Polymer Nanocomposites and Electrical Conductivity

MAT706
Advanced Structure-Properties
Relationship in Materials
10 Electrical Conductivity in Polymer Nanocomposites
Emiliano Bilotti
e.bilotti@qmul.ac.uk
MAT706
Organiser:
Dr Asa H. Barber
Reader in Materials
Deputy Organiser:
Dr Emiliano Bilotti
Lecturer in Materials
Contact: e.bilotti@qmul.ac.uk
Room E403, Engineering Building
Phone: 020-7882-7575
Topics
Topic
Lecturer
Week
Date
Introduction
Asa Barber
24 Sept
Practical
Asa Barber
1 Oct
Practical
Asa Barber
8 Oct
Nanomaterials
Asa Barber
15 Oct
Nanocomposites
Asa Barber
22 Oct
Nanocomposites
Asa Barber
29 Oct
Biological nanomaterials
Asa Barber
12 Nov
Polymer Nanocomposites and

Electrical Conductivity
Emiliano Bilotti
19 Nov
Polymer Nanocomposites
Thermal Properties
Emiliano Bilotti
10
26 Nov
Polymer Nanocomposites and

other Functional Properties
Emiliano Bilotti
11
3 Dec
Revision
Asa /Emiliano
12
10 Dec
Variable Resistor
Ammeter
Battery
V=IR=[V]
R=V/I=[]
A
Voltmeter
e-=1.610-19 C
=RA/L=[m]
=1/=[Sm-1]
Relative Energy
Empty Band
Empty Band
Ef
Band gap
Empty stated
Empty
Conduction
Band
Band gap
Filled Band
Filled stated
Metal
Metal
Metallic bond
Empty
Conduction
Band
Band gap
Filled
Valence
Band
Filled
Valence
Band
Insulator
Semi-Conductor
Covalent or ionic bond
Conductivity, [Sm-1]
109
106
Au Cu
Al
Carbon
CNT
Metals
103
100
Semiconductors
10-3
Si
10-6
10-9
10-12
Polymers
Nylon
Graphene
Discovery of graphene.
Nobel Price for Physics 2010

to Prof. Andre Geim (Manchester Uni)
Conductivity of the crystalline graphite, ~107 S/m
Carbon Nanotubes
How to roll a graphene sheet into a CNT
armchair
zig.-zag
ECNT=1TPa
CNT=100 GPa
Chirality defined by n and m: (n,m)
When n-m is a multiple of 3, the tube

is metallic, otherwise, the tube is a
semiconductor.
Electrical Conductive Polymer/(nano)Composites

How to provide electrical conductivity to a (electrical insulating) polymer?
By addition of electrical conductive particles -> Polymer composites
How many particles we need to add to the polymer?
Electrical Conductive Polymer/(nano)Composites

Conductive fillers: different carbon fillers
Note the sudden increase of conductivity in correspondence of

a critical concentration, called percolation threshold
Importance of aspect ratio of conductive particle!
The percolation threshold for CNTs is typically well below 1 wt%!
Rule of Mixture Vs Percolation

Phenomena
Composite Youngs Modulus
Ec (GPa)
Mechanical Properties
Electrical Conductivity Properties
PP/MWNT
~600
~1
0
Filler vol. %
Rule of Mixture
100
Percolation Phenomena
Please note:
The scale of variation of the physical Properties
The shape of the curve (Linear Vs Exponential)
The amount of filler needed to reach maximum
Percolation Intuitive Concept
Percolation of Conductive Particles

Formation of nanofiller-based network
via particle-particle interactions
Courtesy of Prof. G.-F. Gerard, INSA, Lyon
Double Percolation
A
Phase A
Phase B
CNT
Single Percolation
B
Double Percolation
Percolation Theory
PP / MWNT
0 is a scaling factor
pc: Percolation threshold
t: characteristic exponent
It depends only on the dimensionality
of the system
t 2 for 3D system
t 1.3 for 2D system
pc is inversely proportional
to particle aspect ratio, ar!
Thats why conductive nanoparticles

like CNT are so interesting as fillers!
Percolation Theory
Are the values of pc and max fixed for a given system?
NO!
-1
Conductivity [S m ]
10
0.1
max
0.01
1E-3
Polymer/CNT
4
1E-4
10
Yu et al. NanoLetter 2008
1E-5
10
pc
CNT Vol.% [-]
10
-1]
High Viscosity
10
max [Sm
Low viscosity
10
1E-6
10
-1
10
Sandler et al. Polymer 2003

-2
10
Why?
-3
10
-4
10
-5
Thakre et al. JAPS 2010
10
1E-3
0.01
0.1
10
Percolation Threshold, pc [wt.%]
Dynamic Percolation
-1
(S m )
Compression Moulded Films Vs Compounded Pellets

