samuel dodoo, anna burmistrova, kornelia …2) stimuli responsive polyelectrolyte coatings samuel...
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2) Stimuli 2) Stimuli responsiveresponsive polyelectrolytepolyelectrolyte coatingscoatings
Samuel Dodoo, Anna Burmistrova, Kornelia Gawlitza, Adrian Carl, Marcel Richter, Regine v. Klitzing
Stranski-LaboratoriumTechnical University of Berlin, Germany
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Polymer coatings: MotivationPolymer coatings: Motivation
Nano- and Mesoscopic polymer films (thickness: 1 – 1000 nm)External stimuli: temperature, ionic strength, pH, humidity …
Sensitivity <=> Stability
Design and characterisationof stimuli responsive
surface coatings
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CH3 CH3
OCH3
N*
N+
*
Cl
n
m
CH3
**
SO 3
n
Na+-
**
NH3
n
Cl+
*
n
OR
OO
OR
OOO
OROR
OR
OR
R=COO-Na+
Decher, G.; Hong, J.D.; Schmitt, J. Thin Solid Films 1992, 210, 831.
OR
OO
OH
OO
OHOH
CH2 OH
CH2OCH2CH2OH
O(CH2CH2O)2
CH2CHCH2
OH
N+
CH3
CH3
CH3
Cl
Polycations Polyanions
JR400
PAH
CMC
P(DADMAC-NMVA)
PSS
HA
LayerLayer--byby--layer techniquelayer technique
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1) Ion 1) Ion specificspecific EffectsEffects
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=> Increasing interaction between anions and polycations
0 2 4 6 8 10 12
0
100
200
300
400
500
600
700
Cl-
F-
Thic
knes
s, d
/ Å
Number of layers, N
Br-
Ion specific effects: Effect of anionsIon specific effects: Effect of anions
Increasing ion diameter (decreasing hydration shell)
PSS/PDADMAC
[NaX]=0.25mol/l Si
coiled
dBr-Br-
Br- Br-
Si
flatd
F-
F-
F-
J.E. Wong, R.v.K, Macromolecules, submitted
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Ion specific effects:Ion specific effects: AFM studiesAFM studies
(PSS/PDADAMAC)6 prepared in 0.25 mol/l salt
NaCl
RMS 15 Å
CsClNaBr
25 Å 21 Å
Increasing roughness
with increasing ion size
J.E. Wong, R.v.K, Macromolecules, accepted
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Different types of multilayer growingDifferent types of multilayer growing
0 2 4 6 8 10
thic
knes
s
number of layers
Kovacevic et al., Langmuir, 2002Biesheuvel et al. Langmuir, 2004Garza et al. , Langmuir 2004
-+-+-+-
+Si
linear
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Different types of multilayer growingDifferent types of multilayer growing
0 2 4 6 8 10
thic
knes
s
number of layers
Kovacevic et al., Langmuir, 2002Biesheuvel et al. Langmuir, 2004Garza et al. , Langmuir 2004
-+-+-+-
+Si
linear
exponential
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Different types of multilayer growingDifferent types of multilayer growing
0 2 4 6 8 10
thic
knes
s
number of layers
Kovacevic et al., Langmuir, 2002Biesheuvel et al. Langmuir, 2004Garza et al. , Langmuir 2004
-+-
+Si
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2 4 6 8 10 120
100
200
300
400
500
600
700 100%, 0.1 mol/l 75%, 0.1 mol/l
th
ickn
ess
/ Å
number of adsorbed layers
Preparation in NaBr, 2 different PDADMAC charge densities
Effect of degree of chargeEffect of degree of charge
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2 4 6 8 10 120
100
200
300
400
500
600
700 100%, 0.1 mol/l 75%, 0.1 mol/l 100%, 0.25 mol/l
th
ickn
ess
/ Å
number of adsorbed layers
Preparation in NaBr, 2 different PDADMAC charge densities
Effect of ionic strengthEffect of ionic strength
Transition from linear to exponential increase by increasing ionic strength
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2 4 6 8 10 120
100
200
300
400
500
600
700 100%, 0.1 mol/l 75%, 0.1 mol/l 100%, 0.25 mol/l 75%, 0.25 mol/l
th
ickn
ess
/ Å
number of adsorbed layers
Preparation in NaBr, 2 different PDADMAC charge densities
Effect of degree of chargeEffect of degree of charge
Effect of polymer charge density on the type of growth
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2 4 6 8 10 120
100
200
300
400
500
600
700 75%, 0.25 mol/l NaBr
th
ickn
ess
/ Å
number of adsorbed layers
Effect of type of saltEffect of type of salt
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2 4 6 8 10 120
100
200
300
400
500
600
700 75%, 0,25 mol/l NaBr 75%, 0,25 mol/l NaCl
th
ickn
ess
/ Å
number of adsorbed layers
Comparison NaBr <-> NaCl
Tuning of type of growth by changing salt during preparation
Effect of type of saltEffect of type of salt
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)Dtx(
πDtMC(x,t)
4exp
2
2−=
Deposition of the probing layer
O
O
O
NH
O OH
SC
**
NH3
m *
*
NH3
n
-20 -10 0 10 2020
40
60
80
100
120
140
160 after bleaching after treatment
Gre
y va
lue
/a.u
.
