STUDIES ON SOME PHYSICAL

PROPERTIES OF HIGH Q-
POLYMER
COMPOSITES BLENDED WITH
CONDUCTIVE NANO PARTICLES
GOUTAM GHOSH

UNIVERSITY OF CALCUTTA

1
 Introduction
 adhesives and lubricants
 structural components
for products ranging
from children's toys to
aircraft
 biomedical applications
ranging from
implantable devices to
controlled drug delivery
 photo resist materials
used in semiconductor
manufacturing
 low-k dielectrics for use
in high-performance
microprocessors
 flexible substrates in the
development of
organic light-emitting diodes
 EMI can be reduced
SCENE
  Biological tissues for
cancer research,
 Building materials
Physical  negative index materials
Properties  electromagnetic
shielding
Conducting  propagation of wireless
Polymer
signals.
TIPP
Simple technique to 
measure dielectric and 
conducting properties of 
these conducting polymers 
and their blends. 2
 Introduction
SCENE

Measurement

  Permittivity
Physical  Conductivity
Properties  EMI shielding
Physical
 Electromagnetic
Properties shielding
 X-Ray diffraction
Conducting analysis
Polymer  UV-Visible spectroscopy

a) Intrinsically / inherently conducting

polymers (ICPs)
b)Conducting polymer composites, and
c)Ionically conducting polymers. 3
 INTRINSICALLY CONDUCTING
POLYMERS (ICPs)

possesses the 
mechanical 
electrical,electronic, 
properties, 
magnetic and 
processibility synthetic metal
optical properties 

Bakelite, 
Perspex, Teflon 
and silicone

…
4
…
  Usually prepared by the addition of
conducting fillers in the insulating
polymer matrix

CONDUCTING POLYMER 
COMPOSITES

 Conductive filler commonly used are

metal flakes, graphite, conductive
carbon black, etc.
 Loaded in the common insulating
polymers like PP, PVC, LDPE,EPDM,
EVA

5
 SCENE

Polymer blends are the mixture 
of two or more polymers or 
copolymers.

1 Miscible blends

2 Immiscible blends

3 Compatible blends

4 Polymer alloys

6
 CHARGE TRANSPORT
SCENE

morphology that consists of an

insulating matrix and conductive
filler.
changes from an insulator to a
conductor over a very narrow
range of filler concentration.
conversion of a blend / composite
from an insulator to conducting is
known as percolation
phenomenon.
Three situations are possible: (1)
No contact between the
conductive particles, (2) Close to
proximity, and (3) Physical
7
contact
 IDEA
In highly loaded
 Quantum mechanical tunneling has
composites actual contact SCENE
been used to explain the conduction
between particles does occur through the insulating materials.
and such composites have
 Thermal expansion of the polymers
shown a linear current-
has been used to explain the
voltage characteristic importance of critical volume fraction
in such materials
No contact between the conductive particles
• particles are isolated, the conductivity of the blend / composite
• is only slightly changed.
• remain an insulator although its dielectric properties may change
significantly.

Close to proximity
• electron can jump the gap between the particles, creating current
flow. .
• The process of electron transfer across an insulator gap is
referred to as ‘hopping or tunneling’
Physical contact
• possible when conductive filler is introduced into an insulating
matrix
• form a continuous network throughout the blend / composite.

8
 FREQUENCY
 equation for the conductivity considering the hopping
DEPENDENT mechanism
CONDUCTIVITY σ(ω) = (π / 96) e2kT [N(EF)]2 r05 ω[ln(1 / (ωτ0))]4 
 can be described by the well-known relation
σ(ω) = σdc + Aωn 
 
8.0
7.5 εr'
7.0

Conductivity in S/m
Dielectric Constant
6.5
6.0
5.5
5.0 Dielectric constant of EVA 40
4.5 Conductivity of EVA 40
4.0
3.5
3.0
2.5
2.0
1.5 σ
1.0
0.5
0.0
8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0

