advances in etched ion-track polymer membranes for ... · 25/4/2017 · solid polymers: films,...
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Advances in etched ion-track polymer membranes for environmental and
microelectronic applications
Marie-Claude DUBOIS-CLOCHARDLaboratoire des Solides Irradiés
CEA2/CNRS/Ecole Polytechnique
FRANCE
Laboratoire des solides Irradiés
Mixt laboratory : CEA - Ecole Polytechnique – CNRS, UMR 7642Management: Kees Van Der Beek90 staff members – 6 teams among them XPnano : 8 permanent researchers
The site: the « Ecole Polytechnique » Engineer School
Plateau de Saclay (5km from CEA-Saclay site)
EB facility2,5MeV
PVDF + copo, ETFE, PTFE + terpo
Solid Polymers: films, fibers, nanoparticles…
Ionizing radiations
Film structure, physico-
chemical properties
PUR PP, PE PET PC
Unsaturated bonds, radicals, oxidation
Crosslinking and scission, radiolysis gases
GANIL
LSI
Swift Heavy Ions
Electrons
gamma CEA LIDyL
X, UV USTL
plasmas Faculté de Pharmacie
Irradiation Effects Radiografting
sterilization
ageing stabilityradiolysis
Functionnalization
nanostructuration
Track etching
new
Materials
Irradiated polymers
Research Fields
Energy Environment/HealthNanoelectronic
Fuel cellCancer
Capteurs de pressionA
Fuel cell
Tracks formation
Ion-matter interaction : Energy loss
nm
keV
dx
dE
Deposited Energy per charged particle and per length unit
(dE/dx)Total=(dE/dx)nuclear+(dE/dx)electronic
≈1MeV/u
Nuclear collisions
(dE/dx)nuclear
Electronic interactions
(dE/dx)electronic
Log(Ion-projectile energy)
Log(d
E/d
x)
Tracks
≈1keV/u
Ion-matter interaction
Tracks at the surface of some solids
High sensitivity Weak sensitivity
dE/dxthreshold
~1 keV/uma ~20 keV/uma ~50 keV/uma
Insulators
Polymers
Oxydes
Spinels
Semi-conductors
Amorphous Si
GeS, InP, Si1-xGex
Si, Ge
Metals
Amorphous alloys
Fe, Bi, Ti, Co, Zr
Au, Cu, Ag …
Defaults in a latent track in a polymer film
- Chain scission- Amorphization- Gaz formation (COn, CnHn,…)- Radical formation- Cross-linking- Multiple bonds (ex. C=C, C≡C)
Steckenreiter et al, J. Polym. Sci. A37 (1999) 4318
Kr(720MeV) Kapton
C≡C versus fluence
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
M-C. Clochard, T. Berthelot, C. Baudin, « Procédé d’élaboration de Membranes Conductrices de Protons de Pile à Combustible par 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)
5 patents
Application to Polymer Electrolyte Membrane for fuel cell
A B CA B C
(A) PEMFC for automotive (ex: GENEPAC PSA-CEA), (B) Stack and (C) single cell.
400
500
600
700
800
900
1000
1100
1200
0 200 400 600 800 1000
Nafion 80°C 4 bar, 100% RH80°C 4 bar, 100% RH80°C 2 bar, 100% RH70°C 2 bar, 15% RH
Cell
vo
lta
ge /
mV
Current density / mA.cm-2
61 mS.cm-1 ; 1,2 A.cm-2
Identical efficiency as Nafion
Ion-track membranes for fuel cell: creation of proton conductive channels
Perspectives: how improving the membrane-electrode interface ?
