kaneka core-shell toughening systems for … · kaneka core-shell toughening systems for...
TRANSCRIPT
Douglas J. Sober713-503-1558
Kaneka Texas Corp2 Northpoint Drive
Suite 200Houston, TX 77060
www.kanekatexas.com
Kaneka CoreKaneka Core--Shell Toughening Shell Toughening Systems for Thermosetting ResinsSystems for Thermosetting Resins
What is CoreWhat is Core--Shell Rubber (CSR) ?Shell Rubber (CSR) ?
2-Layer CSRCo-Polymer II designedto be compatible withthermosetting resin.This is the shell.
Co-Polymer I designedfor impact resistance.This is the core.- butadiene/styrene- polybutadiene- siloxane- acrylic
Applications of CSR?Applications of CSR?
• Thermoplastic resins systems.- PVC- ABS
• Thermosetting resins systems for:- Adhesives.- Composites.- Electrical Castings- Coatings- Copper-Clad Laminates
Core Shell Rubber Advantages:Core Shell Rubber Advantages:• Outstanding Toughness Improvement:
- Fracture Toughness- T-Peel Strength- Lap-Shear Strength
• No Depression of Tg.• Wide Cure Window.• Consistent Morphology.• Low Ionic and Surfactant Content.• Extremely Stable.• Compatible / synergistic with Secondary Tougheners.• Nano-size particles do not filter.• Composite parts tend to be very translucent.
How does CSR toughen resins?How does CSR toughen resins?
• Core polymer cavitates on impact dissipating energy. Reduced damage area
• Small, evenly dispersed particlesact as a crack terminator.
• Core polymer relieves inherent stress generated during curing.
Inter-laminarbond & peelstrengthimprovement
Dimensional stability& microcrack resistanceNote: Optimization of particle size and inter-particle
distance (volumetric particle concentration) is critical to achieving the best performance
CSR Manufacturing Process
Epoxy
Solid CSRCan only be broken up to 1500 nm minimum with wide particle size
distribution
KANEKA CSR
Process
Epoxy/CSRKane Ace MX
Agglomeration /Drying
Latex
MX Process
Narrow range of 100 nm particles
Basic Properties of MX system
Core Shell Rubber particles are homogeneously dispersed in epoxy resin with long term stability
Core Shell Rubber particles are homogeneously dispersed in epoxy resin with long term stability
Conventional Solid CSR(10 wt%) in epoxy
New MX CSR(25 wt%) in epoxy
Appearance - Cured system“Transparent”
TEM observation - Cured system
Comparison of Kane Ace MX CSR versus Powder CSR
1µm
MX CSR
Powder CSR
What is Kane Ace MX:What is Kane Ace MX:
Kane Ace MX are concentrates comprised typically of 25% by weight of CSR dispersed in various thermosetting resins. The liquids are easily poured after heating and the individual CSR domains remain uniformly dispersed during storage and formulating.
Kane Ace MX Products:Kane Ace MX Products:
Grade CSR Type / Loading Carrier ResinMX 124 St-Bd 25% Liquid Bis A epoxy (lowest viscosity)MX 125 St-Bd 25% Liquid Bis A epoxy MX 133 St-Bd 25% Liquid Bis F epoxy (lower viscosity)MX 135 St-Bd 25% Low crystallizing liquid Bis F epoxyMX 136 p-Butadiene 25% Liquid Bis F epoxy (lower viscosity)MX 153 p-Butadiene 33% Liquid Bis A epoxyMX 156 p-Butadiene 25% Liquid Bis A epoxyMX 210 St-Bd 25% Epoxidized Phenol NovolakMX 227* St-Bd 25% Epoxidized BPA NovolakMX 338 St-Bd 25% Brominated Di-functional epoxyMX 392 St-Bd 25% Brominated Multifunctional epoxyMX 416 p-Butadiene 25% Multifunctional Epoxy Resin (TGMDA)MX 451 St-Bd 25% Multifunctional Epoxy Resin (TGPAP)MX 554 St-Bd 25% Cyclo-Aliphatic epoxy (MX 601* St-Bd 25% Resole NovolakMX 615 St-Bd 25% Di-allyl BPA (for BMI)MX 660 Siloxane 25% Di-allyl BPA (for BMI)MX 715 St-Bd 25% Polypropylene Glycol carrier (mw 400)MX 717 St-Bd 25% Polypropylene Glycol carrier (mw 1000)MX 719 St-Bd 25% Polypropylene Glycol carrier (mw 2000)MX 960 Siloxane 25% Liquid Bis A epoxy
*Developmental grades not yet available in commercial quantities
Example for Comparative TrialExample for Comparative Trial
Part A:
70 parts liquid Bis A resin 52 parts liquid Bis A resin20 parts epoxy resin B 20 parts epoxy resin B10 parts reactive diluent 10 parts reactive diluent
24 parts MX 125
Part B:
30 parts Part B 30 parts Part B
Mix Ratio Part A to B:
100/30 106:30
Core Shell Concentration:
0% 4.4%
Existing System MX Toughened
Basic Properties of MX system
MX 125 Viscosity as a Function of Concentration
0
20,000
40,000
60,000
80,000
100,000
120,000
140,000
0 5 10 15 20 25 30
CSR concentration (wt%)
Visc
osity
(cps
) 25C
50C
WorkingRange
T-Peel Strength of DGEBA Epoxy/MX 120 System
0
5
10
15
20
25
30
35
T-peel S trength / pli
C S R 0% C S R 5% C S R 10%
0
1000
2000
3000
4000
5000
6000
Lap Shear PSI
0 % Control 5 % CSR 10 % CSR
Lap-shear Strength of DGEBA Epoxy/MX 120
T-peel Strength of MX 120 vs. CTBN in DGEBA Epoxy
C ontrol5%
10%
C TB N
C SR M aster-batch05
1015202530
35
T-peelStrength/pli
Comparison of CSR and CTBNComparison of CSR and CTBNLap-shear Strength of MX 120 vs.
