SUGHAR-SURFACE GROWN SUGHAR-SURFACE GROWN HYBRID FUNCTIONAL LAYERSHYBRID FUNCTIONAL LAYERSP3N-2009P N-2009S. Sekar, E. Feltrin, J. Giermanska, J.-F. Berret ǂ, J.-P. Chapel. Centre de Recherche Paul Pascal, CNRS-Bordeaux UniversityCentre de Recherche Paul Pascal, CNRS-Bordeaux UniversityMatière et Systèmes Complexes, CNRS- Universite Denis Diderot Paris-VII
The complexation between oppositely charged building-blocks in bulk and @ surfaces is controlled by fine tuning theelectrostatic interaction through the ionic strength (I ). Dormant solutions where the interaction is completely switched offelectrostatic interaction through the ionic strength (Is). Dormant solutions where the interaction is completely switched offare generated . By fine tuning Is via dilution, The interaction is switched back on via a controlled dilution step triggering theformation of electrostatic complexes in the bulk and the growth of organic/inorganic functional layers at a surface.formation of electrostatic complexes in the bulk and the growth of organic/inorganic functional layers at a surface.
Electro-steric stabilizationElectro-static stabilization
++ +++ +
Electro-steric stabilization
overcome
+
Fine tuning
Functional surfacesFunctional surfacesElectro-static stabilization
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+
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overcome
Via PE
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or
Fine tuningelectrostatic
Via salt
@ surface
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Salt > 10-3M -10-2M
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+ Via salt
Versatile
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precipitation
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+ +++
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Highly stable towards high Is > 1M
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Controlled co-assembly in bulk
Versatile properties & applications
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Switching on and off the interactionHighly stable cationic & anionic BB
±CeO2 +
+--
+
+ -
+
+-
1000-
--
-
--
-
-Properties & Functions
EDC /NHS
+
++
CeO2
20 nm
- -
-
Formulation
--
-
-
--
-
+
+
-
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--
-+
-
-
100
Hyd
rod
ynam
ic r
adiu
s
- --
+ κ κ κ κ-1<0.5 nm
Intimate mixingIntimate mixing
ClusteredDesalting transition
±CNT
CeO2-PAA-bPEICeO2-PAA20 nm 100
Hyd
rod
ynam
ic r
adiu
s
Isopmorph
Nucleation-growthDormant
Intimate mixingIntimate mixing50 nm
dilutiondialysis
Transparent conductive polymer films (PET)
AFM±CNT
[O]bPEI25k
HOOC
HOOC
COOH
10
0 0.2 0.4 0.6 0.8 1
Hyd
rod
ynam
ic r
adiu
s
900nm
Percolated MWCNT bilayers on Si wafer via LbL
CNTCOOH/CNTNH2
AFM
CNTCNTMWCNTPEI25k
bPEI25k
EDC/NHS
MWCNT-COOH
COOH
MWCNTUniversal Desalting Transition
Ionic strenghth I (M)900nm COOH NH2
electro-sterically stabilized CNT with conjugated PE to enable S L
L
D
CNTCNT
C
C C
O
HN
HN
H2NO
NH NH2
SOCl2 / Ethylenediamine
Universal Desalting Transition[Salt]
X =fct ( κ-1)
[Salt]
X =fct ( κ-1)3000
PE X NP NP X NP PE X PE
with conjugated PE to enable SgL r=R L/D (~2K ΩΩΩΩ. )
EDC/NHS
PAA5k
MWCNT-NH2 MWCNTPAA5k
C
C
C
O
HNH2N
NH NH2
O
OHThroughput RobotThroughput Robot
Overall phase diagram
1000
2000
RH
(nm
) PE X PE CNT X CNT
Anti-corrosive Al surfaces
AFM
± SiO2Polyacrylic acid C (NPs,PEs)C (NPs,PEs)
0 1 2 3 40
1000
Is(M)
Al surfaces--
--
-
-
- -
- + salt Wetting+wicking
CeOCeO22
10-3 M
EDC /NHS
- -
-
3M
C (NPs,PEs)C (NPs,PEs)
ThermodynamicsITC
s
Super hydrophilic & anti UV polymer surface
CeOCeO22
10-3 M 3M3 orders of magnitude ∆S >0 entropy driven interaction
anti UV polymer surface
SiOSiO22Counterions release
∆Hb∼ kBTT∆S0 ∼ 10 k T Per pair of charges (+/-)Growth @interfaces L L & S L
SuperhydrophobicSurfaces (underway)
T∆S0 ∼ 10 kBT Per pair of charges (+/-)Growth @interfaces LbL & SgL
SgLLLbbL L
fct (pH, NPs vs. PEs, κκκκ-1, Weak, Strong)4 × n steps
×n×n
4 × n steps
×n×n
@@onsetonset ‘’‘’bulkbulk’’ ’’ desaltingdesalting transitiontransition
600
800
1000
CeO2-PAA
2k/CeO
2-bPEI
25kNPs
PAA2k
/bPEI25k
PEs
120140160180200 AFM side view
2 dipping in A rinsing dipping in B rinsing
×n
+ -
dipping in A rinsing dipping in B rinsing
×n
+ -
2 dipping in A rinsing dipping in B rinsing
×n
+ -
dipping in A rinsing dipping in B rinsing
×n
+ -
200
400
600
−− −− ∆∆ ∆∆F
/n (
Hz)
406080100120
Exp.
2 steps
rinsing
-+
rinsing
-+
growthgrowth
2 steps
rinsing
-+
rinsing
-+
growthgrowth
0 2 4 6 8 10 12
0
no of bilayers
02040
dipping in A+B rinsingdipping in A+B rinsingdipping in A+B rinsingdipping in A+B rinsing
•Highly stable oppositely charged CeO2 NPs: bulk desalting transition and growth at a surface. submitted , J. Phy. Chem. C (2012)•Highly stable oppositely charged CeO2 NPs: bulk desalting transition and growth at a surface. submitted , J. Phy. Chem. C (2012)
•Stable carbon nanotubes dispersion in very high ionic strength. submitted , J. Phy. Chem. C (2012)
•Curr. Opin. Colloid Interface Sci. (2012) 17, 97-105
•ACS Appl. Mater. Interfaces (2011) 3, 1049-1054
CONTACT :•ACS Appl. Mater. Interfaces (2011) 3, 1049-1054
•Adv. Col. Int. Sci. (2011) 167, 38–48
•PCT WO 2010-120267 - Rhodia Inc./CNRS
[email protected]@crpp-bordeaux.cnrs.fr
Journées Nationales en Nanosciences et Nanotechnologies 2012