Distance/µm
Mobility: Fluorescence Recovery after Mobility: Fluorescence Recovery after PhotobleachingPhotobleaching (FRAP)(FRAP)
Polyanion/polycation D / cm2/sPSS/PAH < 10-15
PSS/PDADMAC 10-14
PSS/PDADMAC (75 %) 10-13
PSS/PDADMAC (NaBr) 10-13
HA/PDADMAC 10-11
FITC-PAH
P. Nazaran, R.v.K. et al. J. Phys. Chem B (2007)
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Internal structure: Exposure to high ionic strengthInternal structure: Exposure to high ionic strength
0 2 4 61E-5
1E-4
1E-3
0.01
0.1
1
0.4 0.8 1.2 1.6 2.0 2.4 2.8
1E-4
1E-3
0.01
D2O 1M NaCl 3M NaCl 4M NaCl
Ref
lect
ivity
tth / deg
tth / deg
Ref
lect
vity
silicon substrate
td
Si/PEI/[(PSS/PAH)2/d-PSS/PAH]6
0 1 2 3 4
1.00
1.02
1.04
1.06 t d
Nor
mal
ized
thic
knes
s
NaCl concentration / M
⇒ Film swelling for cNaCl ≥ 3 M⇒ Non-homogeneous swelling
R. Steitz, R.v.K. (Adam, ILL Grenoble)
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Swelling: Swelling: ““freefree”” water vs. water vs. ““voidvoid”” water (neutron water (neutron reflectometryreflectometry))
d2/d1 φfree φvoid φtotal
(PSS/PDADMAC)9 1.79 0.44 0.10 0.54
(PSS/PAH)9 1.60 0.38 0.11 0.49
(PSS/PAH)9/PSS 1.57 0.36 0.10 0.46
d1
D2O liquid or vapor
d2
φfree
φvoid
Silicon substrate
d1
vacuum
S. Dodoo, J.E. Wong, R. Steitz, R.v.K.
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Swelling in water: Effect of preparation parametersSwelling in water: Effect of preparation parameters
S. Dodoo, R. Steitz, R.v.K.
0,2
0,3
0,4
0,5
0,6 0.10 M 0.25 M 0.50 M
wat
er c
onte
nt
NaF NaCl NaBr
(PSS/PDADMAC)6
Addition of different amount and type of salt during preparation
=> Increasing water content with increasing ionic strength
and increasing anion polarizibility
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Intrinsically compensatedLess mobile (Glassy)Lower amount water
Low Ionic strengthChloride ion100% charged PE
High Ionic strengthBromide ion75% charged PE
Extrinsically compensatedMore mobile (Liquefied)Higher amount of water
Conclusion: ion specific effectsConclusion: ion specific effects
Treatment:Dissolution of complexes byIncreasing ionic strength (stronger for bromide)
Preparationconditions
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2) 2) TemperatureTemperature effectseffects
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Temperature induced increase in the mobility:
Transition from a glassy state to a swollen and liquefied structure accompanied with softening of the film.
