morphology, thickness and composition evolution in supramolecular block copolymers prepared by...
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Morphology, Thickness and Composition Evolution in
Supramolecular Block Copolymers Prepared by Dip-Coating
Robert E. Prud’homme and C. Géraldine Bazuin
Département de chimieUniversité de Montréal
Two objectives:1) to obtain a Ph.D. in polymer science
2) to learn English without accent
Stein’s IUPAC lecture in Montréal in 1990
1973 picture. On the first row, from right to left, Richard Stein, Do Yoon and Robert Prud’homme.In the second row, Judy Stein.
Morphology, Thickness and Composition Evolution in
Supramolecular Block Copolymers Prepared by Dip-Coating
Robert E. Prud’homme and C. Géraldine Bazuin
Département de chimieUniversité de Montréal
Thanks to Sébastien Roland, Alexis Laforgue, David Gaspard,
Cé Guinto Gamys and Christian Pellerin
Naphthol (NOH) Naphthoic acid (NCOOH) DHN
n m
PS block PVP blockTwo key choices:
► dip-coating method► adding a small molecule
H-bond
Block copolymer (BC) self-assembly
In the bulk (melt)• Important parameters: fA, fB , and N
In thin films (ex. spin-coating + annealing, dip-coating)• Additional parameters: surface/interface energetics (air,
substrate) – preferential wetting, domain orientation -, and confinement effects
• solvent evaporation rate, other kinetic effects
Supramolecular block copolymers• addition of a block selective (H-bonding) small molecule, SM
modifies block fractions, interfacial energies, ....
AFM images TEM images
PS-b-P4VP (71.9K-30.2K) (1:1 = VP:DHN)
+ DHN(dip-coatedfrom THFsolution)
(washedwith MeOH)
– DHN
Contact angle measurements
86 o mainly PS at surface (thin layer overlaying
VP nodules)
PS: 92 o
P4VP: 62 o
60 o thin P4VP
layer overlays entire surface
1x1 mm
1x1 m
1x1 m
1x1 m
1x1 m
pore depth: ~7 nmfilm thickness: ~7 nm
stained with I2 (P4VP)
Laforgue, A.; Bazuin, C.G.; Prud’homme, R.E. Macromolecules 2006, 39, 6473.
2x2 m
AFM TEM (I2-stained)
3x3 m
PS-b-P4VP (71.9k-30.2k), 5 mg/mL THF solutions (micellar), SM:VP 1:1, dip-coating rate 2 mm/min, silicon substrates
H-bonded to P4VP
intermediate strength
strong
NOH
a b c d e
(5 mg/mL)
(10 mg/mL)
a’ b’ c’ d’ e’
NCOOH
a* b* c* d* e*
NOH
(5 mg/mL)
a
b c
d
e
a*
b*
c*e*
a’
b’
c’d’
e’
d*
1 10 100
10
100 10 mg/mL PS-P4VP / NOH 5 mg/mL PS-P4VP / NOH 5 mg/mL PS-P4VP / NCOOH 10 mg/mL PS-P4VP 5 mg/mL PS-P4VP
Th
ickne
ss (n
m)
Dip-coating rate (mm/min)
THF solutions
0 10 20 30 40 50 60 70 80 90
0.5
1.0
10 mg/mL PS-P4VP / NOH 5 mg/mL PS-P4VP / NOH 5 mg/mL PS-P4VP / NCOOH
SM
/VP
upt
ake
ratio
Dip-coating rate (mm/min)
Sébastien Roland, R.E. Prud'homme, C.G. Bazuin, ACS Macro Letters 2012, 1, 973.
Sébastien Roland, David Gaspard, R.E. Prud'homme, C.G. Bazuin, Macromolecules 2012, 45, 5463.
1 10 100
10
100 10 mg/mL PS-P4VP / NOH 5 mg/mL PS-P4VP / NOH 5 mg/mL PS-P4VP / NCOOH
Thick
ness
(nm
)
Dip-coating rate (mm/min)
THF solutions, SM:VP 1:1
Dip-coated PS-P4VP (40.5k-17.5k) films
Film
thi
ckne
ss (
nm)
Faustini, M.; Louis, B.; Albouy, P.A.; Kuemmel, M.; Grosso, D. J. Phys. Chem. C 2010, 114, 7637 (Figures 1 and 3)
Sol-gel films
well-known(Landau+Levich, 1942)
new
PS-P4VP/NOH (1:1) (log-log scale)
Faustini, M.; Louis, B.; Albouy, P.A.; Kuemmel, M.; Grosso, D. J. Phys. Chem. C 2010, 114, 7637(Figure 3)
Sol-gel films
h or ho
u
1 10 100
10
100 5 mg/mL PS-P4VP / NOH
Thi
ckne
ss (nm
)
Dip-coating rate (mm/min)
a’
b’
c’d’
e’
NOH
a b c d e
(5 mg/mL)
(10 mg/mL)
a’ b’ c’ d’ e’
NCOOH
a* b* c* d* e*
NOH
(5 mg/mL)
spheres brush (wetting)layer
ǁ , ‗cyl.
