Вы находитесь на странице: 1из 42

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

Electrical Conductivity
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

Electrical Conductivity

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

Electrical Conductivity

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

Controlling Dynamic Percolation


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

Controlling Dynamic Percolation


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.

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

Controlling Dynamic Percolation


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

Controlling Dynamic Percolation


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

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

Self-regulating Heating Compounds


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

Self-regulating Heating Compounds


Model Conductive Fillers

Self-regulating Heating Compounds


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

Self-regulating Heating Compounds


Hybrid Filler System: CNT + Conductive spheres
9

2.8

8.37% V Ag coated glass spheres


10.86% V Ag coated glass spheres
11.91% V Ag coated glass spheres

10

10

2.4

10

2.0

PTC Intensity

Resistivity (cm)

8.37% V Ag coated glass spheres


10.86% V Ag coated glass spheres
11.91% V Ag coated glass spheres

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

Self-regulating Heating Compounds


Polymer blend: HDPE/Plastomer
a

Plastomer

HDPE

conductive
flakes

CNT in Biodegradable polymer


Conductive + Degradation Sensing

car?
36

CNT in Biodegradable polymer


Conductive + Degradation Sensing
(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

CNT in Biodegradable polymer


Conductive + Degradation Sensing
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
Opportunities and Challenges

WoK Search: Graphene + composite*

WoK Search: CNT + composite*

Graphene
Opportunities and Challenges
Folding, scrolling, etc.

Kalaitzidou et al., Compos Part A, (2007).

Even on solid substrates

On Mica

On PVA

On PMMA

End.