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

++

++

+

+++

++

+

++

++

+++

+

+++ +++ + +

++

+++

++

++

++

overcome

Via PE

++ +++

or

Fine tuningelectrostatic

Via salt

@ surface

++ +

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+

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+

+

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Salt > 10-3M -10-2M

++

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++

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+ Via salt

Versatile

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precipitation

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+ +++

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+ +++

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Highly stable towards high Is > 1M

+

Controlled co-assembly in bulk

Versatile properties & applications

++ +

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+ ++ +++ +

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+ ++ + ++ +

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+ ++ +++ +

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Switching on and off the interactionHighly stable cationic & anionic BB

±CeO2 +

+--

+

+ -

+

+-

1000-

--

-

--

-

-Properties & Functions

EDC /NHS

+

++

CeO2

20 nm

- -

-

Formulation

--

-

-

--

-

+

+

-

-

--

-+

-

-

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

chapel@crpp-bordeaux.cnrs.frsribharani@crpp-bordeaux.cnrs.fr

Journées Nationales en Nanosciences et Nanotechnologies 2012