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PhysicalandEngineeringPropertiesofPolymers

Lecture Notes
(SS, 2012)

I Fundamental concepts
1. Conductivity and permittivity
2. Parallel-plate capacitor
I I Polymer in static field
1. Molecular polarization
2. Parallel-plate capacitor with dielectrics
I I I Mechanism of polarization
1. Clausius-Mossotti Equation
2. Langevin function
I V Relaxation phenomena
1. Mechanical relaxation
2. Dielectric relaxation
V Measurement and presentation of dielectric
response
1. Measurement
2. Dielectric relaxation functions
VI Thermodynamical relations
1. Fundamental thermodynamical relations
2. Piezo-, pyro- and ferroelectricity
References:
Electrical Properties of Polymer
T. Blythe and D. Bloor
Cambridge University Press 2008
Dielectric Phenomena in Solids
Kwan Chi Kao
Academic Press, Amsterdam, 2004

PhysicalandEngineeringPropertiesofPolymers

I Fundamental concepts
I -1.1 Conductivity

R
I
s
=
1
o
I
s

R : resistance
p : resistivity
o : conductivity
Good insulator: o 10
-16
(m)
-1
.
I -1.2 Permittivity:
The measure of the resistance that is encountered when forming an electric field in a
medium.
Determined by the ability of a material to polarize in response to the field, and thereby
reduce the total electric field inside the material.
Relates to a material's ability to transmit (or "permit") an electric field.

I -2 Parallel-plate capacitor
I -2.1 Coulombs law
Coulombs law describes the electrostatic
interaction between electrically charged
particles: The magnitude of the Electrostatics
force of interaction between two point charges
is directly proportional to the scalar
multiplication of the magnitudes of charges
and inversely proportional to the square of the
distances between them.

|F
12
| = |F
21
| = k
|q
1
q
2
|
r
12
2

Or as vectors
F
12

= -F
21

= k
q
1
q
2
r
12
3
r
12

k is a constant. In vacuum, k =
1
4ns
0
. e
0
= 8.8510
-12
Fm
-1
, is permittivity of free
PhysicalandEngineeringPropertiesofPolymers
space.
I -2.2 Electric field
An electric field surrounds electrically charged particles and time-varying magnetic
fields. It has mainly the following two properties:
(a) It exerts a force on other electrically charged objects located in the field;
(b) It does work on the charged objects moving along the electric field.

Definition: E

=
P

q

F

: the electric force experienced by the particle


q : its charge
E

: the electric field wherein the particle is located.



Based on Coulomb's Law for interacting point charges, the contribution to the electric
field at a point in space due to a single, discrete charge located at another point in
space is given by the following
E

=
q
4ne
0
r
3
r

Superposition principle
The total electric field due to a quantity of point charges is simply the superposition of
the contribution of each individual point charge
E

= E
1

+E
2

++E
n

=
q

4ne
0
r

3
r
i

n
=1


I -2.3 Gauss law
Gauss law is deduced from Coulombs law in combination with superposition
principle of electric field.
Enclose a point charge +q with a sphere
having a radius of r. According to Coulombs
law, the electric field at any point on the
sphere surface is
E =
q
4ns
0

2
,
pointing out of the surface in the normal
direction. Therefore, the electric flux through
the sphere
1 = _
q
4ne
0
r
2
JS
S

PhysicalandEngineeringPropertiesofPolymers
=
q
4s
0
r
2
} uS =
q
4s
0
r
2
S
4i
2
=
q
s
0

According to the superposition principle of E, above conclusion also holds when a
number of point charges (or a continuous charge distribution) are enclosed inside the
surface.
1 = } E

JS

S
=
q
i
s
0
(=
]dq
s
0
)
Gauss Law: The electric flux through any closed surface is
proportional to the enclosed electric charge.