10
10
10
-1
10
-2
10
-3
10
-4
10
-5
10
-6
10
-7
10
-8
10
-9
10
Hot-pressed composite film

o
Composite Strand @ 210 C
o
Composite Strand @ 190 C
Matrix: TPU
Estane, Lubrizol (USA)
Filler: MWNT
NC7000, Nanocyl (Belgium)
!
Non-equilibrium system!
-10
0.00
0.01
0.02
0.03
0.04
0.05
Dynamic Percolation
CNT weight Fraction
R.Zhang, et al., Comp. Sci. Techn. 2009.
Dynamic Percolation
The principal way to study the dynamic (or kinetic) percolation is via time-dependent tests
T scan tests
Isothermal tests
o
10
10
172 C
o
180 C
o
190 C
(a)
CNT weight fraction
10
-1
10
-4
10
-6
10
5% CNT
3% CNT
2% CNT
1% CNT
-8
10
-10
10
200
-2
10
-3
10
-1
(S m )
-1
(S m )
10
T ( C)
-2
150
o
100
172 C
o
180 C
o
190 C
50
-4
10
10
50
100
150
o
T ( C)
200
t (10 ms)
-5
10
-12
2
6
250
8
6
t (ms 10 )
What is the reason for this increase?...

E. Bilotti, et al. J. Mater. Chem., 2010
Dynamic Percolation
CNT re-aggregation!
Poor dispersion
Poor mechanical
properties and electrical
conductivity
Perfect dispersion Not percolated
Good mechanical
properties
Poor electrical conductivity
Optimal dispersion Percolated
Good electrical conductivity
The classic statistic Percolation Theory assumes random dispersion of conductive

particles in an insulating matrix
In reality the dispersion of nanoparticles, like CNT, is non-ideal and it can vary in time
if sufficient energy is given to the system
CNT re-aggregation - Dynamic Process:
Importance of viscosity of the host polymer!
Controlling Dynamic Percolation

How to make use of the CNT re-aggregation to get larger electrical conductivity
in real manufacturing processes?
Example: Melt spinning of TPU / MWNT monofilaments
0
10
3% CNT
(S/m)
-1
Conductivity [S m ]
10
5 wt.% CNT
3 wt.% CNT
(diluted from 5 wt. MB)
0.1
-1
10
220 C
-2
10
-3
10
-4
10
-5
0.01
10
200
210
220
230
T ( C)
240
Chill Roll speed [m min ]
Conductivity increases
with the die temperature
Conductivity decreases
with the chill roll speed
6
-1
die

Example: Melt spinning of TPU / MWNT monofilaments
10
2
o
240 C
10
220 C
(S/m)
10
-2
10
-4
10
-6
10
-8
200 C
o
260 C
10
-10
10
-12
CNT composite film

Composite Strand @ 210
Composite Strand @ 190
Melt spun fibre @ various T
CNT weight Fraction ( wt.%)

By fine-tuning the processing conditions it is possible to control the dynamic percolation
process of CNT within a thermoplastic polymer and optimise the electrical conductivity

CNT re-aggregation
Hypothesis: It is an energy activated process -> regulated by an Arrhenius-type law
10
n0 (Pa s)
10
n0 (Pa s)
172 C
10
10
2.10
2.15
-1
2.20
-1
2.25
T (K 10 )
10
0 c exp(
182 C
o
E
)
RT
E = 249 kJ mol-1
190 C
10
The energy barrier for CNT re-aggregation

is supposed to be the same as the one
relative to the pure polymer viscosity
200 C
-1
10
10
10
10
-1
ang. Freq. (rad s )
In analogy with the time-temperature superposition principle it is

possible to impose a conductivity-time superposition principle.

Assumption:
Conductive network formation is (or is limited by) a first order
thermally activated phenomenon.
2
10
10
-1
(S m )
and by substituting eqn (1):

-2
10
172 C
o
180 C
o
190 C
T scan
-4
10
-6
In analogy with the time-temperature superposition:
10
10
10
10
t' (ms)
where tT is the time required for a certain change in

conductivity, to take place at a temperature T, and tT*
is the time needed for the same change to take place at a
different temperature
10
10

First Predictive Model for Conductivity of Polymer / CNT melt-spun filaments!
1
10
-1
(S m )
10
-1
10
-2
10
-3
10
3 wt.%
2 wt.%
-4
10
200
220
240
260
T ( C)
Strain Sensors
TPU / MWNT
Assumption:
Tunneling
0(1 )
Carbon nanotubes
Surrounding
polymer
Tunnelling distance
R. Zhang, et al. Phys. Rev. B., 2007
Strain Sensors
Dynamic Strain Sensitivity of TPU/CNT filaments and derived fabrics
2.4
R0=53M
2.2
2.0
R/R0
1.8
1.6
1.4
1.2
1.0
Strain (%)
TPU+3%CNT
0.8
10
8
6
4
2
0
0
50000
100000
150000
time (ms)
200000
250000
300000
Strain Sensors
Electrically Conductive Tapes with High

Strength, High Modulus
Annealing
Drawing
Deng, Skipa, Bilotti et al. Adv. Funct. Mat. 2010
Self-regulating Heating Compounds