‗ cyl.
a*
b*
c*e*
a’
b’
c’d’
e’
d*
1 10 100
10
100 5 mg/mL PS-P4VP / NOH 5 mg/mL PS-P4VP / NCOOH
Thi
ckne
ss (nm
)
Dip-coating rate (mm/min)
a’
sph. brushlayer
ǁ cyl. lamellar(face-down)
a b c
d e f
g h i
T0
T1
T1
T1
T2
S
A
SS
S SS
SSS
A
A AA
A A A
A
TEM micrographs of cross-sectional slices of I2-stained 41.5-17.5 PS-P4VP/NCOOH
1 mm/min
dots (AFM) ® spheres
(micellar solutions)
(visible wetting layer)
scale bar: 100 nm
a b c
d e f
g h i
T0
T1
T1
T1
T2
S
A
SS
S SS
SSS
A
A AA
A A A
A
TEM micrographs of cross-sectional slices of I2-stained 41.5-17.5 PS-P4VP/NCOOH
2 mm/min
stripes (AFM) horizontal cylinders
(visible wetting layer)
scale bar: 100 nm
z : 12 nm2 x 2 µm²3 mm/min
z : 12 nm2 x 2 µm²7 mm/min
z : 10 nm2 x 2 µm²20 mm/min
z : 12 nm2 x 2 µm²40 mm/min
10 mg/mL5 mg/mL
z : 12 nm2 x 2 µm²2 mm/min
z : 12 nm2 x 2 µm²4 mm/min
z : 10 nm2 x 2 µm²20 mm/min
z : 12 nm2 x 2 µm²40 mm/min
PS-P4VP (SM-free)
1 10 100
10
100 10 mg/mL PS-P4VP / NOH 5 mg/mL PS-P4VP / NOH 5 mg/mL PS-P4VP / NCOOH 10 mg/mL PS-P4VP 5 mg/mL PS-P4VP
Thick
ness
(nm
)
Dip-coating rate (mm/min)
z : 12 nm2 x 2 µm²3 mm/min
z : 12 nm2 x 2 µm²7 mm/min
z : 10 nm2 x 2 µm²20 mm/min
z : 12 nm2 x 2 µm²40 mm/min
10 mg/mL5 mg/mL
z : 12 nm2 x 2 µm²2 mm/min
z : 12 nm2 x 2 µm²4 mm/min
z : 10 nm2 x 2 µm²20 mm/min
z : 12 nm2 x 2 µm²40 mm/min
PS-P4VP (SM-free)
SM-free PS-P4VP
dots (spheres) only
0 10 20 30 40 50 60 70 80 90
0.5
1.0
10 mg/mL PS-P4VP / NOH 5 mg/mL PS-P4VP / NOH 5 mg/mL PS-P4VP / NCOOH
S
M/V
P u
ptak
e ra
tio
Dip-coating rate (mm/min)
S. Roland, C. Pellerin, C.G. Bazuin, R.E. Prud’homme, Macromolecules, 2012, 45, 7964.
a
b c
d
e
a*
b*
c*e*
a’
b’
c’d’
e’
d*
1 10 100
10
100 10 mg/mL PS-P4VP / NOH 5 mg/mL PS-P4VP / NOH 5 mg/mL PS-P4VP / NCOOH 10 mg/mL PS-P4VP 5 mg/mL PS-P4VP
Th
ickne
ss (n
m)
Dip-coating rate (mm/min)
NOH
a b c d e
(5 mg/mL)
(10 mg/mL)
a’ b’ c’ d’ e’
NCOOH
a* b* c* d* e*
NOH
(5 mg/mL)
NOH: spheres horizontal cylinders vertical cylindersNCOOH: spheres horizontal cylinders face-down lamellae
0.1 1 10 100
20
40
60
80
100
120
Dioxane Toluene THF CHCl
3
Film
thic
knes
s (n
m)
Dip-coating rate (mm/min)
Other Dip-coating Solvents(10 mg/mL PS-P4VP solution concentration, 1:1 NCOOH:VP)
S. Roland, C.G. Gamys, J. Grosrenaud, S. Boissé, C. Pellerin, R.E. Prud’homme,C.G. Bazuin, Macromolecules 2015, 48, 4823.
Vapor
pressur
e
(kPa)
Viscosity
η
(mN.s.m-
2)
Surfac
e
tensio
n, γ
(mN.m-
1)
Densit
y,
ρ
(g.cm-
3)
D
(x
106)
p-Dioxane 4.95 1.177 32.75 1.034 0.116
Toluene 3.79 0.560 27.93 0.862 0.087
THF 21.6 0.456 26.5 0.883 0.074
Chlorofor
m
26.2 0.537 26.67 1.479 0.050
0.1 1 10 100
20
40
60
80
100
120
Dioxane Toluene THF CHCl
3
Film
thic
knes
s (n
m)
Dip-coating rate (mm/min)
capillarity regime(dip-coating rate slower
than evaporation rate):evaporation ratedominates film thickness
drainingregime
film thickness related to D (at a given dip-coating rate):
dioxane > toluene > THF > CHCl3
Conclusions V-shaped dependence of dip-coated film thickness with dip-
coating rate (capillarity vs. draining regimes)
Films obtained in the capillary regime depend on solvent characteristics (insensitive in the draining regime)
Morphologies depend on SM uptake ratio and solution/solvent characteristics (micellar or not, “tightness” of micelles, …)
Thanks, Prof. Stein, for your mentoring and your
friendship