I -2 Parallel-plate capacitor

Capacitance: C =

v

Unit: 1 F=1
C
v
[Farad]


Homogeneous E: I = E J
Inhomogeneous E

: I = ] E

(x) Jx
d
0

Using Gauss law
QE

JA

=

encl
s
0

Q
encl
: Charge enclosed in the surface

E

JA

= E

JA

iight siue


= E A =

e
0



E =
v
d
=
C
d
- C =

Ld
=
s
0
LA
Ld
=
s
0
A
d

PhysicalandEngineeringPropertiesofPolymers
I I Polymer in static field
I I -1 Molecular polarization
I I -1.1 Molecule dipoles
Dipole moment: p = qs

I I -1.2 Molecular polarization
Polarization: a vector quantity that expresses the magnitude and direction of the
density of permanent or induced electric dipole moments induced in a dielectric
material by the applied field. The SI unit is coulombs per square metre [
C
m
2
].
Macroscopic quantity:
Polarization P = np
n: number density of the dipoles

Microscopically, the applied electric field induces an electric dipole p on each
individual molecule,
p = oE
loc


o : a constant called the polarizability of the molecule.
E
loc

: the local electric field at the molecule.


(a) Electronic polarization (also called Optical polarization)
An electric field will cause a slight displacement of the electron cloud with respect
to the positive nucleus.
Vast fast process: 10
-15
~10
-16
s.

PhysicalandEngineeringPropertiesofPolymers
(b) Atomic or Ionic polarization (Vibrational polarization)
Under electric field, the arrangement of atomic nuclei in a molecule can be
distorted, while in ionic crystals the positive ions shift with respect to the negative
ones.
Slower than electronic polarization: 10
-12
~10
-13
s.

(c) Orientation polarization
Molecules having a permanent dipole tend to align in the direction of the applied field,
giving a net polarization in that direction.
Much slower: 10
-6
~10
-2
s.

Molecular polarizability: o = o
c
+o
u
+o
o

o
c
: electronic polarizability
o
u
: atomic (or ionic) polarizability
o
o
: orentational polarizability


PhysicalandEngineeringPropertiesofPolymers
I I -2 Parallel-plate capacitor with dielectrics
How to calculate E
int
?
Dipole moment: p = qs
Total polarization charge:

P
= Nq = N
p
s

Number of dipoles: N = n A s
So that

P
= n A p
Surface charge density:

P
A
= n p = P
(induced surface density)

Gausss law:
E

JA

=

encl
e
0

-E
ext
A +E
int
A +u =
-
P
e
0
= -
A P
e
0

cIds
-----
E
int
= E
ext
-
P
e
0



Linear approx.: P

= e
0
_E
int


_ : susceptibility tensor. For isotropic media, _ is a scalar.

E
int
= E
ext
+E
P

cIds
----- E
P
= -
P
s
0


E
P
=_E
int

E
int
= E
ext
- _E
int

E
ext
E
int
= 1 +_


QE

JA

= E
int
A =
1
s
0
(
fiee
-P A)

PhysicalandEngineeringPropertiesofPolymers
(e
0
E

+P

) JA

=
fiee

Electric displacement:

= e
0
E

+P

= e
0
E

(1+_)

JA

= e
0
E
int
(1 +_) A =
fiee

fiee
= C I = C E
int
J

cIds
-----
C = e
0
(1+_)
A
d
=e
0
e

A
d


e

= 1 +_
1 denotes the vacuum contribution.

