Polymer Nano-composites

Robert J Young FREng*

School of Materials,
University of Manchester, UK
Collaborators:
Carole Cooper, Matthew Halsall, Kostya Novoselov, Kannan Prabakaran, Libo
Deng, Steve Eichhorn, Shuang Cui, Ian Kinloch, Paweena Sureeyatanapas
* Also Chair Professor, ITC, Hong Kong Polytechnic University
Contents
Advanced Composites
Carbon fibres
Raman spectroscopy
Carbon nanotubes (SWNTs)
Raman spectroscopy
Carbon nanotubes in epoxy composites
Mechanical deformation
Interfacial stress transfer
Nanotube composite nanofibres
Double Walled carbon nanotubes
Graphene
Prediction of Advanced Composites Use in USAF Aircraft
Formula 1 Motorsport
Major advances have been
made since the 1970s by
British Companies
through the use of
advanced composites with
high stiffness and strength
Carbon Fibre Composites
+ Resin =
Carbon Fibres
Composite
Woven
Fabric
Fibre Reinforced Composites
WOVEN ARAMID CARBON/EPOXY
Good multi-directional stiffness
Good energy absorption
F1 Crash Survival with Composites!
First Commercial Carbon Fibre Composite Aircraft
Maiden flight
15
th
December 2009
Boeing 787
Fibre Reinforcement? Composite Micromechanics
Stress distribution along
a discontinuous fibre
Good bonding
Yielding/debonding
Ramans Experiment
observer
sunlight
(white)
violet
filter
violet
scattering
liquid
Raman-
scattered
light
green
green filter
Rayleigh-
scattered
light
violet green
Published 1927
Awarded Nobel Prize
Raman spectroscopy
Inelastic scattering of light
Laser spot size down to 1 m
Spectra obtained for many non-metallic materials
Particularly useful for nanomaterials
Large stress-induced band shifts (stress sensing!)
specimen
laser
beam
scattered
light
Raman Spectra of Carbon Fibres
1000 1500 2000 2500 3000
0
100
200
300
P120
P100
P75
P55
P25
I
n
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n
s
i
t
y

(
A
r
b
i
t
r
a
r
y

U
n
i
t
s
)
Wavenumber (cm
-1
)
1000 1500 2000 2500 3000
0
100
200
300
400
T50
HMS4
T650
T800
T40
T300
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(
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U
n
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t
s
)
Wavenumber (cm
-1
)
Pitch-Based Fibres PAN-Based Fibres
Raman spectroscopy allow the different types of fibres to be characterised
Fibre Modulus
D G
G
G G D
G 2D
Carbon Fibre Deformation G Band Shift
-0.1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
2630
2635
2640
2645
2650
2655
2660
2665
2670
T50
P100
P120
G
'

B
a
n
d

R
a
m
a
n

w
a
v
e
n
u
m
b
e
r

(
c
m
-
1
)
Fibre strain, e
f
(%)
Rate of strain-induced bands shift proportional to fibre modulus
Composites Micromechanics Carbon Fibre/Epoxy
T50 carbon fibre in an epoxy resin undergoing deformation
-0.1
0
0.1
0.2
0.3
0.4
0.5
0 500 1000 1500 2000 2500
e
f
/ %
Distance along fibre (m)
e
m
=0.0%
e
m
=0.4%
e
m
=0.7%
l
c
/2
Different Forms of Nano-Carbon
Nanotube
C
60
Graphene
How well do they reinforce a polymer matrix in a composite?
C
60
Raman Spectroscopy
500 1000 1500
5000
10000
15000
20000
25000
30000
35000
273
433
497
710
568
773
1101 1250
1468
1574
C
60
R
e
l
a
t
i
v
e

I
n
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e
n
s
i
t
y

(
A
r
b
i
t
r
a
r
y

U
n
i
t
s
)
Raman Wavenumber (cm
-1
)
C
60
Particulate Composite
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
1468.6
1468.8
1469.0
1469.2
1469.4
1469.6
Slope =-0.13 cm
-1
/%
TENSION
C
60
in Epoxy Resin

R
a
m
a
n

W
a
v
e
n
u
m
b
e
r

(
c
m
-
1
)
Strain (%)
1462 1464 1466 1468 1470 1472 1474
10000
20000
30000
40000