Frequency in GHz

9
SCOPE OF THE WORK SCENE

1 Emphasis on metrology
2 Introduce relevant electromagnetic qua
3 Suite of measurements and methods
4 Develop relevant equations from first
5 principles in the measurement processe
Uncertainties
6 Accurate determination of Physical Properti

10
 SCENE

Division 1 Division 2
Dielectric Properties Conductivity
Measurement

Physic
al
properties

Division 3
EMI Shielding
Measurement

11
 SCENE

Division 1 Division 2
Dielectric Properties Conductivity
Measurement

Physic
al
properties

Division 3
EMI Shielding
Measurement

12
 HIGH FREQUENCY MEASUREMENT SCENE

Methods
DIELECTRIC  Resonant or non-resonant method is available
MEASUREME
NT

13
 Comparison SCENE

dvantages and disadvantages of Resonant Methods

Pro Cons

 Better accuracy  Not broadband

 Simple in nature  Limitted to high Q-materials
Conclusion

We have used the resonant method

14
 HIGH FREQUENCY MEASUREMENT SCENE

RECTANGULAR SHAPE
 at microwave frequency the measurements depends on the
shape of the sample as well as the position of the sample.

 rectangular sample of length, breadth and thickness W, B and d respectively is

placed inside a rectangular cavity having corresponding dimensions c, b and a,

15
 Theory SCENE

from energy conservation principles If WE = total energy

of the empty cavity, WS = energy contained by the sample
and WC = energy contained in the region of the cavity
outside that of the sample.
WE = WS + WC
1  2 a
2
2  Bac
WE = ε0 4 A µ0
2
ω0  ( 2 ⋅ 2)
2  π2  4
1  2 a
2
2  WBπ d
2 3
= (εS −ε0 ) 4 A µ0 ω  ( 2.3)
2
WS
2  π 2
 3a 2
1  2 a
2
2  bac
WC = ε0 4 A µ0
2
ω  ( 2.4 )
2  π2  4

permittivitv of the sample

ω0 2  3a 3 bc 
ε r
=  2 −1

ω  4π 2WBd 3  +1

  

16
 EXPERIMENTAL RESULTS SCENE

Rectangular samples of Perspex and Teflon having W

=5.6mm. , B = 10mm and of different thickness
increasing from 2.5mm to 6.0mm in steps of 0.5mm were
inserted in the cavity and the resulting change in the
resonant frequency was observed
8.51 GHz for perspex
6 9.46 GHz for perspex
10.46 GHz for perspex
8.51 GHz for teflon
5 9.46 GHz for teflon
10.46 GHz for teflon
Dielectric Constant

0
2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5
Thickness of the sample in mm

17
 EXPERIMENTAL RESULTS SCENE

Three rectangular X-band cavities having lengths

27.5mm, 21.8mm and 18.3mm to resonate respectively at
8.51, 9.46 and 10.47 GHz were used for the measurement
of dielectric constant

18
 EXPERIMENTAL RESULTS SCENE
Measured dielectric constants for perspex at 8.51 GHz
Sample thickness in FREQUENCY
εr
cavity in mm (GHZ)
2.5 8.489 2.59
3 8.452 3.41
3.5 8.402 3.81
4 8.355 3.71
4.5 8.283 3.81
5 8.214 3.70
5.5 8.122 3.70
6 8.007 3.75

Dielectric constants for teflon at 9.46 GHz

Sample thickness
Ω (GHZ) εr
in cavity in mm
2.5 9.470 1.39
3 9.465 1.37
3.5 9.439 1.70
4 9.408 1.85
4.5 9.348 2.12
5 9.310 2.06
5.5 9.249 2.09
6 9.182 2.10

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 HIGH FREQUENCY MEASUREMENT SCENE

CYLINDRICAL SHAPE
DIELECTRIC
MEASUREME
NT  cylindrical sample of diameter d and height h is placed inside
a rectangular cavity excited in the TE101 mode having
dimensions c, b and a,

