of M52N (left) and an experimental grade (right) in a DICYcured DGEBA epoxy.A study at Lehigh University has recently shown that thetoughening of epoxies with MAM block copolymersincreases as the epoxy equivalent weight (EEW) of theDGEBA backbone of the epoxy increases. This studyshowed that M52N in a dicy system exhibited superiorfracture toughness to different micron sized reactiverubber toughening agents (CTBN X13 or X8 with 82%butadiene) for both low and high EEW resins. (Figure 3)High speed impact testing (CEAST Fractovis Dart Drop)was also carried out to see the ability of a modified epoxyto absorb impact energy. CTBN was compared to block copolymer grade M52N in the same DICY system astested above (10% loading of the modifier). Again, block copolymers show superior ability in impact testing ascompared to the neat resin and micron sized rubbermodifiers, absorbing more than twice the energy at failureas shown in figure 4.Figure 3. Fracture toughness of dicy cured epoxies withdifferent EEW resins.The differences in toughening between competitivetechnologies are even more significant in a lower T
g
polyetheramine cured epoxy. In this system with a morePMMA friendly crosslinking agent, the greatestimprovements in toughening are seen with either an SBM(E21) or a traditional MAM (M53).Table 2. Comparison of toughening with Nanostrength
 block copolymers and CTBN in a polyetheramine curedDGEBA epoxy (K
1c
in MPA* m
1/2
;
 
G
1C 
in J/m
2
; T
g
in
°
C
 
)
ControlCTBNX13 10%E2110%M5310%K
1C
 
0.76 1.98 2.91 2.78
G
1C
 
183 1640 3940 3437
T
g
 
92 85 97 97
Figure 4. High speed impact energy of toughened epoxies.
Impact Testing
00.511.522.53
NeatM52N- 10%CTBN-10%
   E  n  e  r  g  y   A   b  s  o  r   b  e   d   (   J   )
500 nm
 
500 nm
 
 
DGEBA/DICY
study done with Ray Pearson,Lehigh University 
00.511.522.5180190200210220230240250
DGEBA EEW
   K
   1   C
   (
   M   P   A   *  m
   1   /   2
   )
Neat10%M52N10% CTBN X 810% CTBN X13

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