Overcurrent heating device
ON
OFF
Conductive path
Trace Heating Cable
30
filler

HDPE/ Carbon Nanotubes (CNT)
9
10
0
10
NT
C
-1
resistiviy (log cm)
10
-2
Conductivity (S/cm)
10
-3
10
-4
10
-5
10
PTC
8
10
-6
10
-7
10
-8
10
0.5
1.0
1.5
2.0
2.5
Filler Concentration (% V)
CNT
31
ECNT=1TPa
CNT=100 GPa
3.0
20
40
60
80
100
120
o
Temperature ( C)
140
160
180

Model Conductive Fillers

Effect of filler size on PTC
8
10
10
10
-1
10
Conductivity (S/cm)
10
-3
10
-4
10
-5
10
Flake size
-6
10
-7
10
-8
10
PTC Intensity
5 microns
20 microns
100 microns
-2
100 microns
20 microns
5 microns
5
4
3
2
-9
10
-10
10
-11
10
-12
10
12
16
20
24
4.0
4.5
5.0
6.0
6.5
7.0
7.5
Ag coated glass (% V)
Filler Content (% V)
Vs
5.5
Vs
8.0
8.5
9.0
9.5

Hybrid Filler System: CNT + Conductive spheres
9
2.8
8.37% V Ag coated glass spheres

10
10
2.4
10
2.0
PTC Intensity
Resistivity (cm)

10
10
1.6
1.2
10
0.8
3
10
0.4
10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.15
0.20
0.25
0.30
0.35
0.40
0.45
MWNT content (% V)
MWNT content (% V)
0.50
0.55
0.60

Polymer blend: HDPE/Plastomer
a
Plastomer
HDPE
conductive
flakes
CNT in Biodegradable polymer

Conductive + Degradation Sensing
car?
36

(a)
Biopolymer: PLA
PLA+5%CNT
Voltmeter
Hot plate
37
At selected immersion
periods,
specimens
were removed from the
vials,
dried
until
constant weight.
Pico-ameter
Sample
Computer
- +
V-source
M. Fang et al. Polymer 2013

In Water at 50 C
Typically resistivity decreases upon degradation in both media.

The composite with a CNT loading around the percolation threshold gives the highest
sensitivity and strongest signal change.
38
M. Fang et al. Polymer 2013
Graphene
Opportunities and Challenges
Graphene
WoK Search: Graphene + composite*
WoK Search: CNT + composite*
Graphene
Folding, scrolling, etc.
Kalaitzidou et al., Compos Part A, (2007).
Even on solid substrates
On Mica
On PVA
On PMMA
End.

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MAT706

10 Electrical Conductivity in Polymer Nanocomposites

Polymer Nanocomposites and

Polymer Nanocomposites and

Covalent or ionic bond

Nobel Price for Physics 2010

Conductivity of the crystalline graphite, ~107 S/m

Chirality defined by n and m: (n,m)

When n-m is a multiple of 3, the tube

Electrical Conductive Polymer/(nano)Composites

How many particles we need to add to the polymer?

Electrical Conductive Polymer/(nano)Composites

Note the sudden increase of conductivity in correspondence of

The percolation threshold for CNTs is typically well below 1 wt%!

Rule of Mixture Vs Percolation

Electrical Conductivity Properties

Percolation Intuitive Concept

Percolation of Conductive Particles

Courtesy of Prof. G.-F. Gerard, INSA, Lyon

Thats why conductive nanoparticles

Yu et al. NanoLetter 2008

CNT Vol.% [-]

Sandler et al. Polymer 2003

Thakre et al. JAPS 2010

Percolation Threshold, pc [wt.%]

Compression Moulded Films Vs Compounded Pellets

Hot-pressed composite film

CNT weight Fraction

R.Zhang, et al., Comp. Sci. Techn. 2009.

CNT weight fraction

What is the reason for this increase?...

Perfect dispersion Not percolated

Optimal dispersion Percolated

Good electrical conductivity

The classic statistic Percolation Theory assumes random dispersion of conductive

Controlling Dynamic Percolation

Chill Roll speed [m min ]

Controlling Dynamic Percolation

CNT composite film

CNT weight Fraction ( wt.%)

Controlling Dynamic Percolation

The energy barrier for CNT re-aggregation

ang. Freq. (rad s )

In analogy with the time-temperature superposition principle it is

E. Bilotti, et al. J. Mater. Chem., 2010

Controlling Dynamic Percolation

and by substituting eqn (1):

In analogy with the time-temperature superposition:

where tT is the time required for a certain change in

Controlling Dynamic Percolation

R. Zhang, et al. Phys. Rev. B., 2007

Electrically Conductive Tapes with High

Deng, Skipa, Bilotti et al. Adv. Funct. Mat. 2010

Self-regulating Heating Compounds

Trace Heating Cable

Self-regulating Heating Compounds

resistiviy (log cm)

Self-regulating Heating Compounds

Self-regulating Heating Compounds

Self-regulating Heating Compounds

8.37% V Ag coated glass spheres

8.37% V Ag coated glass spheres

Self-regulating Heating Compounds