0 .1M N aC l 1M N aC l 0 .1M N aB r 1M N aB r10 -15
10 -14
10 -13
10 -12
Ion ic cond ition o f film p repa ra tion
Diff
usio
n co
effic
ient
/ cm
²/sec
R oom tem p. 65° C
Effect of heatingEffect of heating
(PSS/PDADMAC[75%)])6 against water
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DADMAC
N+
CH3CH3
Cl
Na-SS
Na+
SO3
O NH
CH3CH3
NIPAM
O NH
CH3CH3
SO3 H+
AMPS
OO
N
CH3CH3
+
DEAEM
• Block-copolymers
• statistical copolymers
EffectEffect of of chargecharge distributiondistribution: : NIPAMNIPAM--copolymerscopolymers
U. Voigt, V. Khrenov, K. Tauer, M. Hahn, W. Jaeger, R. v.K., J. Phys: Condens. Matter (2003)
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0,00 0,02 0,04 0,06 0,0810-4
10-3
10-2
10-1
100
101
102
103
104
20 °C 40 °C 50 °C 60 °C
I/I0
Q [Å-1]
-100 0 100 200 500 600
2
3
4
5
6
7
D2O
Si
20 °C 40 °C 50 °C 60 °C
Nb
x 10
-6 [Å
-2]
z [Å]
Neutron reflectometry at solid/liquid interface: (PSS-b-PNIPAM/PDADMAC)n
Small decrease in thickness
Irreversible shrinking process
Irreversible annealing of the film
=> Strong interdigitation
10 20 30 40 50 60560
565
570
575
580
585
590
595
600
Film
thic
knes
s [Å
]
Temperature [°C]
R. Steitz, V. Leiner, K. Tauer, V. Khrenov, R.v.K. Appl. Phys. A (2002)
Effect of temperature on solvent swollen films Effect of temperature on solvent swollen films - +
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Stimuli responsive coatings Stimuli responsive coatings
Strategy: Formation of stimuli-repsonsive coating by adsorption of microgel particles
=> Effect of geometrical confinement on sensitivity
ΔT ΔpH?
in bulk at interfaces
? ΔpH, ΔT
Hydrogel microparticles
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Control of Control of hydrogelhydrogel particle densityparticle density
Explanation for 2D pattern: • Capillary attraction vs. dipolar repulsion• Shrinking of swollen (single) particles
After spin coating, pH 2
After rinsingin pH 2
S. Schmidt, T. Hellweg, H. Motschmann, R. v. K. Polymer (2008)
P(NIPAM-co-AA) particles on Si/PEI
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0,2 0,4 0,6 0,8 1,0 1,2
1E-4
1E-3
0,01
0,1
1
0,4 0,5 0,6
0,01
0,02
0,03
0,04
Ref
lect
ivity
theta / deg
25°C 40°C 25°C
Ref
lect
ivity
theta / deg
Swelling / shrinking of Swelling / shrinking of hydrogelhydrogel particlesparticles
Neutron reflectometry => reversibility
(HMI 2006)
P(NIPAM-co-AA) particles (pH = 2)Ellipsometry => decrease in LCST
25°C, air 25°C, H2O 55°C, H2OSFM (amb./liquid) => Compactisation (T > LCST)
400 nm: 90% D2O200 nm: 80% D2O
15 μm
S. Schmidt, T. Hellweg, H. Motschmann, R. v. K. Polymer (2008)M. Karg, T. Hellweg, R.v.K. et al. Langmuir (2008) S. Schmidt, T. Hellweg, R.v.K., Langmuir (2008)
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Fresh from the labFresh from the lab: Fluctuation length close to phase transition: Fluctuation length close to phase transition
GISANS (D16, ILL Grenoble)6.-17.11.2008
15 20 25 30 35 40 45 50 55 600
1
2
3
4
ξ / n
mT / °C
M. Medebach, R.v.K., Cooperation: P. Müller-Buschbaum, TU Munich
=> Increase in fluctuation length ξ close to Tc
Tc
P(NIPAM-co-AA) particles on Si/PEI (pH = 6)
Ornstein Zernike => fluctuation length ξ
Zone close to the surface
remains unaffected
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Conclusion: Temperature sensitivityConclusion: Temperature sensitivity
Polyelectrolyte multilayers:
•Sensitivity to temperature rather low due to
interdigitation
Thermosensitive coatings by adsorption of hydrogel microparticles
• Control of particle density
• Reversible shrinkage and swelling
• Small shift of the LCST to lower temperature
• Unchanged interphase between solid surface
and „continuum“ of the particle
ΔT
-+-+-+-
+Si
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New strategies for embedded biocatalysts:• Stabilisation of catalyst• Selective permeability• Easy separation• Fast response to external stimuli
Current projectsCurrent projects
Cooperation:CoE „Unicat“ (Berlin-Potsdam):M. Ansorge-Schumacher TU BerlinH. Möhwald MPI-KG, PotsdamRainer Haag, FU Berlin
Self-assembly at interfaces (bottom up)
GISANS: new set-up
at ISIS (BMBF project)
Patterned surfaces
10 – 50 nmhν (VIS)
Actuation by lightAu particles
(-> Photovoltaics)