20
 Theory SCENE

from energy conservation principles If WE = total energy

of the empty cavity, WS = energy contained by the sample
and WC = energy contained in the region of the cavity
outside that of the sample.
WE = WS + WC
1  2 a2 2  Bac
W = ε0 4 A µ 2
ω ( A ⋅1)
E
2  π2 0 0   4
 2 a2 2  2π h d
7 3 4
1
= (εS −ε0 ) 4 A µ0 ω  ( A.2)
2
W S
2  π 2 2 2
 9a c
1  2 a2  bac
W = ε0 4 A µ0 2ω2  ( A.3)
C
2  π 2
 4

permittivitv of the sample

 ω0 2  36a 3 bc 3 
ε r
=  2 −1 7 4 3  + 1

ω π d h

  

21
 EXPERIMENTAL RESULTS SCENE

Measured Dielectric Constant Of Cylindrical And

Rectangular Samples Of Perspex At 8.51 GHz
Sample ΕR εr
thickness in cavity in (CYLINDRICAL) (Rectangular)
mm

3 3.36 3.41
4 4.13 3.71
5 3.89 3.70
6 3.69 3.70
7 3.6 3.65
8 3.55 3.60

8.5 GHZ teflon sample

6 8.5 GHZ perspex sample
6 9.46 GHz teflon sample
9.46 GHZ perspex sample
5

5
Dielectric Constant

0
2 3 4 5 6 7 8
Height of the Cylindrical Sample in mm

22
 SCENE
HIGH FREQUENCY MEASUREMENT

Rectangular Shape
CONDUCTIVIT  The change of complex angular frequency of a resonant
Y
MEASUREMEN
cavity due to the introduction of a sample is.
T ∗ ∗
∫∫∫ ∆ ε E1 ⋅ E 2 dv + ∆ µ H 1 ⋅ H 2 dv
ω 2 − ω1 v
≈− s ..1
ω2 ∗ ∗
∫∫∫ ε 1 E1 ⋅ E 2 dv + µ 1 H 1 ⋅ H 2 dv
vc

 If a rectangular sample is placed inside a

rectangular cavityfor TE011 mode
a  πz   πx 
E1 = 2 A  ωµ 0 ⋅ sin   sin   e jωt
π  a c
2  2 a 2 2 2  bac
∫∫∫ 1
E dv =  4 A 2 µ 0 ω0 
vc  π  4
.

23
 Theory SCENE

For thin samples E1=E2
C W
+
2  2 a 2 2  d 2 πz
2 2 2
2 πx B
∫∫∫ 2
E dv =  4 A 2 µ 0 ω 0  ∫ sin dz ∫ sin dx ∫ dy .. 8a
vs  π  0 a C W c 0
−
2 2

 2 a 2 2 2  WBπ 2d 3
= 4 A 2 µ0ω0  ⋅ 2
..8b
 π  3a

Conductivity can be calculated as

 f 13 − f 12 f 2 3a 3 bc 
ε =
'
r ⋅ 3 
+1 ..9
 f 2
3
2WB π 2
d 
Q1 −Q2 ω02 3a 3 bc
σ= ⋅ ε ⋅ ..10
Q1Q2 ω 0 4WBπ2 d 3

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EXPERIMENTAL RESULTS SCENE

25
 EXPERIMENTAL RESULTS SCENE

maximum error increaseswith

increasing conductivity of the materials
and was found to be 64% for
Bakelite and 95% for EVA.25V.