TENSION
C
60
in Epoxy Resin
on PMMA Beam
Strain
0.0%
1.4%
R
e
l
a
t
i
v
e

I
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s
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t
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(
A
r
b
i
t
r
a
r
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U
n
i
t
s
)
Raman Wavenumber (cm
-1
)
C
60
Epoxy Composite
He-Ne Laser (633nm red line)
Raman spectrum of HiPco SWNTs
500 1000 1500 2000 2500 3000
G' Band
RBM
D Band
G Band


I
n
t
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n
s
i
t
y

/

a
.
u
.
Raman wavenumber / cm
-1
G Raman band
Stress- and polarization-sensitive
RBM - radial breathing mode
Band position 1/diameter
Deformation of Carbon
Nanotubes in Composites
Nanotubes as Fibres
Stress Sensing of Carbon Nanotubes in Composites
2550 2600 2650 2700 2750
200
300
400
500
600
700
800
900
1000
0%
1.2%
TENSION
SWNT

R
e
l
a
t
i
v
e

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s
i
t
y

(
A
r
b
i
t
a
r
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U
n
i
t
s
)
Raman Wavenumber (cm
-1
)
SWNT/Epoxy Composite
The large stress-induced band shift
implies the nanotubes have
a high value of Youngs modulus
Dispersion of 0.1% of SWNTs in a
polymeric resin deformed on a beam
Cooper CA, Young RJ , Halsall M.
Composites: Part A 2001;32(3-4):401-411.
G Band
Band shift under 4-point bending
0,00 0,05 0,10 0,15 0,20 0,25
2609
2610
2611
2612
2613
2614
2615
2616
y=2615.004 - 15.497 x
R=0.99398
R
a
m
a
n

s
h
i
f
t

(
c
m
-
1
)
% Strain
Nanotube Composite beam
Band-shift rate
-15.5 cm
-1
/% strain
Optical
Strain
Gauge
Estimation of Nanotube Modulus
Raman band shift rate can be related
to modulus by following the shift
of the same G Raman band
for carbon fibres of known modulus
0 100 200 300 400 500 600 700 800 900
0
5
10
15
20
25
30
35
40
45
50
Carbon Fibres
P75
P120
P100
P55


R
a
m
a
n

B
a
n
d

S
h
i
f
t

R
a
t
e

(
c
m
-
1

/

%
)
Tensile Modulus (GPa)
( )
S S d
2 0
2 2
2
2
1
=

cos sin
( )
S S d
o 3 0
2 2
2
=

sin cos sin

Band shift rate for random 2-D orientation

Band shift rate for random 3-D orientation
where S
0
is the measured SWNT shift rate
Cooper CA, Young RJ , Halsall M., Composites: Part A 2001;32(3-4):401-411.
Calculated
Modulus
2-D
(GPa)
SWNT 780
210
204 83
MWNT
-50 cm
-1
%
-1/
TPa
Individual Carbon Nanotubes
Nanotubes as Molecules
(0,0)
C
h
= (10,5)
a
2
a
1
x
y
Structures of Carbon Nanotubes
http://www.photon.t.u-tokyo.ac.jp/~maruyama/
Unit cell for a (6,3) tube
The tube diameter d
t
is given by
The chiral angle is given by
d
t
Geometry of Chirial Single Walled Nanotubes
/ ) ( 246 . 0
2 / 1 2 2
m nm n d
t
+ + =

+
=

) 2 (
3
tan
1
n m
m

AFM image 1010 m

2
Preparation*
Chemical vapour deposition on a Si
Substrate containing nanometer size iron
catalyst particles. The Si substrate had
been oxidised to have a thin SiO
2
surface coating.
The nanotubes nucleate and grow from
well-isolated catalyst particles and
nanotube bundles are not formed.
*The isolated nanotubes were prepared by Drs N Wilson &
J McPherson of University of Warwick following the
method of J urio et al (Phys. Rev. Lett., 86 (2001) 1118)
Individual nanotubes AFM
Diameter of laser spot ~2 m
Raman spectra of individual single-walled nanotubes
Laser Polarisation
2 m
Nanotubes must be in the correct orientation and in resonance
50 100 150 200 250 300 350
0
10000
20000
30000
40000
50000
60000
267
226
171
I
n
t
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n
s
i
t
y