PhysicalandEngineeringPropertiesofPolymers
I I I Mechanism of polarization
I I I -1 Clausius-Mossotti Equation
I I I -1.1 Lorentz local electric field
E
loc

: The field acting on an individual


polarisable entity such as an atom or molecule

Lorentz field:
E
loc

=E
int

+
P

3s
0
+E
N


E
N

: the field due to the molecules inside the


sphere. For cubic lattices, E
N

= 0.
E
loc
= E
int
+
P
3s
0
= E
int
+
s
0
L
int
3s
0
= (1 +

3
)E
int
=
s
r
+2
3
E
int


I I I -1.2 Clausius-Mosotti Equation
Microscopic property: polarizability o.
P = noE
loc


Macroscopic property: Susceptibility _.
P = _e
0
E
int


noE
loc
= _e
0
E
int

cIds
-----
no
e

+ 2
S
E
int
= (e

-1)e
0
E
int

Clausius-Mosotti Equ.:
e

-1
e

+2
=
no
Se
0


Dipole density n =
p
M
W
N
A

p : density; H
W
: molar mass; N
A
: Avogadros number (6.0210
23
).
ModelfortheLorentzlocalfield
PhysicalandEngineeringPropertiesofPolymers
e

-1
e

+2
H
W
p
=
N
A
o
Se
0


(P
N
=
N
A
o
Se
u
: Molar polarization)

Lorenz-Lorentz equation:
If no orientation polarization is present (e.g. at very high frequency), e

= n
2
, where
n is refractive index.
n
2
-1
n
2
+2
H
W
p
=
N
A
o
Se
0


I I I -2 Langevin function: polar molecules
Polarization: P = n p(cos0)
Torque: I

= p E

, |I

| = pEsin0

Potential energy: w = -p E

= -pEcos0
Many dipoles: Average potential energy (w)
Average cosine: (cos0) =
(w)
-L



According to Boltzmann statistics, probability for energy to be between W and
W+dW:

p(w) = c
-wk1
Jw

(w) =
] wp(w)Jw
L
-L
] p(w)Jw
L
-L


(cos0) =
(w)
-pE
= -
1
pE
] wp(w)Jw
L
-L
] p(w)Jw
L
-L


Substitution y =
w
k1
, x =
L
k1
,
cIds
----- w = kIy, Jw = kIJy

Orientationofamoleculardipole
Boltzmanndistribution
PhysicalandEngineeringPropertiesofPolymers
(cos0) = -
1
pE
] kIyc
-
kIJy
x
-x
] c
-
kIJy
x
-x

= -
1
x
|-(1+)c
-j
]
-x
x
|c
-j
]
-x
x

= -
1
x
-(1+x)c
-x
+(1-x)c
x
-c
-x
+c
x

=
c
x
+c
-x
c
x
-c
-x
-
1
x

= cothx -
1
x
= I(x) Langevin function



I(x) =
x
S
-
x
3
4S
+

Typically, p = 1u
-30
Cm , even at very high E = 1u
8
v
m
, pE = 1u
-22
} = 1mev.
kI = 2Smev
So that x =
L
k1
< 1
I(x) =
x
S
P = n p
L
3k1
= n

2
3k1
E

Orientational polarizability:

2
3k1

Langevinfunction
PhysicalandEngineeringPropertiesofPolymers
Total effective polarizability: o
eff
= o
0
+

2
3k1


Substituting into Clausius-Mosotti Equation:
P
M
=
e

-1
e

+2
H
W
p
=
N
A
Se
0
(o
u
+
p
2
SkI
)

























Temperaturedependenceofmolarpolarization
PhysicalandEngineeringPropertiesofPolymers
I V Relaxation phenomena
I V-1 Mechanical relaxation
Stress: o
]
=
P
i
A
]

o = _
o
11
o
12
o
13
o
21
o
22
o
23
o
31
o
32
o
33
_
Strain: =
I
I

Strain tensor:
kI
=
1
2
[
{
l
x
k
-
{
k
x
l

k
: displacement
Linear relationship: o =
: Youngs (elastic) modulus

I V-1.1 Tensile creep compliance
(t) =

33
o
33
0
=
1
(t)


I V-1.2 Stress-relaxation experiment
Time dependent tensile modulus: (t) =
c
33
(t)
:
33
0
(t)