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 HIGH FREQUENCY MEASUREMENT SCENE

CYLINDRICAL SHAPE
 If a cylindrical sample is placed inside a rectangular cavityfor TE101
mode
 2 a 2 2 2  d 2 π z 2π 2 πρφ r

∫∫∫v E2 dv =  4 A π 2 µ 0 ω 0  ∫0 sin a dz ∫0 sin c ρ dφ ∫ dρ

2
(6)
s 0

 2 a 2 2 2  2π 7 d 3r 4
=  4 A 2 µ 0ω  ⋅ (7)
 π  9a c
2 2

 Real and Imaginary part of the permittivity, tangent Loss and Conductivity can be
calculated form
 f13 − f12 f 2 9a 3bc 3  σ = ε r'' ⋅ 2π f1.ε 0 (11)
εr =
'
⋅  +1 (8)
 f 23 4π 7 d 3 r 4  Therefore,
Q1 − Q2 f12 9a 3bc 3 Q1 − Q2 f12 9a 3bc 3
ε r'' = ⋅ 2 ⋅ (9)
Q1Q2 f 2 8π 7 d 3 r 4 σ= ⋅ ε0 ⋅ 6 3 4 (12)
Q1Q2 f 2 4π d r
ε r''
and tan δ = (10)
ε r'

27
EXPERIMENTAL RESULTS SCENE

28
 EXPERIMENTAL RESULTS SCENE

The maximum error increases with increasing

conductivity of the materials. And was found
to be 34% for 2% carbon and 65% for 3% carbon.

29
 EXPERIMENTAL RESULTS
Field pattern inside the cavity SCENE

 
0.225 0.225

0.200 8.5 GHz 0.200

9.5 GHz
0.175 0.175
COMPLEX PERMITTIVITY 

10.5 GHz
0.150 ε
r
0.150

  LOSS TANGENT
0.125 0.125

0.100 0.100

0.075 0.075
0.018 0.018
0.016 0.016
0.014 0.014
0.012 tanδ 0.012
0.010 0.010
0.008 0.008
0.006 0.006
0.004 0.004
0.002 0.002
0.000 0.000
2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5
SAMPLE THICKNESS IN MM

Variation of measured complex permittivity and tangent loss of silicon as a

function of sample thickness at frequencies 8.49 GHz, 9.55 GHz, 10.47 GHz.
30
 SCENE
LOW FREQUENCY MEASUREMENT

Rectangular Shape
CONDUCTIVIT  conductivity measurements were carried out by a two-probe
Y
MEASUREMEN
technique recorded by a Kiethley electrometer model - 614.
T

31
 EXPERIMENTAL RESULTS SCENE

Variation of frequency can be achieved using APLAB

4910 LCR Meter

 sigma1.2V
 sigma.1v
CONDUCTIVITY

0.1

0 1 2 3 4 5 6 7
10 10 10 10 10 10 10 10
FREQUENCY

Variation of conductivity with frequency from 13 Hz to 1MHz for 3% carbon-

wax system

32
 SCENE
EMI SHEILDING
MEASUREMENT
 Set-Up
S

 Measurement

33
 Three subject areas

 original medium in the cavity is no-loss;

 sample is homogeneous and is much smaller than 
the cavity

 electromagnetic field ouside the sample does not 
change.

34
 Magnetic
Cavity wall is 1 starrer are
perfectly 2 used to
conducting achieve
3 homogeneous
4 sample

High-Q
Polymers
are used in
the work

35
 Photo Icons with motives SCENE

Cavity

Complete Set- Network

up
Analyser

Microwave
Source 36
 Conclusion
SCENE

σ = σoωn  depends on n, hence 
 changing considerably with 
composition. 
suggested the charge transport
 was dominated by the inter-
domain hopping process and the 
charges become increasingly 
In the high frequency 
delocalized with increase of do-
regime, the 
pant content.
conductivity became 
high for all the cases 
suggesting the 
effectiveness of these 
blends for the 
application as EMI 
shielding material

37
prasun.jis@gmail.com  38
 … these methods can be utilised
determine their properties accurat
For different applications such as
anti-static layers, EMI shielding material,
transparent flexible conductive films and
coatings, etc., these blends serve
as very useful materials

prasun.jis@gmail.com  39