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" Radiografted track-etched polymer membranes for research and application »

Marie-Claude DUBOIS-CLOCHARD

Laboratoire des Solides Irradiés, UMR 7642

www.cea.fr - www.lsi.polytechnique.fr

Laboratoire des solides Irradiés

Mixt laboratory : CEA - Ecole Polytechnique CNRS, UMR 7642

Management: Kees Van Der Beek

90 staff members 6 teams among them XPnano : 9 permanent

researchers

The site: the " Ecole Polytechnique » Engineer

School

Plateau de Saclay (5km from CEA-Saclay site)

EB facility

2,5MeV

Ionizing radiations

Supply new physico-chemical properties

Swift Heavy Ions

Electrons*

Rays CEA LIDyL

Irradiation effects

Radiografting

Defaults formation

Functionnalization

Nanostructuration Innovative materials

*Clochard et al., Polymer (2004)

Chain scissions

Amorphization

Multiple bonds

Crosslinkings

Radicals

IRRADIATED POLYMERS

RESEARCH FIELDS

Energy Environment/He

alth

Nanoelectronics

A

Fuel cell Cancer Pressure sensors

Ion-Matter interaction

Electronic

interaction (non-elastic)

Nuclear

interaction (elastic)

Electronic excitation and

ionization

Coulombian screening

between particles:

Collision of solid spheres

e- e- e-

Fast Vion

Slow Vion

Ion-Matter Interaction

Highly excited

cylindrical zone = latent track Atoms

Dislocations

+ Vion>>Ve

Vion<

Ion-Matter Interaction

Nuclear collisions

(dE/dx)nuclear

Electronic interactions

(dE/dx)electronic

Log(Ion-projectile energy)

Log(dE/dx)

Tracks

Transferred kinetic energy T

2 2 2 42
2 1.2 bpvm eZT e eff 2 2 2 1vm eZb e eff pĺ" 7:S:7:7max2mev2

All electrons are emitted at 90° to ion-

projectile trajectory

Track formation in a thin polymer film

GANIL

SME beam line

E ~10 MeV/uma

Emmanuel Balanzat

Irradiation Latent Tracks

Vacuum, O2,

N2, SO2, NH3"

Grafting

monomer + T°

Radio-grafting in latent tracks

Natacha BETZ " Ion Track Grafting » NIM B 105 (1995) 55-62

Natacha Betz

- Chain scission - Amorphization - Gaz formation (COn, CnHn - Radical formation - Cross-linking

Defaults composing the latent track in polymers

M-C. Clochard, T. Berthelot, C. Baudin, "

Radiogreffage » CEA French patent (BD 1727) FR 0757875 ext PCT WO/2008/062726 (2007)

T. Berthelot, M-C Clochard, " Membranes Conductrices de Protons pour Pile à Combustibles présentant un gradient de protons et

Procédés de Préparation desdites Membranes» CEA French patent (BD 10047) FR 0757873 ext PCT WO/2009/103925 (2007)

T. Berthelot, M-C Clochard, " Membranes Conductrices de Protons pour Pile à Combustible et Procédés de Préparation desdites

Membranes» BD11266 French patent FR0955854 ext PCT WO/2010/062512 (2009)

E. Gallino, M-C Clochard, A. Morin, G. Gebel, "Suspension aqueuse comprenant des particules de catalyseur métallique et des particules

de polymère spécifique utilisable pour la fabrication de couche active d'électrode" CEA-X-CNRS FR1252533 (2012)

ENERGY

5 patents

Polymer Electrolyte Membrane for fuel cell

How works a PEM fuel cell?

