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![Page 1: Morphology, Thickness and Composition Evolution in Supramolecular Block Copolymers Prepared by Dip-Coating Robert E. Prud’homme and C. Géraldine Bazuin.](https://reader036.fdocuments.us/reader036/viewer/2022062519/5697bfb71a28abf838c9ea6e/html5/thumbnails/1.jpg)
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
![Page 2: Morphology, Thickness and Composition Evolution in Supramolecular Block Copolymers Prepared by Dip-Coating Robert E. Prud’homme and C. Géraldine Bazuin.](https://reader036.fdocuments.us/reader036/viewer/2022062519/5697bfb71a28abf838c9ea6e/html5/thumbnails/2.jpg)
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
![Page 3: Morphology, Thickness and Composition Evolution in Supramolecular Block Copolymers Prepared by Dip-Coating Robert E. Prud’homme and C. Géraldine Bazuin.](https://reader036.fdocuments.us/reader036/viewer/2022062519/5697bfb71a28abf838c9ea6e/html5/thumbnails/3.jpg)
1973 picture. On the first row, from right to left, Richard Stein, Do Yoon and Robert Prud’homme.In the second row, Judy Stein.
![Page 4: Morphology, Thickness and Composition Evolution in Supramolecular Block Copolymers Prepared by Dip-Coating Robert E. Prud’homme and C. Géraldine Bazuin.](https://reader036.fdocuments.us/reader036/viewer/2022062519/5697bfb71a28abf838c9ea6e/html5/thumbnails/4.jpg)
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
![Page 5: Morphology, Thickness and Composition Evolution in Supramolecular Block Copolymers Prepared by Dip-Coating Robert E. Prud’homme and C. Géraldine Bazuin.](https://reader036.fdocuments.us/reader036/viewer/2022062519/5697bfb71a28abf838c9ea6e/html5/thumbnails/5.jpg)
Naphthol (NOH) Naphthoic acid (NCOOH) DHN
n m
PS block PVP blockTwo key choices:
► dip-coating method► adding a small molecule
H-bond
![Page 6: Morphology, Thickness and Composition Evolution in Supramolecular Block Copolymers Prepared by Dip-Coating Robert E. Prud’homme and C. Géraldine Bazuin.](https://reader036.fdocuments.us/reader036/viewer/2022062519/5697bfb71a28abf838c9ea6e/html5/thumbnails/6.jpg)
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, ....
![Page 7: Morphology, Thickness and Composition Evolution in Supramolecular Block Copolymers Prepared by Dip-Coating Robert E. Prud’homme and C. Géraldine Bazuin.](https://reader036.fdocuments.us/reader036/viewer/2022062519/5697bfb71a28abf838c9ea6e/html5/thumbnails/7.jpg)
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.
![Page 8: Morphology, Thickness and Composition Evolution in Supramolecular Block Copolymers Prepared by Dip-Coating Robert E. Prud’homme and C. Géraldine Bazuin.](https://reader036.fdocuments.us/reader036/viewer/2022062519/5697bfb71a28abf838c9ea6e/html5/thumbnails/8.jpg)
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
![Page 9: Morphology, Thickness and Composition Evolution in Supramolecular Block Copolymers Prepared by Dip-Coating Robert E. Prud’homme and C. Géraldine Bazuin.](https://reader036.fdocuments.us/reader036/viewer/2022062519/5697bfb71a28abf838c9ea6e/html5/thumbnails/9.jpg)
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.
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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)
![Page 11: Morphology, Thickness and Composition Evolution in Supramolecular Block Copolymers Prepared by Dip-Coating Robert E. Prud’homme and C. Géraldine Bazuin.](https://reader036.fdocuments.us/reader036/viewer/2022062519/5697bfb71a28abf838c9ea6e/html5/thumbnails/11.jpg)
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
![Page 12: Morphology, Thickness and Composition Evolution in Supramolecular Block Copolymers Prepared by Dip-Coating Robert E. Prud’homme and C. Géraldine Bazuin.](https://reader036.fdocuments.us/reader036/viewer/2022062519/5697bfb71a28abf838c9ea6e/html5/thumbnails/12.jpg)
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
![Page 13: Morphology, Thickness and Composition Evolution in Supramolecular Block Copolymers Prepared by Dip-Coating Robert E. Prud’homme and C. Géraldine Bazuin.](https://reader036.fdocuments.us/reader036/viewer/2022062519/5697bfb71a28abf838c9ea6e/html5/thumbnails/13.jpg)
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.
![Page 14: Morphology, Thickness and Composition Evolution in Supramolecular Block Copolymers Prepared by Dip-Coating Robert E. Prud’homme and C. Géraldine Bazuin.](https://reader036.fdocuments.us/reader036/viewer/2022062519/5697bfb71a28abf838c9ea6e/html5/thumbnails/14.jpg)
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)
![Page 15: Morphology, Thickness and Composition Evolution in Supramolecular Block Copolymers Prepared by Dip-Coating Robert E. Prud’homme and C. Géraldine Bazuin.](https://reader036.fdocuments.us/reader036/viewer/2022062519/5697bfb71a28abf838c9ea6e/html5/thumbnails/15.jpg)
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
![Page 16: Morphology, Thickness and Composition Evolution in Supramolecular Block Copolymers Prepared by Dip-Coating Robert E. Prud’homme and C. Géraldine Bazuin.](https://reader036.fdocuments.us/reader036/viewer/2022062519/5697bfb71a28abf838c9ea6e/html5/thumbnails/16.jpg)
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
![Page 17: Morphology, Thickness and Composition Evolution in Supramolecular Block Copolymers Prepared by Dip-Coating Robert E. Prud’homme and C. Géraldine Bazuin.](https://reader036.fdocuments.us/reader036/viewer/2022062519/5697bfb71a28abf838c9ea6e/html5/thumbnails/17.jpg)
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
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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.
![Page 19: Morphology, Thickness and Composition Evolution in Supramolecular Block Copolymers Prepared by Dip-Coating Robert E. Prud’homme and C. Géraldine Bazuin.](https://reader036.fdocuments.us/reader036/viewer/2022062519/5697bfb71a28abf838c9ea6e/html5/thumbnails/19.jpg)
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
![Page 20: Morphology, Thickness and Composition Evolution in Supramolecular Block Copolymers Prepared by Dip-Coating Robert E. Prud’homme and C. Géraldine Bazuin.](https://reader036.fdocuments.us/reader036/viewer/2022062519/5697bfb71a28abf838c9ea6e/html5/thumbnails/20.jpg)
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.
![Page 21: Morphology, Thickness and Composition Evolution in Supramolecular Block Copolymers Prepared by Dip-Coating Robert E. Prud’homme and C. Géraldine Bazuin.](https://reader036.fdocuments.us/reader036/viewer/2022062519/5697bfb71a28abf838c9ea6e/html5/thumbnails/21.jpg)
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
![Page 22: Morphology, Thickness and Composition Evolution in Supramolecular Block Copolymers Prepared by Dip-Coating Robert E. Prud’homme and C. Géraldine Bazuin.](https://reader036.fdocuments.us/reader036/viewer/2022062519/5697bfb71a28abf838c9ea6e/html5/thumbnails/22.jpg)
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, …)
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Thanks, Prof. Stein, for your mentoring and your
friendship