(
a
.
u
.
)
Raman Wavenumber (cm
-1
)
Weak
Silicon
Band
(17,2)
(9,7)
(10,3)
Isolated Single-Walled Nanotubes Breathing Modes
Resonance Raman Scattering strong RBMs
Nanotube Composite Nanofibres
Kannan P., Eichhorn S.J . and Young R.J .
Deformation of isolated single wall carbon nanotubes in
electrospun polymer nanofibres,
Nanotechology, 18 (2007) 235707
Debundling, isolation, and identification of carbon nanotubes in
electrospun nanofibers
Small, 4 (2008) 930933
Electrospinning poly(vinyl alcohol) composite nanofibres
Rate of flow = 0.08-2 ml/hour
Voltage = 15-25 kV
Tip-to-collector distance = 60-120 mm
Conditions:
Polymer poly(vinyl alcohol)
Solvent deionised water
SWNTs - 0.04%
Electrospun poly(vinyl alcohol) composite nanofibres
Dilute solution of PVA containing 0.04% SWNTs spun in a strong electric field
PVA composite nanofibres were produced containing low loadings of SWNTS
Transmission
Electron
Micrograph
Composite nanofibres Scanning Electron Microscopy
Nanofibre bundle
Isolated nanofibre
500 1000 1500 2000 2500 3000
10000
20000
30000
40000
Isolated nanofibre
Nanofibres
Nanotubes


I
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(
a
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u
.
)
Raman Wavenumber (cm
-1
)
(a)
500 1000 1500 2000 2500 3000
4000
6000
8000
10000
(b)
200 225 250 275 300
251


Raman Wavenumber (cm
-1
)
2475 2550 2625 2700 2775


Raman Wavenumber (cm
-1
)


Raman Wavenumber (cm
-1
)
I
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(
a
.
u
.
)
Raman spectra of SWNTs in PVA nanofibres
Nanotubes are debundled and separated by:
- high shear forces
- strong electric field
Raman spectra Isolated nanofibre
HeNe laser
1.96 eV
Experimental Kataura plot Identification of SWNT
200 250 300 350
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6


E
M
11
E
S
22
E
S
11
E
i
i

(
e
V
)

RBM
(cm
-1
)
1.96 eV
HeNe
Laser
Metallic (Raman with tunable laser) Fantini et al, PRL 93 (2004) 147406
Semiconducting (Spectrofluorometric analysis) Bachilo et al, Science 298 (2002) 2361
(10,3)
RBM
HiPco
Nanotubes
Near Infrared Laser 785 nm (1.59 eV)
200 250 300
270
247
234
227
217
204


I
n
t
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n
s
i
t
y

(
a
.
u
.
)
Raman Wavenumber (cm
-1
)
200 250 300


270
239
234
227
270
239
234
227
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Raman Wavenumber (cm
-1
)
Nanotube Debundling and Separation
HiPco bundles Individual Nanofibres
Radial Breathing Modes
Nanofibre Composite Microstructure
Nanotubes aligned along nanofibre axis
Nanotubes debundled and isolated
Low nanotube volume fraction (only 0.04% by weight)
Only nanotubes in resonance are seenin the Raman spectrum
N.B. Not to scale
2 m laser spot
Deformation of SWNTs in PVA nanofibres
0.0 0.1 0.2 0.3 0.4 0.5
1586
1588
1590
1592
G Band