William Grove, 1839

2H2 + O2 2H2O

Anode (oxydation) - fuel

2H2 4H+ + 4 e- (0V)

Cathode (reduction) air or oxygen

O2 + 4 H+ + 4 e- 2 H2O (1,23V)

ABC ABC (A) PEMFC for automotive (ex: GENEPAC PSA-CEA), (B) Stack and (C) single cell. - Limit of use = temperature (~ 90°C) . Catalytic activity is not optimized . CO Poisoning . Advanced degradation for T>90°C (cycles) - Mechanical properties of Nafion are affected by the hydration - High cost

Reference polymer membrane = Nafion®

Working T°C : 60-70°C

Pressure: 1-5 bars

Lifetime: 3000-4000h

C F2 C F2 C F2 F C

OCF2CFCF3

OCF2CF2SO3H

C F2 C F2 C F2 F C

OCF2CF2SO3H

AB nxnx Dupont de Nemours (A : Nafion®) and Dow Chemical (B : Dow®) Our idea is to create rectilinear chanels to diminuish the overal resistance and to strengthen the mechanical property of polymer membrane (non-irradiated part) in limiting the water uptake. 1 cm

Ion track grafted film

(PVDF-g-PSSA)

Non-grafted film

(PVDF) C H2 C F2 C H2 H C SO3H xy

Electrophilic substitution

Polymer Electrolyte Membrane : PVDF-g-PSSA

PVDF-g-PS dopé au Césium

5.107ions/cm2Y=1.7wt%

PVDF-g-PSSA

1010ions/cm2Y=140wt%

H+ 400
500
600
700
800
900
1000
1100
1200

02004006008001000

Nafion 80°C 4 bar, 100% RH

80°C 4 bar, 100% RH

80°C 2 bar, 100% RH

70°C 2 bar, 15% RH

Cell voltage / mV

Current density / mA.cm-2

0 0.2 0.4 0.6 0.8 1

00.20.40.60.811.2

40 mA.cm-2

40 mA.cm-2

80 mA.cm-2

80 mA.cm-2

200 mA.cm-2

200 mA.cm-2

400 mA.cm-2

400 mA.cm-2

-Im(Z) / Ohm.cm 2

Re(Z) / Ohm.cm2

A -0.05 0 0.05 0.1 0.15 0.2 0.25

00.050.10.150.20.250.3

600 mA.cm-2

600 mA.cm-2

1200 mA.cm-2

1200 mA.cm-2

-Im(Z) / Ohm.cm 2

Re(Z) / Ohm.cm2

B

Fuel cell test

61 mS.cm-1

1,2 A.cm-2

Clochard et al, J. of Power Sources 195 (2010) 223-231

Electrochemical Impedance Spectroscopy

Polarization curves

How improving the membrane-electrode interface ?

Future

Understanding exchanges in active

phases in the MEAs

Coming soon in 2015 at LSI:

electrochemical cell adapted for TEM in situ (Equipex TEMPOS)

Phys. Chem. Phys., 2013, 15, 1123611247

Commercial ink Ink containing

radiografted PVDF NPs

Radiografted PVDF-g-PVI NPs

as new binders for high T°C fuel cell S. Galbiati, P-E. Coulon, G. Rizza, M-C. Clochard, M.Castellino, M. Sangermano, C.Nayoze, A. Morin " Poly(vinylimidazole) radiografted PVDF nanospheres as alternative binder for high temperature PEMFC electrodessubmitted)

Nafion

Electrode/membrane INTERFACE

after fuel cell test

New ink

0 0,2 0,4 0,6 0,8 1

050100150200

Current density (mA/cm2)

Comparison of polarization curves of Nafion® NRE

212 with the novel electrodes at 70°C in presence of

H2 and O2 at 100% RH (black line) and 40% RH (grey line); in presence of H2 and air, 40% RH (dashed line).

Developed

at GSI (Germany)

Track revealing : track-etching = nanoporous

membranes

Commercial products (Nuclepore,

Poretics) Millipore

13ions/cm2

30 min 1 h

2 h 1 h 30

30 min 1 h

2 h 1 h 30

Proportionality of nanopore radii with etching time -PVDF (Kr31+ 10 MeV/uma)

Nanopores characterization

X 100 000

PACE, CEA Saclay

Didier Lairez

1)Pore reflections on pore walls

2)Pore radii r

Periodic Modulations of the

signal by Bessel function: SANS FESEM

SANS gives also information on pore rugosity

Pa(r) is gaussian of

average value r0 and its standard deviation

FESEM of 375 nm pore diameter in

a -PVDF membrane

How to chemically modify pore interior?

if < 1µm, radical or peroxyle species are still trapped inside cristalline domains etching why not using chemical modifications induced by SHI radiation already

9000nm

PVDF, 5e8 ions/cm2, Øpore=50nm

O. Cuscito

Electron Paramagnetic Resonance (EPR) spectra per mass unit (mg1) for heavy ions irradiated film before etching (latent tracks) and after 1h track etching. In this latter case, non-horizontal baseline is due to paramagnetic impurities (KMnO4 from etching bath).

