1. Novel Toughening Technology for Epoxy Thermosets Steve Hoyles, Nikhil Verghese, Michael Ross, Marv Dettloff and Ha Pham The Dow Chemical Company
11/22/2018

2. Outline Self assembled toughening technology background
Example Application Area #1: M&PC Coatings
Example Application Area #2: Powder Coatings
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3. Purpose:. Utilize self assembled block. copolymer technology to
Purpose: Utilize self assembled block copolymer technology to increase the ductility of epoxy thermosets without negatively impacting other properties.
11/22/2018

4. There are two approaches to increased ductility…
Flexibilization
Backbone Stiffness
Crosslink Density
Plasticizers and diluents
Toughening
Interfacial strength
Particle size
Polydispersity
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5. Other Technologies Plastisizer Aliphatic backbone CTBN Core Shell
Embrittlement
Chem Resist
Aliphatic
backbone
Reactivity
CTBN
Corrosion
Core Shell
Rubbers
Viscosity
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6. Flexibility versus Toughening
Flexbilization
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7. Self Assembled Block Copolymers
Cured epoxy
curing
Curing agent
Epoxy
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8. Macrophase Separation (example CTBN technology)
Cure
Self Assembly (current technology)
Cure
Epoxy
Curing Agent
Polymer
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9. Self-Assembly vs. Macrophase Separation
Macrophase (e.g. CTBN)
Low concentrations (5-10 vol%)
self -assemble into dispersed morphologies
Less detrimental effect on
glass transition temperature, Tg,
modulus, E
Controlled structure size
Can retain optical clarity
No pollution of continuous phase
High concentrations (10-20 vol%)
macro phase separation
Detrimental effects on
glass transition temperature, Tg,
modulus, E
Hard to control structure size
loss of optical clarity
agglomeration
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10. TEM Images of Self Assembled Morphologies
Wormlike Micelle
Spherical Micelle
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11. Second Phase Toughening Mechanism
Tensile Direction
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12. Typical Tensile behavior5 10 15 20 25 30
Strain (%)
Stress (Pa)
Modified
Unmodified
Reduction of
yield stress
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13. Effect on Material Properties
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14. Effect on Tg and Modulus
Results from a plaque
1.E+09
1.E+08
Storage Shear Modulus, G' (Pa)
1.E+07 
1.E+06
DER epoxy resin cured with Phenolic Hardener: CONTROL
Modified with 5wt.% Toughening Agent
1.E+05 50
100
150
200
250
300
Temperature (°C)
 Trademark of The Dow Chemical Company
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15. Outline Self assembled toughening technology background
Example Application Area #1: M&PC Coatings
Example Application Area #2: Powder Coatings
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16. XU19108.00 Effective at 5-10 Vol% of total dry solids
neat viscosity = 4000 cPs
Density = 1.03 g/l
100% solids
can be incorporated during paint grind phase or let down
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17. Clear Coat Testing Ancamine 1618* Ancamide 2353* NC541LV **
modified IPDA adduct
cut in benzyl alcohol
Ancamide 2353*
TETA polyamide
NC541LV **
phenalkamine
* Air Products
** Cardolite
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18. Clear Film Formulations
Prepared by Draw Down
B1000 panels and free films from tin plate
Cured at 60°C
DFT = 110 +/- 5 microns
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19. Typical Impact Testing Result
panels shown cured with Ancamine 1618
110 +/- 5 microns
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20. Free Film Tensile Results
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21. Pigmented system Based on D.E.R. 331 cured with Ancamide 2353
Pigmented with red iron oxide, extender and an anticorrosive pigment
XU19108 was added at both 6.8% and 13.3% by volume dry paint
Coatings spray applied on bare cold rolled steel panels
Cured for 14 days at room temperature.
DFT = 3.5 mils
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22. Pigmented standard formulation
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23. Pigmented system Test Results
Standard
6.8 Vol%
13.3 Vol%
PVC
37.5%
38.6%
VOC
330.2 g/l
312.0 g/l
300.4 g/l
Viscosity
, 25°C
110 K.U.
98 K.U.
93 K.U.
Sprayable vol. solids
62.2%
64.3%
65.7%
Hardness 6H 3H
Dry Adhesion 2B 4B
Direct Impact 15 20 22
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24. Abrasion resistance
Taber abrasion resistance is negatively impacted by the addition of XU
Tests run on clear coats cured for 14 days at 25°C with Ancamide 2353 with and without the toughening agent at 10 vol% loading
ASTM D4060, 1000 g weight
The unmodified sample lost 66.1mg per 1000 cycles
The modified sample lost 108.1mg per 1000 cycles
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25. Effect on Gel and cure times
Ancamine 1618
Minimal effect on gel time
Effect is that of a non-functional diluent
decreases the concentration of reactive groups
NC541LV
Ancamide 2353
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26. Significant Adhesion Improvement
5.5% modification
Ancamide 2353 cured
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27. difference in corrosion
Salt Spray Results
There is no apparent
difference in corrosion
resistance between
the standard and the
modified system
ASTM B117, 1000 hours on cold rolled steel Ancamide 2050 cured
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28. Outline Self assembled toughening technology background
Example Application Area #1: M&PC Coatings
Example Application Area #2: Powder Coatings
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29. Pipe Coating Formulation
14.5 vol%
6.9 vol%
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30. Pipe Coating Testing Formulations were dip applied
8”x1”x3/8” sand blasted bars
4 point bend at sub-ambient temperatures
instron test frame
number of hard cracks recorded
Glass transition temperatures measured from free films
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31. Test Results
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32. Low Temperature 4 point bend performance
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33. Conclusions Self assembled second phase toughening agents
improved impact resistance
improved adhesion
without negatively affecting viscosity or Tg
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