Nanostrength®

Block Copolymers
for Epoxy
Toughening
100 nm
PABu

PMMA

PMMA / Epoxy
Nanostrength® for epoxy toughening

 Arkema Overview
 Nanotechnology Platform at Arkema

 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 Adhesives

2
Arkema 2007 overview
Sales by region

Europe
(excl. France)
39%
North
Sales: €5.7 bn ($8.5B) America
25%

France
Capital employed: €3.1
€3 1 bn 18%
Row Asia
5% 13%
2007
Capex: 4% of sales
Sales per year
In € bn
R&D: 3% of sales
5.52 5.67 5.70

15 200 employees
15,200

2005 2006 2007

3
R&D accelerates product innovation
Overview (2007) R&D by segment

3% of sales Breakthrough

1 350 researchers
1,350 12%
Vinyll
Vi
Products 12%
Near 100 joint projects with universities
51% Performance
6 R&D centers Products
Industrial 25%
Portfolio around 5,700 patents Chemicals

2005

Recent breakthroughs

4
Nanotechnology Platform at Arkema

Our customers :
Compounds, Thermosets,
Pigments, Engineering resins,
Paints, Coatings,
Adh i
Adhesives,…
Functionalized
CRP* initiator Specialty Block
& Copolymers
FlexiBloc® &
CRP* FlexiBloc®
macroinitiator Reactive Block
Copolymer
Block Copolymers
p y

5
Nanotechnology Platform at Arkema

Block copolymers for epoxy toughening

6
Classical vs. Controlled Free Radical
 Classical Radical  Controlled Radical
Polymerization Polymerization

 No control of  “Living”chain ends

termination experience reduced
 Wide polydispersities termination
 Random sequencing  Reduced
off monomer units
it polydispersities
 Block copolymers
possible

7
Complete Control of Block Structure

 Block copolymers

Classical Block copolymers

Random Diblock ABA triblock ABC triblock

copolymer copolymer copolymer copolymer
 Incompatibility between blocks  organization at the nanometer
scale

8
 Nanostrength® Triblock Polymers

 Controlled Radical Polymerization (CRP) ABA, AB

Poly[(Methyl)methacrylate]
P l [(M th l) th l t ] -b-
b poly(Butyl
l (B t l A
Acrylate)
l t ) -b-
b poly[(Methyl)methacrylate]
l [(M th l) th l t ]
Poly[(Styrene] -b- poly(Butyl Acrylate) -b- poly[(Styrene]

 Functional comonomers can be added (AA, MAA, PEGMA, HEMA,…)

 Anionic polymerization SBM

polyStyrene -b- polyButadiene -b- poly[(Methyl)methacrylate]

 Outstanding g control of molecular weight,

g molecular weight g
distribution, composition, chain architecture, functionalization

9
Block Copolymers for Epoxy Toughening
 Structural Adhesives (Automotive, Industrial, Assembly, Wind
Energy, Electronics …)

 Coating (Solvent, Powder,…)

 Composites
p ((Aerospace,
p , Sports
p and Leisure,…)
, )

 Epoxy compounds

Nanostrength® is suited for every application that needs

an increase in resistance to crack propagation while
maintaining Tg and Modulus of the systems.

Due to the unique nanostructuration achievable with

Nanostrength®, it is possible to achieve identical toughness
to competiti
competitive
e modifiers (CTBN) but
b t using
sing red
reduced
ced loading
levels.
10
 Block Copolymers for Epoxy Toughening
Advantages of Nanostrength®:
• Toughening with little loss of Tg or Modulus
• Outstanding toughening at lower loading due to unique modifier
morphologies
• Ease of Processing
Processing- additive dissolves in epoxy resin
• Nanoscale self-assembled particles allow for toughening of:
1. Thin adhesive bond lines
2. Thin coatings
3. Composites with small inter-fiber spacing
CTBN / TP Core-Shell Nanostrength

1 ~ 5 µm 0.1 ~ 0.8 µm 10 ~ 100 nm

11
Block Copolymers for Epoxy Toughening

Low Tg systems: DGEBA + JeffamineTM T403

M53 CTBN
Loading Level K1C G1C Tg K1C G1C Tg
0% 0.76 183 92 0.76 183 92
2.5% 1.66 1873 92
5% 1.71 1933 92
7.5% 1.95 2348 93
10.00% 2.78 3437 97 1.98 1640 85

 Superior toughening at equivalent loadings

 Equivalent toughening at lower loadings

12
Block Copolymers for Epoxy Toughening

Intermediate Tg systems: DGEBA + DICY

M52N CTBN
Loading Level K1C Tg K1C Tg
0% 0.88 +- 0.1 148.1 0.88 +- 0.1 148.1
2.50% 1.32 +- 0.12 146.4 1.03 +- 0.12 TBD
5.00% 1.64 +- 0.08 144.2 1.32 +- 0.12 139.1
10.00% 1.82 +- 0.11 135.4 1.62 +- 0.08 129.2

