Nanoscale hybrid objects: from 3D SANS study to tunable 2D arrays

formationGéraldine Carrot

Laboratoire Léon Brillouin, CEA-Saclay.

10 nm Polymerization in organic or aqueous medium Study of the structure via SANS (3-D) Use of Contrast MatchingOrganization in 2D and neutron reflectivity

SiO2

Platinum nanoparticles

Pt

Nano-objects based on polymer-graftedinorganic nanoparticles

Bio-application as bio-sensor (glucose probe)

3 nm

Short chains Long chains

dd

Silica nanoparticles

Density of chainsChain lengths

Colloidal suspension in water or in organic solvent

Necessary to avoid aggregation

Control of the surface state

By grafting polymer chains:

Dormant specie

Active specie K = ka / kd

ka

kdCH2 C X

R1

R2

CH2 C

R1

R2

+ Cu(I)X / Ligand + Cu(II)X2 / Ligand

Controlled polymerization principle:

SiO2SiO2SiO2SiO2 SiO2SiO2

O

OO O

O

Br

OO

(CH2)3

CH3

OO(CH2)3

CH3

OO(CH2)3

CH3

Br

OO

(CH2)3

H3C

OO

(CH2)3

H3C

OO

(CH2)3

H3C

Br

O

O

(CH2)3

H3C

O

O

(CH2)3H3C

O

O

(CH2)3H3C

OOO

O

O

Br

O

(CH2)3

CH3

O

O

(CH2)3

CH3

O

O

(CH2)3

CH3

Br

OO(H2C)3

OO(H2C)3

OO(H2C)3

Br

O

O

(H2C)3

CH3

O

O

(H2C)3

CH3

O

O

(H2C)3

CH3

Br

O O

(CH2)3

O O

(CH2)3

CH3

O O

(CH2)3

CH3CH3

Br

O

O

(CH2)3

CH3

O

O

CH2)3(

CH3

O

OCH3

(CH2)3

H3C

CH3

H3CO

OHOH

OH

OH

OH

OH

HOHO

HO

HO

HOHO

HOHO

OHOH

S

O Br

OSi

SO

Br

OSi

S O

Br

OSi

S O

Br

OSi

S

OBr

OSi

SO

Br

O

O

OO

O

OSi

SO

Br

OH

OH

OH

OH

HO

HO

HO

O

OO O

O

OOO

O

O

HS

OSi

SH

OSi

SH

O Si

SH

OSi

SH

OSi

HS

O

O

OO

O

OSi

HSOH

OH

OH

OH

HO

HO

HO

Br

O

Br MABu

n

n

n

n

n

n

n

n

Cu/PMDETADMAP

Controlled radical polymerization from silica nanoparticles

0

0.05

0.1

0.15

0.2

0 100 200 300 400 500

Conversion

Conversion

temps (min)0

0.05

0.1

0.15

0.2

0.25

0 10 20 30 40 50 60

Cinétique

ln([M]0/[M])

t 2/3

0

2000

4000

6000

8000

1 104

1.2 104

1

1.1

1.2

1.3

1.4

1.5

0 0.05 0.1 0.15 0.2

Mn

Mw/M

n

Conv. (%)

Kinetic study of the polymerization via SANS :dispersion state of particles

Desaggregation of the particles as the polymerization proceed

D solvent

Polymer

SiO2

“Polymer matching”

q (Å-1)

0

50

100

150

200

0.01 0.1

I (cm-1)

1st kinetic point

Finalpoint

H solvent

0.0001

0.001

0.01

0.1

1

10

100

0.001 0.01 0.1 1

I (cm-1)

q (Å-1)

After purification: back tothe same state of aggregationthan the initial particles

El Harrak A., Carrot G.,Oberdisse J., Boué F. Macromolecules 2004, 37, 6376-6384.

of the signal at low q

Kinetic study of the polymerization via SANS :Corona growth

0.001

0.01

0.1

1

10

100

0.01 0.1

q (Å -1)

I (cm-1)

Initial point

Final point“Silica matching”

30 min

60 min

230 min

420 min

Polymerization time

Oscillation at the intermediate q with a shift toward low qIncrease of the corona size

of the quantity of polymer

Corona model

R2

R1

0

1 1 0 - 6

2 1 0 - 6

3 1 0 - 6

4 1 0 - 6

5 1 0 - 6

0 0 .0 2 0 .0 4 0 .0 6 0 .0 8 0 .1

I.q4

q (Å-1)

Polymer-grafted silica nanoparticles after purification: corona characterization

q-2Nagg = 5e ≈ 70 Å with 30% of polymerρcore = ρ solvant

Vcorona = 1.28 .10-17 cm-3

Mcorona = 4.0.10-18 gWith Mw=12000 g/mol

198 chains per particle

G. Carrot, A. El Harrak, J. Oberdisse, J. Jestin, F. Boué SoftMatter, 2006, 2, 1043.

“Silica matching”

0.001

0.01

0.1

1

10

100

1000

0.001 0.01 0.1 1q(Å-1)

0.01 0.11E-4

1E-3

0.01

0.1

1

I(q) (

cm-1)

q (Å-1)

Grafted silica nanoparticles in aqueous phase*

0.01 0.10.01

0.1

1

10

q-2

I(q) (

cm-1)

q(Å-1)

R = 20,3 Åσ= 0.28

*Thesis of Jérôme Vinas, CROPS, Marseille, D. Bertin, D.Gigmes

Am Si(OR)3 HO OSiAmO

OSilice+

hydrolyse

condensation

HO

HO

Silice

Same signal asthe bare particles

Polymer signal inSilica matching Si

Polymer matching

ATRP from platinum nanoparticles

-80.7PtPMAB810.540100000PtMAB8-2

36.283.6PtPMAB815.4334100000PtMAB8-1

29.583.1PtPMAB715.3113100000PtMAB7-2

34.288.0PtPMAB719.2455100000PtMAB7-1

Tg (°C)%Polymer

Polymerization batch

Conv.%

Reaction time

Theoretical Mn

Sample

(1) H. Perez et al. Chem. Mater. 1999, 11, 3460-3463. (3) G. Carrot, H. Perez Polym. Prep. 2006, 827(2) H. Perez et al. Chem. Mater. 2001, 13, 1512. (4) G. Carrot, F. Gal, H. Perez, Langmuir, in Press.