CTBN in DGEBA Epoxy
Control
5%
10%
C T B N
C SR M aster-batch0
1000
2000
3000
4000
5000
6000
Lap-shearStrength/psi
Types of Fractures
Depending on the stress field in the vicinity of the crack tip, three principle fracture modes are possible: Mode I, Mode II, and Mode III.
Mode I bending is tensile, Mode II is shear, Mode III is tearing
Toughening Effect of Epoxy/ Kane Ace MX SystemToughening Effect of Epoxy/ Kane Ace MX System
Three-Point Bending
force
specimen: 6cm x 1.2cm x 0.5cm
pre-crack: 0.6cm depth by blade-tapping
head speed: 1mm/min.
stress
strain
strength
energy
ASTM 5045 CastingASTM 5528 Reinforced
Fracture Toughness of DGEBA Epoxy/MX 120
00.5
11.5
22.5
3
K1c/ MPam1/ 2
CSR 0% CSR 10%
DDSpiperidine
Fracture Toughness of DGEBA Epoxy/MX 120
0
500
1000
1500
2000
2500
G 1c/Jm 2
C SR 0% C SR 10%
DDS
piperidine
Comparison of CSR and CTBNComparison of CSR and CTBNFracture Toughness and Glass Transition Temperature
of MX 120 vs. CTBN in DGEBA Epoxy
0
100
200
300
400
500
600
control CSR Master- batch CTBN
G1c
/J/
m2
0
50
100
150
200
250
Tg/
C
Tg
9291.700Vinylester/MX153(85/15)
1640.823Vinylester
G1C(J/m2)K1C (MPa⋅m1/2)
Fracture Toughness of Vinylester / MX153 system
Vinylester: Reichhold 9800-05A, Casting: 50C/17hr-120/2hr
Lead-Free Data Sheets IPC-4101B:
Slash Sheet # 99 101 121 124 126 129
Tg min 150 110 110 150 170 170Tg max
Td min 325 310 310 325 340 340
Fillers yes yes no no yes noFlame retardant RoHS BR RoHS BR RoHS BR RoHS BR RoHS BR RoHS BRCuring Agent N/A N/A N/A N/A N/A N/A
Flammability V-0 V-0 V-0 V-0 V-0 V-0
Z-Axis alpha 1 max 60 60 60 60 60 60Z-Axis alpha 2 max 300 300 300 300 300 300% max 3.5 4.0 4.0 3.5 3.0 3.0
T-260 30 30 30 30 30 30T-288 5 5 5 5 15 15T-300 AABUS AABUS AABUS AABUS 2 2
UL MOT AABUS AABUS AABUS AABUS 130 130
Amendment 2
THE REACTION OF DICY WITH EPOXY RESIN:
BASE MATERIAL WORKSHOP
(DICY)
Phenol Novolak Resinspopular curing agentsfor lead-free FR-4
EFFECT OF CROSS LINK DENSITY ON LAMINATE PROPERTIES:
BASE MATERIAL WORKSHOP
TG/Td PEELSTRENGTH
INTERLAMADHESION
CHEMICALRESISTANCE
FRACTURETOUGHNESS
THERMALRESISTANCE
Z-AXISCTE
CROSS LINKDENSITY OF
SYSTEM
Good Good Good GoodBad Bad Bad
Life ScienceProducts
Synthetic fiber
Electronic Products
Foodstuffs Products
Expandable Products
Co Q10
Functional Plastics
Global Revenue: $5.3 billion 2006“#1 Producer of CSR
Toughening Agents Worldwide”
Kaneka Corporation• Today Kaneka is a world leader in the creation of
innovative technologies in areas such as polymers, construction materials, and pharmaceuticals.
• Kaneka is a global organization with production facilities on four continents and approximately 7000 employees.
• Revenue for our latest fiscal year (ended March ‘06) is estimated worldwide at approximately $5.3 billion.
Kaneka Global Manufacturing• Kaneka currently manufactures “Modifiers” at four sites
around the world. These include:
Kaneka Japan Asia Takasago, JapanKaneka Texas USA Pasadena, TexasKaneka Belgium Europe Oevel, BelgiumKaneka Malaysia Asia Kuantan, Malaysia
• These four sites provide Kaneka with an annual capacity of modifiers of approximately 400 million pounds.
Kaneka Texas Corporation• A wholly owned subsidiary opened in 1983, Kaneka
Texas (KTC) is responsible for marketing several Kaneka product lines throughout the Americas.
• Business operating at KTC include:• 1.) Polymer Modifiers (Kane Ace)• 2.) CPVC Resins (Kanevinyl)• 3.) Foamed Olefins Resins (Eperan, Eperan PP)• 4.) Modified Silicone for Sealants (MS Polymer)• 5.) Polyimide Film (Apical)• 6.) Nutrients (CoQ10)