1
Macroscopic assemblies of aligned nanotubes
studied by X-ray diffraction and microdiffraction
Laboratoire de Physique des Solides (UMR CNRS 8502), bât. 510, Université Paris Sud, 91405 Orsay cédex, France
http://www.lps.upsud.fr/Utilisateurs/launois/
Pascale Launois
2
Vincent Pichot
PhD thesis at LPS Orsay (2003-2006)
Present address: Institut Franco-Allemand de Saint Louis (ISL) &
Institut de Physique et Chimie des Matériaux (IPCMS), Strasbourg, France
Mathieu Pinault, Martine Mayne-L’Hermite and Cécile Reynaud
Laboratoire Francis Perrin (LFP), CEA/CNRS, Saclay, France
Manfred Burghammer and Christian Riekel
ESRF, Grenoble, France
Stéphane Badaire, Pierre Miaudet, Cécile Zakri and Philippe Poulin
Centre de Recherche Paul Pascal (CRPP), CNRS, Bordeaux, France
3
Scheme
1. Introduction
2. Multi-walled carbon nanotube carpetsGrowth mechanisms
3. Single-walled carbon nanotube fibers Mechanical properties
versus structural properties
4. Conclusion
4
1. Introduction
Single-Walled carbon Nanotube (SWNT) - 1993
Diameter ~ nmLenght ~ μm
Chiralangle
Multi-Walled carbon Nanotube(MWNT)
1991
5
YEAR
ARTICLES with‘ALIGN’ and ‘NANOTUB’
in title
P. Launois and P. Poulin,Encyclopedia of Nanoscience and
Nanotechnology 4, 1 (2004)
Highly anisotropic
of aligned NTs
Exceptional propertiesElectronic properties
SWNT: semiconductor or metallic (unique)Withstand high current density ~109 A/cm2
(Cu wire: 106 A/cm2)
Field emission
NTs >> Mo tips
Mechanical properties
Young modulus Y ~ 1 TPa Tensile strain σR~ 45 GPa
(steel: Y~0.1 TPa, σR~ 2 GPa)High flexibility
Nano-devices Macroscopic samples
Collins and Avouris, Scientific American (2001)
6
High yield production
Fibers
23 μm
B. Vigolo et al, Science 290, 1331 (2000)
L.M. Ericson et al, Science 305, 1447 (2004)
P. Miaudet et al, Nanoletters 5, 2212 (2005)
Carpets/forests
cm
C. Singh et al, Chem. Phys. Lett. 372, 860 (2003)
M. Mayne-L’Hermite et al., Proceeding of the chemical vapor deposition-XVI
and EUROCVD-14, vols. 2003–2008 : p. 549 (2003)
7
Carpets/forests
Potential applications
Chemical separation and sensing
B.J. Hinds et al, Science 303, 62 (2004)
N. Grobert et al, Appl. Phys. Lett. 75, 3363 (1999)
High density magnetic storage
Very high toughness fi bulletproof vests, protective textiles
or helmets
Fibers
A.B. Dalton et al, Nature 423, 703 (2003)
570 J/g> spider
dragline silk
Strain
Stre
ss
55J/g> kevlar
P. Miaudet et al, Nano Letters 5, 2212 (2005)
Toughness
8
X-ray scattering studies(LPS - Orsay, LURE - Orsay, ESRF- Grenoble)
Carpets/forests
MWNT carpetssynthesized by
CatalyticVapour Deposition (CCVD)
Prerequesitive for development of applications:
growth mechanisms?
Fibers
SWNT/polyvinyl alcohol (PVA)fibers
Mechanical properties
versus
structural properties
- SWNT alignment
- PVA structure and alignment
- SWNT-PVA interactions
9
2. MWNT carpets
The aerosol-assisted CCVD method
850°C
M. Pinault, M. Mayne-L’Hermite, C. ReynaudLaboratoire Francis Perrin, CNRS/CEA-Saclay, France
Siliconsubstrate
NT carpet
10
ϕ=0°
y
X-rayscarpet
Si substrate
2D detector
Structure and morphology from X-ray scattering
cfc γ Fe (220)
C~3.45Å MWNT long axis: preferential orientation ^ carpet basis
(002)MWNT
V. Pichot, P. Launois, M. Pinault, M. Mayne-L’Hermite, C. Reynaud, Appl. Phys. Lett. 85, 473 (2004)
γ Fe nanowires inside nanotubes
-Confinement effect-Preferential orientation <110>
τ
[110] // NT[100] // NT[111] // NT
τ
ϕ=15°
[110]
11
Tip growth?
