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Lecture 13: Influence of Chain Architecture on Microdomain
Transcript of Lecture 13: Influence of Chain Architecture on Microdomain
Lecture 13: Influence of Chain Architecture on Microdomain Characteristics
• Pursuit of New Block Polymer Structures…– AB: Diblocks, Rings, Multiblocks, Miktoarm Stars,
Star-Diblocks
– ABC: Terblock, Miktoarm Stars
• Novel Microdomain Patterns Arising:– The Theorist’s Nightmare: Stadler’s Goldmine – Processing: a neutral(?) solvent– Critical Nχ AB depends on Architecture– Architecture can drive block mixing
Possible Chain Architectures from an A/B/C Terpolymer
Predicting the Future of ABC Polymers
Text removed due to copyright restrictions.
Please see the final paragraphs of Mogi, Yasuhiro, et al. “Preparation and Morphology of Triblock Copolymers of the ABC Type.” Macromolecules 25 (1992): 5408-5411.andAuschra, Clemens, and Stadler, Reimund. “New Ordered Morphologies in ABC TriblockCopolymers.” Macromolecules26 (1993): 2171-2174.
Typical Experimental Procedure
Complex Morphologies in ABC BCPs
Formation of Ordered Microdomainsby Self Assembly
Linear AB Copolymer Linear ABC Terpolymer
Spheres Cylinders DoubleGyroid
DoubleDiamond
Lamellae
0-21% 21-33% 33-37% 37-50%
IMDS
"A" block "B" block
Junction pointIncreasing volume fraction of minority phase polymer
Image removed due to copyright restrictions.
Please see Bates, F. S., and Fredrikson, G. H. “Overview of ABC Structures and Thermodynamics.” Physics Today 52 (February 1999): 32
Figure by MIT OCW.
MORPHOLOGY DIAGRAM FOR TERPOLYMERS
“Stadler’s Goldmine”
Ternary-likeMorphology Diagram
Image removed due to copyright restrictions.
Please see Fig. 9d in Tschierske, Carsten. “Non-conventional soft matter.” Ch. 6 in Annual Report on Progress in Chemistry C: Physical Chemistry 97 (2001): 191-267.
ISV vs SIV 1:1:1
S.P. Gido, D.W. Schwark, E.L. Thomas, M.C. Goncalves,Macromolecules, 26, 2636 (1993)
Sequence Matters: A/B/C
Concentric cylinders of P2VP, surroundedby a PI annulus in a matrix of PS
Note: Noncircular IMDS
P2VP
P2VP
ISVSIV
Why? Chi parameter and avoiding segment-segment contact
33/33/33 = Lamellae or Coaxial Cylinders
Images removed due to copyright restrictions.
Please see Fig. 2 in Gido, Samuel P., et al. “Observation of a Non-Constant Mean Curvature Interface in an ABC TriblockCopolymer.” Macromolecules 26 (1993): 2636-2640.
“Knitting Pattern”Microdomain Morphology
PS-PEB-PMMA Linear triblock
PS
GlidesPlane group Mirrors
c2mm 2 folds
PMMA PEB
Image removed due to copyright restrictions.
Please see Fig. 1 and 4e in Breiner, Ulrike, et al. “Structural Characterization of the ‘Knitting Pattern’ in Polystyrene-block-poly(ethylene-co-butylene)-block-poly(methyl methacrylate) Triblock Copolymers.” Macromolecules 31 (1998): 135-141.
Theorist’s Nightmare, Uli’s Knitting
PS-PEB-PMMA Linear triblock
Image removed due to copyright restrictions.
Please see Fig. 4b in Breiner, Ulrike, et al. “Structural Characterization of the ‘Knitting Pattern’ in Polystyrene-block-poly(ethylene-co-butylene)-block-poly(methylmethacrylate) Triblock Copolymers.”Macromolecules 31 (1998): 135-141.
ABC Terpolymer Microstructure
Grain Boundaries &Defects
Image removed due to copyright restrictions.
Please see Fig. 4a in Breiner, Ulrike, et al. “Structural Characterization of the ‘Knitting Pattern’ in Polystyrene-block-poly(ethylene-co-butylene)-block-poly(methylmethacrylate) Triblock Copolymers.”Macromolecules 31 (1998): 135-141.
Non-CMC IMDS in PS/PEB/PMMA TriblockJunction Distribution
No JunctionsOn IMDS!
RuO4 PSStaining
Q: Influence on Mechanicals?
Image removed due to copyright restrictions.
Please see Fig. 5a and 4b in Breiner, Ulrike, et al. “Structural Characterization of the ‘Knitting Pattern’ in Polystyrene-block-poly(ethylene-co-butylene)-block-poly(methyl methacrylate) TriblockCopolymers.” Macromolecules 31 (1998): 135-141.
TEM Image2 differently shaped PEB domains
Types of Junctions
C1 and C2
Architecture: Manipulating the IMDSAt fixed Composition
IntroduceIMDS Curvatureto relieve chainstretching
More Complexity: Multiple IMDS
Concept:Locally preferredIMDS Curvature #2
#1
Miktoarm A/B Star Copolymers
Miktos = mixed
Architectural Influence on the Morphology Diagram
Leibler, 1980
Matsen and Schick1996
ε = 1lA = lB
3.0
2.5
2.0
1.00.0 0.2
bicB
cylB cylA
sphB
sphA
lam bicA
0.4 0.6
φB
0.8 1
1.5
ε =
(nA
/nB)(
1 A/1
B)1
/2
G
LC
S S`
C'
Disordered
CPS`CPS
00
0.2 0.4 0.6 0.8 1.0
20
40
60
80
χN
fA
10.5weak
segregation limit
Nχ ~ 10
strongsegregation
limitNχ >> 100
Figures by MIT OCW.
n = number of armsl = statistical segment
ε = n /n (lA/lB).5A B
Milner, 1994
ABC Polymers
Many Macromolecular Architectures...
Two junctions One junctionConfined to IMDS Surfaces Confined to LinesDependence on the block sequence All blocks interact
M M A
AB
C
P SA B C
SYNTHESIS AND PHASE SEPARATION OF MODEL 3-MIKTOARM
STAR TERPOLYMERS
SYNTHESIS AND PHASE SEPARATION OF MODEL 3-MIKTOARM
STAR TERPOLYMERS
P I P S
P M M Ao r P 2 V P
Synthesis (Anionic Polymerization, Controlled Chlorosilane Chemistry)
Molecular Characterization (SEC, MO, LALLS, NMR)Morphology (TEM, SAXS)
PMMAor
P2VP
PI PS
ABC Miktoarm Star Terpolymers
References:
A/B Chain Architecture and Asymmetry Effects on the Morphology DiagramS. T. Milner, Macromolecules 27, 2227 (1994)
Theoretical ABC Morphology Diagrams for Strong SegregationW. Zheng and Z-G Wang, Macromolecules 28, 7215 (1995)
Overview of ABC Structures and ThermodynamicsF. S. Bates and G. Fredrickson, Physics Today, 32, Feb (1999)