R
a
m
a
n

w
a
v
e
n
u
m
b
e
r

(
c
m
-
1
)
Strain (%)
(a)
0.0 0.1 0.2 0.3 0.4 0.5
2600
2602
2604
2606
2608

R
a
m
a
n

w
a
v
e
n
u
m
b
e
r

(
c
m
-
1
)
Strain (%)
G' Band
(b)
Deform individual nanofibres in tension
Shifts of G and G bands demonstrates stress transfer to nanotubes
Youngs
Modulus
> 0.8 TPa
Composite Reinforcement by Nanotubes
Summary
Large shifts of the nanotube G band are found under stress
This indicates reinforcement by the nanotubes
Larger band shift are found for the SWNTs than MWNTs
This implies better reinforcement by SWNTs
How efficient is the stress transfer between the layers in MWNTs?
Double walled carbon nanotubes
(DWNTs) may have the answer!
SWNT
Nanotube-polymer interface
Wall-wall interface
DWNT MWNT
Raman spectra of the SWNTs give us the polymer-outer wall interface
We have seen that this interface is effective.
MWNTs the contribution from all the layers is not distinguishable.
DWNTs Advanced Materials, 21 (2009) 3591
Single, Double and Multi-walled Nanotubes
Preparation of Double Walled Carbon Nanotubes
SWNTs
Peapods
DWNTs
500C
1300C
C
60
Formation of Peapods
High resolution TEM
(GAD Briggs et al, Oxford)
Raman Spectrum of Original SWNTs
2500 2600 2700 2800
2630
I
n
t
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s
i
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y

(
a
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u
.
)
Raman shift (cm
-1
)
G'
SWNTs
100 200 300 400
146
160
164
178
189
I
n
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i
t
y

(
a
.
u
.
)
Raman shift (cm
-1
)
SWNTs
RBMs
G Band
Well-defined Raman spectrum 1.96 eV laser
Population of different SWNTs > 1.3 nm in diameter
100 200 300 400
152
166
175
190
196
256
282
288
302
323
345
338
356
366
I
n
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n
s
i
t
y

(
a
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u
.
)
Raman shift (cm
-1
)
DWNTs
2500 2600 2700 2800
G'
1
DWNTs
2592
2630
I
n
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s
i
t
y

(
a
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u
.
)
Raman shift (cm
-1
)
G'
2
DWNT Raman Spectrum
RBMs
G Band
Additional RBMs
2
nd
G band
The presence of the inner walls has a major effect on the spectrum
Dresselhaus: Double resonance process is occurring independently in each layer
N.B. Wide split due to larger difference in diameters
SWNT G Band Shift in Tension and Compression
-1.0 -0.5 0.0 0.5 1.0
-8
-6
-4
-2
0
2
4
6
Tension
Compression

G
'

(
c
m
-
1
)
Strain (%)
Slope: -10.5 cm
-1
/%
Peapods
-1.0 -0.5 0.0 0.5 1.0
-6
-4
-2
0
2
4
6 Tension
Compression

G
'

(
c
m
-
1
)
Strain (%)
Slope: -12.7 cm
-1
/%
SWNTs
Large band shifts at low strain, -0.5% to +0.5% (E
effective
for SWNT ~ 760 GPa)
Band shift stops when interface fails
SWNTs Peapods
Interface!
Shifts of the G Band Components in DWNTs
-1.0 -0.5 0.0 0.5 1.0
-6
-4
-2
0
2
4
6
Tension
Compression

G
'
1

(
c
m
-
1
)
Strain (%)
Slope: -1.1 cm
-1
/%
DWNTs
-1.0 -0.5 0.0 0.5 1.0
-6
-4
-2
0
2
4
6
Tension
Compression

G
'
2

(
c
m
-
1
)
Strain (%)
Slope: -9.2 cm
-1
/%
DWNTs
G
1
G
2
Inner walls Outer walls
Only the G band from the outer wall shifts
Poor stress transfer between inner and outer walls
Prediction of Effective MWNT modulus, E
eff

+
=
T
g
T
A
A
k
E
A A
A
E
1
0
1
eff
1 1
) (
k Stress transfer efficiency factor
E
g
-Youngs modulus of graphene
A
1
- cross-sectional area of the outermost shell,
A
T
- total area of the MWNT excluding the annulus and
A
0
- area of the annulus along the centre of the nanotube
L. Zalamea, H. Kim, R.B. Pipes, Comp. Sci. and Tech., 2007, 67, 3425-3433
Shear stress transfer
between the walls
Prediction of Effective Modulus of MWNTs
1 2 3 4 5 6 7 8 9 10
0.0
0.2
0.4
0.6
0.8
1.0
k=0.4
k=0.2
k=0.8
k=0.6

