SUGHAR -SURFACE GROWN HYBRID FUNCTIONAL LAYERS
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SUGHAR-SURFACE GROWN HYBRID FUNCTIONAL LAYERS P 3 N-2009 S. Sekar , E. Feltrin, J. Giermanska, J.-F. Berret ǂ , J.-P. Chapel. Centre de Recherche Paul Pascal, CNRS-Bordeaux University Matière 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 the electrostatic interaction through the ionic strength (I ). Dormant solutions where the interaction is completely switched off electrostatic interaction through the ionic strength (I s ). Dormant solutions where the interaction is completely switched off are generated . By fine tuning Is via dilution, The interaction is switched back on via a controlled dilution step triggering the formation 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 stabilization Electro-static stabilization + + + + + + Electro-steric stabilization overcome + Fine tuning Functional surfaces Functional surfaces Electro-static stabilization + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + overcome Via PE + + + + + or Fine tuning electrostatic Via salt @ surface + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + Salt > 10 -3 M -10 -2 M + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + Versatile + precipitation + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + Highly stable towards high I s > 1M + Controlled co-assembly in bulk properties & applications + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + Switching on and off the interaction Highly stable cationic & anionic BB ±CeO 2 + + - - + + - + + - 1000 - - - - - - - - Properties & Functions EDC /NHS + + + CeO 2 20 nm - - - Formulation - - - - - - - + + - - - - - + - - 100 c radius - + κ κ κ κ -1 <0.5 nm Intimate mixing Intimate mixing Clustered Desalting transition ±CNT CeO 2 -PAA-bPEI CeO 2 -PAA 20 nm 100 ydrodynamic Isopmorph Nucleation-growth Dormant Intimate mixing Intimate mixing 50 nm dilution dialysis Transparent conductive polymer films (PET) AFM ±CNT [O] bPEI 25k HOOC HOOC COOH 10 0 0.2 0.4 0.6 0.8 1 Hy 900nm Percolated MWCNT bilayers on Si wafer via L b L CNT COOH /CNT NH2 AFM CNT CNT MWCNTPEI 25k bPEI 25k EDC/NHS MWCNT-COOH COOH MWCNT Universal Desalting Transition Ionic strenghth I (M) 900nm electro-sterically stabilized CNT with conjugated PE to enable S L L D CNT CNT C C C O HN H N H 2 N O N H N H 2 SOCl 2 / Ethylenediamine [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 S g L r=R L/D (~2K Ω.) EDC/NHS PAA 5k MWCNT-NH 2 MWCNTPAA 5k C C C O H N H 2 N N H N H 2 O OH Throughput Robot Throughput Robot Overall phase diagram 1000 2000 R H (nm) PE X PE CNT X CNT Anti-corrosive Al surfaces AFM ± SiO 2 Polyacrylic acid C (NPs,PEs) C (NPs,PEs) 0 1 2 3 4 0 I s (M) Al surfaces - - - - - - - - - + salt Wetting+wicking CeO CeO 2 10 -3 M EDC /NHS - - - 3M Thermodynamics ITC Super hydrophilic & anti UV polymer surface CeO CeO 2 10 -3 M 3M 3 orders of magnitude ∆S >0 entropy driven interaction SiO SiO 2 Counterions release ∆H b ∼ k B T T∆S 0 ∼ 10 k T Per pair of charges (+/-) Growth @interfaces L L & S L Superhydrophobic Surfaces (underway) T∆S 0 ∼ 10 k B T Per pair of charges (+/-) Growth @interfaces L b L & S g L S g L L b L L fct (pH, NPs vs. PEs, κ -1 , Weak, Strong) 4 × n steps × n × n 4 × n steps × n × n @onset onset ‘’ ‘’bulk bulk’’ ’’ desalting desalting transition transition 600 800 1000 CeO 2 -PAA 2k /CeO 2 -bPEI 25k NPs PAA 2k /bPEI 25k PEs 120 140 160 180 200 AFM side view 2 dipping in A rinsing dipping in B rinsing + - dipping in A rinsing dipping in B rinsing + - 2 dipping in A rinsing dipping in B rinsing + - dipping in A rinsing dipping in B rinsing + - 200 400 600 - - - - ∆ ∆ ∆ ∆F/n (Hz) 40 60 80 100 120 Exp. 2 steps rinsing - + rinsing - + growth growth 2 steps rinsing - + rinsing - + growth growth 0 2 4 6 8 10 12 0 no of bilayers 0 20 40 dipping in A+B rinsing dipping in A+B rinsing dipping in A+B rinsing dipping in A+B rinsing •Highly stable oppositely charged CeO 2 NPs: bulk desalting transition and growth at a surface. submitted , J. Phy . Chem. C (2012) •Highly stable oppositely charged CeO 2 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] [email protected] Journées Nationales en Nanosciences et Nanotechnologies 2012
Transcript of SUGHAR -SURFACE GROWN HYBRID FUNCTIONAL LAYERS
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
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Fine tuning
Functional surfacesFunctional surfacesElectro-static stabilization
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Fine tuningelectrostatic
Via salt
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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 +
+--
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+ -
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1000-
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-Properties & Functions
EDC /NHS
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CeO2
20 nm
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Formulation
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--
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100
Hyd
rod
ynam
ic r
adiu
s
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+ 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--
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- + salt Wetting+wicking
CeOCeO22
10-3 M
EDC /NHS
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3M
C (NPs,PEs)C (NPs,PEs)
ThermodynamicsITC
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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
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CeO2-PAA
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2-bPEI
25kNPs
PAA2k
/bPEI25k
PEs
120140160180200 AFM side view
2 dipping in A rinsing dipping in B rinsing
×n
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dipping in A rinsing dipping in B rinsing
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2 dipping in A rinsing dipping in B rinsing
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dipping in A rinsing dipping in B rinsing
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−− −− ∆∆ ∆∆F
/n (
Hz)
406080100120
Exp.
2 steps
rinsing
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rinsing
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growthgrowth
2 steps
rinsing
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rinsing
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growthgrowth
0 2 4 6 8 10 12
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no of bilayers
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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