S

N H 2

S

N H 2

2 )

1) NaBH 4

S

N H 2

S N H 2

S

H 2 N

S

H 2 N

S

N H 2

SH 2 N PtS N H 2

2

PtCl

C lCl

ClS

N H

S

N H

S

N H

S N H

S

H N

S

H N

S

N H

SHN Pt

O

B r

O B r

O

B r

O

B rO

B r

O

B r

B r

Br

(CH3)2BrCCOB r

DMAP

0 200 400 600 800 1000 12000.0

0.1

0.2

0.3

Con

v%

time (min)0 20 40

0.0

0.1

0.2

0.3

Ln(M

o/M)

t2/3

Surface polymerizations from platinum nanoparticles *

PtPt PtPt

PtLangmuir FilmsPt

Pt Pt Pt

PtPt Pt

compressioncompression

G. Carrot, F. Gal, C. Cremona, H. Perez, Langmuir, in Press.

30 40 50 60 70 80 900

20

40

60

80

100

(b)

(311),(222)(220)

(200)

(111)

Inte

nsity

(arb

. uni

ts)

Two Theta in degree

0.01 0.1

1E-3

0.01

0.1

1

I(q)

q (Å-1)

“Polymer matching”

“Platinum matching”

Study of the nano-objects in solution via SANS

57PtPMA8-(2) p =10.5 %

68PtPMA8-(1) p = 15.4 %

75PtPMA7-(2) p = 15.4 %

95PtPMA7-(1) p=20 %

Rg (Å) Samples

Radius of giration obtained by the fit of the signal in the Guinier regime

0.01 0.11E-5

1E-4

PtPMABu8-1 PtPMABu8-2

I(q)(q

2 )

q (Å-1)

Pt Pt

0.01 0.1

0.01

0.1

1

I(q) (

cm-1)

Wavevector q (Å-1)0.01 0.1

0.01

0.1

1

I(q)(c

m-1)

Wavevector q (Å-1)

Fit of the spectra with a Star model

Zimm-Stockmayer-Benoît model:

)13()()()(

2222

−==

ffqRfqRqR E

gBg

Lg=x

“Platinum matching”

Pt Pt

⎥⎦

⎤⎢⎣

⎡−++−−−−−= ))3(

2)exp()2()2exp()1(

2(2)(

2ffx

fxff

fxff

xxF

Sample Number of

branche, f

Rg gaussienne

RgL

(Å)

Rg branche

RgB

(Å)

Rg Star,Rg

E

(Å)

Number of chains per nm2

Mn of 1 branche,

MB (g.mol-1)

Mn from TGA

(g.mol-1)

PtPMA7-1

5.3 122 53 85.8 0.42 12055 13222

PtPMA7-2

5.2 102 44.3 72.33 0.42 8600 11000

PtPMA8-1

8 119 42.4 70.35 0.63 7723 8558

PtPMA8-2

7 97 36.9 60.8 0.55 5844 7940

Determination of the number of chains and molecular weight

0.01 0.1

1E-3

0.01

0.1

1

I(q) (

cm-1)

q (Å-1)

Pt

Star model

0 50000 1000000

10

20

30

40

P(m

N/m

)

S/Object (Ų)

Langmuir Films-Compression Isotherms

PtPMAB 7-2 (◊) Conv. 15%PtPMAB 7-1 (▲) Conv. 20%Compression

Reversibility

Compression at 2 mN/m 26 mN/m Decompression at 2mN/m

3D-Organization of particles in 2D films

cross-linked

multilayers(with or without Pt)

Alternating H and D

Dispersion of PS-g-Pt NP in cross-linkedfilms via spin-coating and N3 reactions

ANR 2007: Multiclick

Neutron reflectivity

« 3D » cross-linked hybrid multilayer filmsANR 2007 Multiclick Neutron reflectivity

No interdiffusionbetween layers

Alternated polymerlayers using H and D

S. Al-Akhrass, F. Gal, D. Damiron, P. Alcouffe, C. Hawker, F. Cousin, G. Carrot,E. Drockenmuller, Soft Matter (in press).

« 3D » multilayers filmsANR 2007 Multiclick

0.00 0.02 0.04 0.06 0.08 0.10

10-9

10-8

10-7

Particles/PS : 1/5 Particles/PS : 4/5

RQ

4 [Å-4]

Q [Å-1]

S. Al-Akhrass, F. Gal, D. Damiron, P. Alcouffe, C. Hawker, F. Cousin, G. Carrot,E. Drockenmuller, Soft Matter (in press)

Dispersed Pt NP

Neutron reflectivity

Thanks

J. Oberdisse, Université de MontpellierA. El Harrak, PhD student LLB, J. Jestin, CNRS LLB, F. Boué, CNRS LLB

H. Perez, CEA, SPAM-DRECAMFrançois Gal, PhD student LLB

F. Cousin, CEA LLBE. Drockenmuller, Université de LyonS. Al-Akhrass, Université de Lyon