I V-1.3 Dynamic mechanical relaxation experiment
o
33
(t) = o
33
0
c
ot

33
(t) =
SS
u
c
ot

Generally
33
0
=
33
0
c
-q


Complex tensile compliance

() =

SS
(t)
o
SS
(t)
=

33
0
c
-q
c
ot
o
SS
u
c
it
=
i
-i''
Or complex dynamic tensile modulus

() =
o
SS
(t)

SS
(t)
=
1

()
=
i
+i''

33
(t)
33
(t)

Time
,

Dynamicmechanicalrelaxation
PhysicalandEngineeringPropertiesofPolymers
I V-2 Dielectric relaxation
Analogy:
Mechanical stress o Electric field E
Mechanical strain Electric displacement D
(or polarization P)

Static polarization: P
s
= _
(o=0)
e
0
E
Effect of an applied electrical field:
dP
dt
=
P
s
-P(t)
:

: relaxation time
Boltzmann statistics: (I) =
0
exp (
L
c
k1
)
E
u
: activation energy

I V-2.1 Static electric field
Solution for E = _
u (t < u)
E
0
(t u)


P(t) = P
s
(1 -c
-t:
)

P
s
= _
(0)
e
0
E; P

= _
()
e
0
E
P
s
-P

= (_
(0)
-_
()
)e
0
E = (e
s
-e

)e
0
E = ee
0
E
e : relaxation strength.

I V-2.2 Frequency domain response
E = E
0
c
ot
P
s
= _
(0)
e
0
E
0
c
ot

P

(t) = P

0
c
ot
= P
0
c
-q
c
ot

JP
Jt
=
P
s
-P(t)

= iP

u
c
it
=
_
(0)
e
0
E
0
c
ot
-P

u
c
it

0
(1 +i) = _
(u)
e
u
E
u
yiclJs
---P

0
=
_
(u)
e
u
E
u
1 +i

_() =
_
(u)
1 +i

E on
P
s
P
time
Polarization

1
>

PolarizationunderstaticE
PhysicalandEngineeringPropertiesofPolymers
Debye relaxation:
_() =
e
1+o:
+_
()
or e() =
e
1+o:
+e
()


Real part: e'() =
e
1+o
2
:
2
+ e
()

Imaginary part: e''() =
e
1+o
2
:
2

e() = e
i
() -ie
ii
() and tano =
s
||
s
|



e
i
, e
ii
,and tano asafunctionof
(e
s
= 1u, e

= 2, = 1u
-10
s)
PhysicalandEngineeringPropertiesofPolymers
V Measurement and presentation of dielectric
response
V-1. Measurement
Parallel-plate capacitor: C

= ee
0
A
d

Charge on capacitor: (t) = C

I(t)
I(t) = I
0
c
ot

Current: I

(t) =

(t) = C

(t) = I

0
c
ot

= C

iI
0
c
ot
= ee
0
A
d
I
0
c
ot
i
I

0
= (e
i
-ie
ii
)e
0
A
J
iI
0
= (e
ii
+ie')e
0
A
J
I
0


_
I
R
= e
ii
e
0
A
d
I
0
(in phase)
I
C
= e
i
e
0
A
d
I
0
(
n
2
auvanceu)


Loss tangent: tono =
s
||
s
|



(a)Samplecapacitor (b)ComplexIVrelationship
PhysicalandEngineeringPropertiesofPolymers
V-2. Dielectric relaxation functions
Debye dispersion:
Real part: e'() =
e
1+o
2
:
2
+ e
()

Imaginary part: e''() =
e
1+o
2
:
2


Eliminate from both parts, one obtains:
_e
i
-
e
s
+e

2
]
2
+(e
ii
)
2
= [
e
s
-e

2

2


Real dielectric material:
Cole-cole plot: e -e

=
s
s
-s

1+(o:)
1-o

Cole-Davison: e -e

=
s
s
-s

(1+o:)
1-

Havriliak-Negami: e - e

=
s
s
-s

{1+(o:)
1-o
]
1-




PhysicalandEngineeringPropertiesofPolymers
VI Thermodynamical relations
VI -1. Fundamental thermodynamical relations
Intensive variable: can not be added when two objects are combined, such
as temperature T;
Extensive variable: can be added, such as mass.