• On-going research
– Understanding exchanges in active phases in the MEAs
– Electrochemical cell adapted for TEM in situ
(Nan’eau PROJECT)Phys. Chem. Phys., 2013, 15, 11236—11247
Commercial ink Ink containing radiografted PVDF NPs
Gamma irradiation
M M
MM
MM
M
PVDF nanoparticles
Covered with ionomer
functionalisation
purification
Gamma irradiation
M M
MM
MM
M
PVDF nanoparticles
Covered with ionomer
functionalisation
purification
-25
-20
-15
-10
-5
0
5
10
3200 3300 3400 3500 3600 3700
Electrons (100 kGy)Rayons gamma (10 kGy)
Inte
nsité n
orm
alisée
par
la m
asse
Champ (Gauss)
-6
-4
-2
0
2
4
6
3200 3300 3400 3500 3600 3700
Electrons (100 kGy)Rayons gamma (10 kGy)
Inte
nsité n
orm
alisée
par
la m
asse
Champ (Gauss)
Alkyl radicals under vaccuum
O2
R
ROO
Irradiations
g
PVDF +
monomer
Irradiations + grafting
Other monomers of interest: vinyl imidazole doped phosphoric acid for high T°C fuel cell applications
In-situ radiografting
monomer
Track revealing : track-etching
Track etching
Template synthesis
PPy nanotubesCylindrical and conical metallic nanowires
Template synthesis: Nanoelectronics - spintronics
Biziere, Nicolas; Gatel, Christophe; Lassalle-Balier, Rémy; Clochard, Marie-Claude;Wegrowe, Jean-Eric; Snoeck, Etienne "Imaging the fine structure of a magneticdomain wall in a Ni nano-cylinder » Nanoletters (2013)
TEM magnetic holography
For the first time, we have imaged2 head-to-head magnetic walldomains on single nanowire. Thisresult have been confirmed parcalculation.
Challenge for MRAM
Controlling magnetic domain wallplaying on the nanowire geometry
Pressure sensor(G. Melilli)
P.Do Chung et al., MRX (2014)
A B
C D
1 µm
500 nm
Gold patternPVDF
Fine gold layer on the bottom
1,5 mm
500 nm
Thick gold layer on the top coveringthe etchedtracks
resin
Tracks in PVDFz plan
Track etched PVDFxy plan
z
xy
Developed at GSI (Germany)
Commercial products (Nuclepore, Poretics) Millipore®, Whatman®…
Ions species: C… Xe… U Fluence: 1…1013ions/cm2
1srt application: membranes for filtration
Membrane recent developments:fabrication on hybrid membranes based on nanoporous graphene
Characterization of nanoporous graphene-on-PMMA substrate
Graphene sidePMMA side
Graphene side profile
Graphene side
PMMA side
-1,0 -0,5 0,0 0,5 1,0-4
-3
-2
-1
0
1
2
3
4
U(m
V)
I(A)
R=3126
Gold contact 2
Goldcontact 1
NPG-on-PMMA membrane
SiO2
Electrical behaviour
magnetoresistance
Perspectives: excellent candidates for water desalination and/or field emissiontransitors…
Remanence of radicals after etching
How to chemically modify pore interior?
Remaining radical fraction profile per track
Decay : 1/r2
Rmoy(nm)
f averaged and normalized to a single track
Images CLSM of PVDF-g-PAA membranes modified withethylenediamine prior to radiografting.Images are xz-plan (cross-section) re-building of xy-planseries.
Red: Fluorescein isothiocyanate reacts with aminefunctions, i.e. oxydation
green: Alexa Fluor R hydrazide reacts with carboxylic acids,i.e. poly(acrylic acid).
Radiografting localization: Double labelling
Z
Applied Research: Early warning sensorsfor monitoring toxic metal ionsCAPTOT Technology
Travis Wade receiving the award of « Salon Pollutec » ex-project ECOSISTEM
CAPTOT Technology
Sensor for toxic metal ions
membrane
9 m
50 nm
35 nm
35
nm
Au
Autop bottom
10
20
30
40
50
60
70
80
-0,8 -0,6 -0,4 -0,2 0 0,2 0,4
25 ppb Co, Ni, Pb and Cu
Cu
rren
t (
A)
Potential (V vs Ag/AgCl)
Co
Ni
Pb
Cu Au
bottomtop
membrane
2.5 cm
7.5
cm
0
5
10
15
20
0.1 1 10 100
y = 6.2149 + 7.1206log(x) R2= 0.98664
pe
ak c
harg
e /
C
[Pb2+
] / g/L
Prices OSEO et POLLUTEC en 2012
Labscale demonstrator
ab
c d
Controlled radical polymerization inside nanopores
Radiation induced RAFT mechanism
(I) Initiation I
IMonomer
ki
P1
(II) Pm +S