Dicyandiamide (Dicy) is hardener

representative of:
- Adhesives
- Sports and Leisure composites
- Coatings

13
A Self-assembling Nanotechnology
- Affinity between epoxy monomers and PMMA
- Repulsion between epoxy monomers and the middle block(s)
 Nanophase separation of PBuA blocks:

M-A-M DGEBA

PABu

PMMA

PMMA / Epoxy
E

PABu

PMMA

PMMA / Epoxy

14
Toughening of epoxy systems
• Many mechanisms contribute to epoxy toughness :

• Shear yielding
• Multiple crazing
• Crack pinning
• Crack bridging
• Crack deflection
• ….
Toughening
T h i iis more th than flflexibilization.
ibili ti
Flexibilization lowers the modulus of the material to
decrease brittleness (CTBN - flexibilizer) by reacting
to the backbone of the epoxy. Nanostrength® (and
core shells)
h ll ) maintain
i t i modulus
d l while hil ttoughening.
h i

Pearson (1993)
H
Huang, Y
Y., and
d Ki
Kinloch,
l h A.J.,
AJ JJ. M
Mater.
t S Sci.,
i 2727, 2763 (1992)
(1992).

15
Toughening of epoxy systems
The most efficient mechanisms to toughen are
system & condition dependant:
• Low Tg systems, high T° or low speed testing conditions:
 Shear yielding
Matrix network has enough
mobility to activate plasticity

• High Tg systems,
systems low T° or high speed testing conditions::
 Multiple crazing Matrix network too cross-linked to
 Crack bridging activate p
plasticity
y
 C
Crackk pinning
i i
 Crack deflection

R.A.
R A Pearson
Pearson, "An
An overview of organic toughening agents for epoxy resins
resins", ERFD Spring 2000 Conference
Conference,
April 16-18, 2000, San Antonio, TX

16
Toughening of epoxy systems

 Existing tougheners have specific toughening mechanisms:

 Liquid
q reactive rubbers  shear y
yielding
g
 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
formation
Unique morphologies lead to better toughening
Crack Bridging
Crack Pinning (strong matrix adhesion)
Crack Deflection
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Toughening of epoxy systems
Cavitation of nanodomains

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Toughening of epoxy systems

Modifier morphology in cured epoxy dependent on:

•Crosslinking/Resin chemistry
•Block Copolymer Chemistry
M51, M52, M53: PMMA-block-PBuA-block-PMMA

DGEBA + M-DEA
M DEA DEGBA + Jeffamine
T403
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 Toughening of epoxy systems
Block Copolymer Chemistry dictates Modifier MAM exp1

Morphology
5µm
+10% +10% +10%
Ref
MAM exp1 MAM exp2 MAM M22N
 DGEBA + DDS

MAM exp2

3µm

Development of functionalized grades to further improve M22N

nanostructuration with all types of epoxy systems:
2µm
M22N or M52N: PMMA/DMA-block-PBuA-block-PMMA/DMA
PMMA/DMA block PBuA block PMMA/DMA

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Toughening of epoxy systems
Modifier Morphology dictates Properties
Low Tg systems
DGEBA + Jeffamine
J ff i T403

M53 gives
M22N gives
“spider web”
excellent
agglomeration
nanostructuration
for superior
for p
perfect
t
toughening
h i
transparency

Neat
Epoxy
M22N M53
K1C 0.76 1.54 2.78
G1C 183 880 3437

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Toughening of epoxy systems
Low Tg systems DGEBA + Jeffamine T403
Plastic Deformation of the samples
with block copolymers

250

200

150
Force (N)

Neat
10% M53
100 10% CTBN

50

0
0 0.2 0.4 0.6 0.8 1 1.2
Displacement (mm)
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Toughening of epoxy systems
Balance of properties:

Fluidity at 80°C
Superior
S i 1.0
DGEBA+ Jeffamine T403
toughening with 0.8

some viscosity 0.6

penalty with 10% Tg

0.4
Fluidity at 40
40°C
C

M53
0.2
or
0.0 Neat
10% CTBN
Equivalent 10% M53

viscosity and 2.5% M53

toughening,
g g, GIC E

improved Tg
and modulus at
¼ of the loading KIC

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Block Copolymers for Epoxy Toughening
Intermediate Tg systems: DGEBA + DICY
M52N CTBN
Loading Level K1C Tg K1C Tg
0% 0.88 +- 0.1 148.1 0.88 +- 0.1 148.1
2.50% 1.32 +- 0.12 146.4 1.03 +- 0.12 TBD
5.00% 1.64 +- 0.08 144.2 1.32 +- 0.12 139.1
10.00% 1.82 +- 0.11 135.4 1.62 +- 0.08 129.2

K1C= 1.54 K1C= 1.82

Nanospherical
p micelles for M52N gives worm-like micelle
perfect transparency (exp. structure for excellent
grade) toughening
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Toughening of epoxy systems
Balance of properties:
Fluidity at 40°C Neat
Superior CTBN 10%
toughening and M52N 10%
Tg at equivalent M52N 5%
loading
Tg Fluidity at 80°C