Growth mechanisms?
Role of iron nanowires?X. Zhang et al.,
Chem. Phys. Lett. 362, 285 (2002)
Base growth?
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Base growth mechanism
M. Pinault, V. Pichot, H. Khodja, P. Launois, C. Reynaud and M. Mayne-L’HermiteNano Lett. 5, 2394 (2005)
B*≈ 2 min 30
B≈ 7 min 30
B*≈ 1 min 30
B≈ 7 min 30
B+F (2.5 wt%)I3
5 min5 min5 min10 min10 minT+F(5 wt%)P1
(5)(4)(3)(2)(1)
Varying parameters during the sequential injectionConstant parameterSample
Sequential growth
F=ferrocene, T=toluene, B=benzene, B*=benzene containing 13C isotope
t = 0
(1)
(2)
(3)
(4)
(5)substrate 100 µm
P1Carbon progress (using 13C detection with nuclear microprobe)
I3
13
XRD analysis: the catalyst particles
MWNT (∆)Silicon substrate (+) Particles (o) : isostructural iron oxide phases maghemite or magnetite, γ-Fe2O3 or Fe3O4
(311)
substrate10 μm
2 min
1 μm
M. Pinault, M. Mayne-L’Hermite, C. Reynaud, V. Pichot, P. Launois and D. BallutaudCarbon 43, 2968 (2005)
14
beam position (μm)
(311
) int
ensi
ty (a
.u.)
Si I1 I2
Si substrate
I1
I2
V. Pichot, P. Launois, M. Pinault, M. Mayne-L’Hermite, C. Reynaud, M. Burghammer and C. Riekel,AIP proceedings vol 786, H.Kuzmany et al. Eds., p. 158 (2005)
Iron oxyde particles:located at the carpet basis
Microdiffraction (ID13, ESRF): catalyst particles location
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Base growth
NTiron
iron oxyde
16
Microdiffraction: NT alignment V. Pichot, P. Launois, M. Pinault, M. Mayne-L’Hermite, C. Reynaud, M. Burghammer and C. Riekel,AIP proceedings vol 786, H.Kuzmany et al. Eds., p. 158 (2005)
-180 -90 0 90 180
inte
nsity
(a.u
.)
τ (°)
HWHM
when stopping synthesis: the argon gas flushes the remaining aerosol to the reactor
aerosol injection is suddenly stopped
Crucial role of the synthesis procedure
on NT alignment
0 50 100 150
10
20
30
HW
HM
(°)
beam position (µm)
Si substrate
0 50 100 150
10
20
30
HW
HM
(°)
beam position (µm)
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In brief…
→ Base-growth mechanism
→ Nature and structure of catalyst particles: iron oxyde maghemite or magnetite γ-Fe2O3 or Fe3O4
→ NT alignment / synthesis procedure
Interest of microdiffraction
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3. SWNT fibers
Aqueous dispersion of SWNTwith sodium dodecyl sulfate (SDS)
is injected in a rotating solution of polyvinyl alcohol (PVA)
Condensation of NT+PVA in a ribbon
Rinsed ribbon suspended in air
FiberSWNT/PVA 50/50 wt %
PVA
Ribbon
NT+SDS
Fiber processing
B. Vigolo, A. Pénicaud, C. Coulon, C. Sauder, R. Pailler, C. Journet, P. Bernier and P. PoulinScience 290, 1331 (2000)P. Poulin, B. Vigolo, A. Pénicaud and C. Coulon, CNRS Patent 0002272 (2000)
CRPPBordeauxFrance
PVA = [ -CH2CHOH- ]n
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Aim: to modify NT orientation in a fiberto analyze physical properties as a function of orientation
Post-synthesis treatment
ll0
Solvent
m
The fibers are rewetted in a solvent for PVA and are dried under tensile load
B. Vigolo, P. Poulin, M. Lucas, P. Launois, P. Bernier, Appl. Phys. Lett. 81, 1210 (2002)P. Poulin, B. Vigolo, P. Launois, P. Bernier, CNRS patent 0110611 (2001)
0
0
lll −
Draw ratio =
20
Structural analysis by X-ray diffraction