Z
S R
(1) (2)
Z
S RSPm
(3)
Z
SPm S
+ R
(III) PnMonomer
kP
Pn+1 RMonomer
kP,1
P1
(IV) Pn
S
Z
S Pm+
(4)
Z
S PnSPm
Z
SPn S
Pm+
(V) Pn Pm+ Pn+m
<kt>
k
k k
k
SHI irradiation Radicals trapped in the crystallites of PVDF(I) Initiation I
IMonomer
ki
P1
(II) Pm +S
Z
S R
(1) (2)
Z
S RSPm
(3)
Z
SPm S
+ R
(III) PnMonomer
kP
Pn+1 RMonomer
kP,1
P1
(IV) Pn
S
Z
S Pm+
(4)
Z
S PnSPm
Z
SPn S
Pm+
(V) Pn Pm+ Pn+m
<kt>
k
k k
k
SHI irradiation Radicals trapped in the crystallites of 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-benzylsulfanylthiocarbonylsulfanyl propionic acid (BPATT)
0
5
10
15
20
25
30
0.01 0.1 1 10 100
y = 11.203 + 8.0783log(x) R2= 0.98638
y = 4.3341 + 8.2961log(x) R2= 0.99045
Peak
cha
rge / µ
C
Log [Pb2+
] / ppb
00
5
10
15
20
25
30
0.01 0.1 1 10 100
y = 11.203 + 8.0783log(x) R2= 0.98638
y = 4.3341 + 8.2961log(x) R2= 0.99045
Peak
cha
rge / µ
C
Log [Pb2+
] / ppb
0
2
4
6
8
10
12
0 10 20 30 40 50
Pe
ak c
harg
e / µ
C
Degree of grafting / wt%
RAFT-mediated radical polymerization = improvementof sensors sensitivity
Enhancement of the efficiency of the sensors for water quality detection by a factor two
Murat Barsbay, Olgun Güven, Haad Bessbousse, Travis L. Wade, François Beuneu, Marie-Claude Clochard « Nanopore size tuning ofpolymeric membranes using RAFT-mediated radical polymerization J. Memb. Sci. (2013)
Hg2+ detection
Mercury drop electrode
+ relatively expensive
+ somewhat portables
+ wide range of detectable ions
- Mercury
- Difficult to use
+ very sensitive
Ion Selective Electrodes
+ cheap
+ Portable
+ real-time analysis
- Interferences
- Limited to some ions
+ easy to use
- Lack of sensitivity
Limit of detection for Hg2+ 0.01 ppb
Existing portable technologies CAPTÔT performances
0
20
40
60
80
100
120
140
160
-1 -0,5 0 0,5 1 1,5
I / µ
A
Potential vs Ag wire / V
Hg --> Hg2+
Au
oxygen
a)
15
20
25
30
35
40
45
50
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7
Potentiel vs Ag wire / V
0.100 g/l
0.050 g/l
0.010 g/l
I / µ
A
0
5
10
15
20
25
0 0,02 0,04 0,06 0,08 0,1 0,12
I /
A
concentration / g/l
b)
Source: CEA BEM may 2012
International market
Equipment sales distribution
*1 time/month analyses for a theoretical level of pollution between 10 and 50 ton/year** Daily analyses for a theoretical level of pollution >3000 tons/year
• Identified industrials
Licencing ? (5 patents)10 prototypes / year+ strip-electrodes
IDEX
Valorization: toward a technological transfert
• Potential targets: Water actors: BRGM, KWR(NL), Cogent(UK), Suez Environnement, Veolia
(SARP)…Analyses companies: SGS, (CETIM)HYTEC, Methrom(US),Trace Detect (US), Sens Aqua (No), Liquum (Fin),Applitek (Be), Elta (Fr), Trace2O (UK), Palmsens (NL),Mesureo(Fr), thermofisher(Fr), Modern Water (UK), Private medical analyses laboratories …
2016-2018
From a demonstrator to a prototype
with integrated potenstiostat
Demonstrator 1st generation (2008)
Demonstrator 2nd generation
Artview of the final prototype
Prototype 1st generation(2017) a reality!
Perspective: Uranium detection using CAPTOT
CAPTOT is based on polymer radiograftingtechnique and ASV.
ASV is an established technique for the determination of Uranium trace levels (< 1ppb) in water.[1] .
CAPTOT is planned to be used as a tool to dynamically test performances towards UO2
2+ uptake and release of the radiografted functionnalisations(prof. Al-Sheikhly team).
From:[1] M.B. Gholivand et al. “Cathodic adsorptive stripping voltammetric determination of uranium(VI) complexed with 2, 6-pyridine dicarboxylic acid” Talanta 65 (2005) 62–66.
UO2 ← UO22+ + 2e-
Perspectives in nanofluidics
… a world to explore!
Ionic conductivity experiment Results
Size selection
Coming back to fundamentals…
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