Remaining radicals after etching

Decay : 1/r2

Remaining radical fraction profile per track in PVDF

Rmoy(nm)

f averaged and normalized to a single track x 35000 x 95000

Spherolytic structure

Crystalline lamellae

Amorphous intra-

crystalline zone

Amorphous inter-crystalline zone

Nucleation site

Crystalline structure of PVDF

Images CLSM of PVDF-g-PAA membranes

modified with ethylenediamine prior radiografting. Images are xz-plan (cross-section) re-building of xy- plan series.

Red: Fluorescein isothiocyanate reacts with amine

functions, i.e. oxydation green: Alexa Fluor R hydrazide reacts with carboxylic acids, i.e. poly(acrylic acid).

Radiografting localization: Double labelling

Z

Confocal Laser Scanning Microscopy

of a track-etched PVDF membrane (5x106 cm-2)

Mean deviation = 0.023rd

Angle deviation of the pores

X Y Z a b c d

Controled radical polymerization inside nanopores

Radiation induced RAFT mechanism

(I)InitiationI I

Monomer

ki P1 (II)Pm+S Z SR (1)(2) Z SRSPm (3) Z SPmS + R (III)PnMonomer kP

Pn+1RMonomer

kP,1 P1 (IV) Pn S Z SPm+ (4) Z

SPnSPm

Z SPnS Pm+ (V)PnPm+Pn+m k kk k SHI irradiationRadicalstrappedin the crystallitesof PVDF (I)InitiationI I

Monomer

ki P1 (II)Pm+S Z SR (1)(2) Z SRSPm (3) Z SPmS + R (III)PnMonomer kP

Pn+1RMonomer

kP,1 P1 (IV) Pn S Z SPm+ (4) Z

SPnSPm

Z SPnS Pm+ (V)PnPm+Pn+m k kk k SHI irradiationRadicalstrappedin the crystallitesof PVDF

AFM : nanopore filling

R=25nm

PVDF-g-PAA membrane

78Kr31+, fluence 1010 ions/cm2

Prof. Olgun Güven

8wt%

14wt% 31wt%

43wt% 63wt%

RAFT = 3-

benzylsulfanylthiocarbonylsul fanyl propionic acid (BPATT) The IAEA is the world's center of cooperation in the nuclear field. It was set up in 1957 as the world's "Atoms for Peace" organization within the United Nations family. The Agency works with its Member States and multiple partners worldwide to promote safe, secure and peaceful nuclear technologies.

Coordinated Research Projects (3-years projects)

Potable water

Necessary for life

Toxic heavy metals

(Pb(II), Cd(II),

Hg(II), Cr(VI),

Developing countries

EUROPEAN RULES ON HEAVY METALS

The directive 2008/105/EC on water

adresses priority substances : Mercury (0.05 µg/L), Lead (7.2 µg/L), Cadmium (from 0.08 to 0.25 µg/L depending the hardness of water), Nickel (20 µg/L) tolerated EQS for superficial waters

The directive on potable water imposes

threshold values for the Cu, Pb, Cd, As, Cr and Ni in the range of few µg/L (ppb) and below.

The directive for Industrial effluents of the 6

jan. 2011 Hg et Cr (VI).

These directives push to the real-time

and on-site analysis to prevent from any ecological disaster

Advantages:

- Sensitivity (pre- concentration) - Quick - Simple use - Low-cost IAEA Project 14622 : RTRA funding Project ECOSISTEM

T.L. Wade, M-C Clochard

European Patent Office

reference 08305237 Bessbousse H et al Anal Chem (2011), Rad. Phys. Chem (2015) 10 20 30
40
50
60
70
80
-0,8-0,6-0,4-0,200,20,4

25 ppb Co, Ni, Pb and Cu

Current (

A)

Potential (V vs Ag/AgCl)

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