P. Launois, A. Marucci, B. Vigolo, P. Bernier, A. Derré and P. Poulin, J. Nanosci. Nanotechnol. 1, 125 (2001)V. Pichot, S. Badaire, P.-A. Albouy, C. Zakri, P. Poulin and P. Launois, submitted
X-rays2D detector
k0 k 2θB
Fiber
Q
Radial scan ⇒ composition of the fiber
SWNTbundles
amorphousPVA
Azimuthal scans fl orientation
HiPCO SWNT/ PVA fiberτ
21
V. Pichot, S. Badaire, P.-A. Albouy, C. Zakri, P. Poulin and P. Launois, submitted
• Distribution of orientations p(θ) z
•
0 20 40 60
15
20
25
w (°)
draw ratio (%)
from experiments from calculations
0 20 40 60
1
2
3
4
f
draw ratio (%)
from experiments from calculations
fl Two-phase model, oriented and non-oriented fractionsp(θ) = (p1(θ)+f p2)/(1+f), p1: Gaussian function (HWHM w), p2=1/(4π)
Calculations:affine model
of induced orientations at constant volume
NT orientation improved for increasing draw ratios
z’ ≡ NT long axis θ
ϕx
y
z
22
Mechanical propertiesare improved
for better nanotubes alignment
Mechanical properties
V. Pichot, S. Badaire, P.-A. Albouy, C. Zakri, P. Poulin and P. Launois, submitted
E=22GPa
σR=170MPa
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Continuum mechanics Role of PVA neglected
T. Liu and S. Kumar, Nanoletters 3, 647 (2003)
)(cos2111)(cos22115,0
4
1
12
1221
2
21
12
122θθ ⎟
⎠⎞
⎜⎝⎛ +−++⎟
⎠⎞
⎜⎝⎛ −−+
=
Ev
GEEEEv
GE
E
E1, E2, G12 and v12 = longitudinal modulus, transverse modulus, in-plane shear modulus and Poisson’s ratio of a nanotubes bundle
For perfect alignment, Young modulus → E1/2=320 GPa >> 20 GPa measured
Agreement correct…
but not very good:
role of PVA-NT interactions?
24
Rubber
Draw ratio 300%
From P.A. Albouy, LPS, Orsay France
Cis-polyisopropene
Stearic acid
G.R. Michell , Polymer 25, 1562 (1984)
‘I(τ) may be considered to be the consequence ofsmearing or convoluting the scattering which wouldbe associated with a single orienting structure Iu(τ),
with the orientation function D(τ)’
The observed anisotropy in the scatteringmay be much smaller than
the anisotropy in the molecular orientation
τ
V. Pichot, S. Badaire, P.-A. Albouy, C. Zakri, P. Poulin
and P. Launois, submitted
HiPCO SWNT/ PVA fibers
AmorphousPVA
NT
PVA chains alignment is templated by that of NTs
Same Gaussian fit
Evidence for PVA-NT interactions
25
AmorphousPVA
NT
PVA partial
crystallisationFrom V. Pichot
PhD thesis, Université Paris XI
France (2005)
P. Miaudet, S. Badaire, M. Maugey, A. Derré, V. Pichot, P. Launois, P. Poulin and C. Zakri,Nano Letters 5, 2212 (2005)
Solvent drawing Hot drawing
Improved mechanical properties for improved alignment and PVA crystallization
E=22GPa
σR=170MPa
55J/g> kevlar
E~30GPa
σR~1600MPa
See also:Cadek et al, Nano Lett. 4, 353 (2004)Coleman et al,Adv. Func. Mat. 14, 791 (2004)
Role of the PVA structure
26
In brief…
→ Mechanical properties are improved for improved NT alignment
→ PVA alignment is templated by NTs
→ Mechanical properties depend on PVA-NT interactions
and on PVA structure
(amorphous/crystalline)
→ High toughness for hot drawn fibers
27
4. Conclusion
X-rays
Carpets Fibers
Base growth mechanism
Iron oxyde catalytic particles
Iron nanowires inside NTs
• Iron oxyde/iron?
• Iron-NT interactions?
• How to obtain αFe ferromagnetic nanowires?
NT<110>
γFe
iron oxyde
Mechanical properties improved for
improved NT alignment
Opened questions…
• PVA-NT interactions?
• Role of PVA for mechanical properties?