i, ] = 1, , 6
k, l = 1, ,S
Intensive variable
(force)
Extensive variable
(displacement)
Thermodynamics Temperature T Entropy S
Mechanics Stress o

Strain


Electricity Electric field E
k
Displacement
k

Magnetism Magnetic field E
k
Induction B
k


Free enthalpy (Gibbs Function) G:
0(I, o, E, E) = u -SI -

-
k
E
k
-B
k
E
k

During reversible process Ju = u
Total differential of G for reversible processes:
J0 = -SJI -

Jo

-
k
JE
k
-B
k
JE
k

Or
J0 =
o0
oI
_
c,L,H
JI +
o0
oo

_
1,L,H
Jo

+
o0
oE
k
_
1,c,H
JE
k
+
o0
oE
k
_
1,c,L
JE
k

S = -
u
1

c,L,H
,

=
u
c
i

1,L,H
,

k
=
u
L
k

1,c,H
,
B
k
=
u
H
k

1,c,L
.

VI -2. Piezo-, pyro- and ferroelectricity
In polymers, magnetism can often be neglected: Total differentials of
mechanical strain , of electric displacement D and of entropy S:
PhysicalandEngineeringPropertiesofPolymers
JS =
oS
oI
_
c,L
JI +
oS
oo
]
_
1,L
Jo
]
+
oS
oE
I
_
1,c
JE
I

J
]
=
o
]
oI
_
c,L
JI +
o
]
oo

_
1,L
Jo

+
o
]
oE
I
_
1,c
JE
I

J
I
=
o
I
oI
_
c,L
JI +
o
I
oo
]
_
1,L
Jo
]
+
o
I
oE
k
_
1,c
JE
k

Direct and inverse piezo- and pyroelectricity:
J
]I
=
o
]
oE
I
_
1,c
=
o
I
oo
]
_
1,L

p
k
=
oS
oE
k
_
1,c
=
o
I
oI
_
c,L

Piezoelectric charge coefficient J
3
for the three coordinate axes (i = 1,
2, 3):
J
3
=
o
3
oo

_
L
3
,1

Inverse piezoelectric effect (strain coefficient J
3
)
J
3
=
o

oE
3
_
c
i
,1

Constant electric field E
3
:
J
3
=
oP
3
oo

_
L
3
,1

Experiment: Electrode charge Q
3
as a function of applied force F

:
J
3
i
=
A

A
3
o
3
oF

_
0,1

Taking changes of sample dimensions into account:
J
3
i
=
A

A
3
o(P
3
A
3
)
o(o

)
_
0,1
cIds
-----J
3
i
=
oP
3
oo

_
0,1
+
P
3
A
3
oA
3
oo

_
0,1

PhysicalandEngineeringPropertiesofPolymers
Employing the elastic compliance s
]
L
at constant electric field E:
J
3
i
= J
3
+P
3
(s
1
L
+ s
2
L
) = J
3

Piezoelectrical charge or strain coefficient:
J =

c

L
=
:
L

c
j
C
N
=
m
v
[
Piezoelectrical charge or stress coefficient:
c =

:

L
=
c
L

:
j
C
m
2
=
N
vm
[
Piezoelectrical field or strain coefficient:
g =
L
c

=
:

c
j
vm
N
=
m
2
C
[
Piezoelectrical field or stress coefficient:
b =
L
:

=
c

:
j
v
m
=
N
C
[
Relation between the four coefficients:
d
g
= e|
c
and
c
h
= e|
:
(Dielectric permittivity)
c
d
= c|
L
and
h
g
= c|

(Elastic modulus)
Electro-mechanical coupling factor (energy ratio):
k
2
=
L|
out
c:|
in
=
c:|
out
L|
in
= Jb = cg (dimensionless)