Equivalent
q
toughening and
viscosity with
enhanced Tg at
½ of the loading

KIC E

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Nanostrength® for Epoxy Toughening
KIC T (°C) Even greater advantages with Nanostrength®
160 C cure (MPa.m )
0.5 in more “toughenable” DICY cured systems

Reference 0.72 108

•lower cure temperature
10% M52N 2.4 118
10% CTBN 1.88 112 •higher Epoxy Equivalent Weight (EEW) resin

DGEBA/DICY Neat
study done with Ray Pearson
Pearson, Lehigh University 10%M52N
10% CTBN X 8
2.5 10% CTBN X13

1.5
K1C

0.5

0
180 190 200 210 220 230 240 250
DGEBA EEW

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Toughening of epoxy systems
High Speed Impact Resistance DGEBA + Dicyandiamide (DICY)

Impact Testing

2.5 •More than 2X

improvement in impact
Absorbed (J)

2 energy (CEAST
Fractovis dart drop)
1.5
with block copolymers
copolymers.
Energy A

1 •10-30% improvement
in peak force at break.
0.5

0
Neat M52N- 10% CTBN-10%

27
Toughening of epoxy composites

High Tg systems RTM6

DGEBA + M
M-DEA
DEA Fluidity at 100°C
10
1.0

M53 0.8
Loading Level K1C G1C Tg
0.6
0% 0.74 258 170
10.00%
% 1 01
1.01 530 168 0.4
Tg Fluidity at 120°C
0.2

DGEBA + DDS 0.0

Neat
M52N M51
M52
Loading Level K1C G1C Tg PSU
0% 0.9 283 229
10.00% 1.08 428 227

KIC E
Excellent toughening and good
maintenance of Tg M51, M52: Lower MW MAM
meets RTM specs for viscosity

28
Toughening of epoxy adhesives
30 Neat
Nanostrength-10%
25
a)

CTBN-10%
CTBN 10%
Strength (MPa

20

15
Lap Shear S

10

0
DICY Jeffamine D230 DETA
Study 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)
•Significant
cured epoxies

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Toughening of epoxy systems
Dissolution of block copolymers in epoxy

Dissolution time in low Mw epoxy

p y resin •Block copolymers
will dissolve in
90°C
50
135°C
epoxy resin; no
45 need for dispersion
40
•Block copolymers
35
dissolve quickly at
e (min)

30
elevated
25 temperatures with
Time

20 minimal shear
15
•Transparency of
10
solution does not
5
always indicate
0 dissolution!
M52 M53 M52N

30
SBM Block Copolymers for Epoxy Toughening

Neat
 PMMA block gives excellent Epoxy E21 E41
compatibility to epoxy systems DGEBA/Jeffamine
which are less polar (similar to Tg 92 97 TBD
non-functionalized MAM) K1C 0.76 2.91 TBD
 Butadiene block has a lower Tg G1C 183 3940 TBD
((-70 C)) than butylacrylate
y y ((-40 DGEBA/MDEA
T
Tg 170 176 177
C) so improved toughening at
K1C 0.74 0.93 1.08
lower temperatures possible
G1C 258 TBD 418
 Higher differences in chi Phenolic Novolac
parameters
t allows
ll for
f shorter
h t Tg 175 TBD 180
(lower MW) block copolymers to K1C 0.63 TBD 0.86
still nanostructure -> Lower G1C 152 TBD 282
viscosity ypproducts p
possible

31
Toughening of epoxy systems

 Advantages
Advantages:  Drawbacks
Drawbacks:
 S
Superior
i Toughening
T h i to  N d to dissolve
Need di l at high
hi h
competitive products temperature in epoxy
 Equivalent toughening at much  Increase of viscosity (mitigated
lower loadings ($ advantages) by use at lower loadings)
 Versatile block copolymer
chemistry allows for the proper
grade to be selected for given
g g
epoxy systems
 Balance of Properties: Limited
loss of Tg and Modulus
 High reproducibility (controlled
by Thermodynamic)/ no need for
dispersion

32
Commercial Nanostrength® Grades
SBM grades
E21 - Medium MW with high butadiene content, good for structural
applications; excellent toughening with PMMA friendly cross-linking
agents (Jeffamine, MDEA)
E41 - Low MW with medium butadiene content, low increases in viscosity,
good for electronic or viscosity sensitive applications

MAM grades
M52 medium MW,
M52- MW low viscosity
M53-High molecular weight, excellent toughening with PMMA friendly
cross-linking agents (Jeffamine, MDEA)
M52N- Functionalized MAM; best toughening with PMMA unfriendly cross-
M52N cross
linking agents (DICY, DDS); composite and adhesive applications
M22N- Highly functionalized MAM for excellent compatibility and
nanostructuration (transparent applications or highly polar systems)

33