E
e
f
f
/
E
g
Number of Walls, n
k=0.0
k=1.0
n = 1,2,3,..,
E
g
Graphene
Modulus
~1 TPa
Stress
transfer
efficiency
DWNTs
Need either small diameter of nanotubes or to cross-link their walls (Peng et al.)
Graphene
Strong resonance Raman spectrum
Collaborators:
Kostya Novoselov
Andre Geim
Ian Kinloch
Lei Gong (PhD student)
Single layer identified
in Manchester
(Novoselov, Geim et al, Science 2004*)
* >2000 citations to date!
Young modulus ~ 1000 GPa
Graphene Composites
Graphene: E = 1 TPa,
f
= 150 GPa
1. Is there good reinforcement from an one atom thick filler when
all atoms in contact with matrix?
2. Does continuum mechanics apply to a one atom thick crystal?
Mechanically-exfoliated Graphene
1500 2000 2500 3000
0
10000
20000
30000
40000
50000

>5 Layers
3 Layers
1 Layer
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(
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)
Raman Wavenumber (cm
-1
)
Mechanically-Cleaved
Graphene
2 Layers
G'
G
Optical micrograph
Raman spectra
Raman spectroscopy allows the number of layers to be counted
Deformation of a Graphene Monolayer
Optical micrograph
Raman G Band Shift
Single layer on the surface
of a PMMA beam
2500 2550 2600 2650 2700 2750
I
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i
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y

(
a
.
u
.
)
Raman wavenumber (cm
-1
)
Relaxed
Unloaded
0.7% strain
G' Band
Deformation of a Graphene Monolayer Composite
-0.1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
2610
2615
2620
2625
2630
2635
2640
2645
2650

Loading
Unloading
R
a
m
a
n

w
a
v
e
n
u
m
b
e
r

(
c
m
-
1
)
Strain (%)
stick/slip
High shift rate
implies a high
Youngs modulus
for graphene
I TPa
Mapping of Axial Strain across the Graphene Monolayer
0 2 4 6 8 10 12
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.4%
S
t
r
a
i
n

(
%
)
Position, x (m)
ns = 10
x
y

=
) cosh(
2
cosh
1
m
ns
l
x
ns
e e
g
Strain in
graphene
where
) / ln(
2
m
t T E
G
n
g
=
Elastic stress transfer
Mapping of Axial Strain down the Graphene Monolayer

=
) cosh(
2
cosh
1
m
ns
l
x
ns
e e
g
Strain in
graphene
where
) / ln(
2
m
t T E
G
n
g
=
Elastic stress transfer
0 5 10 15 20 25 30
0.0
0.1
0.2
0.3
0.4
0.5
0.6
S
t
r
a
i
n

(
%
)
Position, y (m)
x
y
Line calculated for ns = 10 at 0.4% strain
Mapping of Axial Strain across the Graphene Monolayer
0 2 4 6 8 10 12
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.6%
S
t
r
a
i
n

(
%
)
Position, x (m)
x
y
g
g
tE x
e
i
4
d
d

=
Interfacial failure at high strain
Interfacial shear stress,
i
, given by

i
1 MPa
How long does the graphene flake need to be?
0 2 4 6 8 10 12
0.0
0.1
0.2
0.3
0.4
0.5
0.6
S
t
r
a
i
n

(
%
)
Position, x (m)
0.4%
ns = 20
90 % of
max strain
0.5 l
c
= 1.6 m
l
c
~ 3 m
10 l
c
=30 m
Hence ideally need > 30 micron wide flakes
Solvent exfoliation (e.g. Coleman et al) make flakes only microns in size
Need to make larger flakes or functionalise
Interfacial Shear Stress
0 2 4 6 8 10 12
-6
-4
-2
0
2
4
6
ns = 10, 20, 50
I
n
t
e
r
f
a
c
i
a
l

S
h
e
a
r

S
t
r
e
s
s

(
M
P
a
)
Position, x (m)
Maximum value of
i
= 2 MPa
For carbon fibre composites, typically 20 to 30 MPa
Interfacial stress transfer will only be taking place through van der Waals
bonding across an atomically smooth surface hence not unsurprising it is low
) 2 / cosh(
sinh
m f i
ns
l
x
ns
e nE

=
Conclusions
Raman spectroscopy can be used for stress sensing in
nanomaterials
C
60
offers little reinforcement in composites
Carbon nanotubes demonstrate some characteristics similar to
small carbon fibres.
Stress transfer in nanotube composites can be followed from
Raman band shifts.
Spectra can be obtained from isolated nanotubes.
Electrospinning allows debundling and isolation of nanotubes.
Double walled nanotubes have poor internal stress transfer.
Graphene shows Raman features similar to other forms of
carbon and the same phenomena can be studied.