DIELECTRIC SPECTROSCOPY

& Comparison With Other Techniques

DIELECTRIC SPECTROSCOPY
measures the dielectric and electric properties of a medium as a function of frequency (time)

is based on the interaction of an external electric field with the electric dipole moment and charges of the medium

Dielectric properties
Complex dielectric permittivity relative to vacuum *()=()-i() Complex conductivity *()=()+i() Complex electric modulus *()=()+i() as a function of temperature

Medium in an external electric field

Electric Field

D=0E+P P=0sE s= s+1

D=0sE

Medium in an external electric field

Relation between macroscopic and microscopic quantities
P= 1 V

p
i

Dipole moments can have an induced or a permanent character Permanent dipole moments, Induced polarization, P
P= 1 V

i + P =
i

N + P V

Is determined by: The interaction between the dipoles The local electric field at the location of the dipole

Medium in an external electric field

Relation between macroscopic and microscopic quantities No interaction between dipoles and local electric field equal to the outer applied field thermal energy interaction energy between the dipole and the electric field

2
3kT

1 2 N s = 3 0 kT V

Langevin equation

Interactions between molecules, effect of polarization of environment

2 N 1 s = Fg kT V 3 0

Onsager-Kirkwood-Froehlich equation

s ( + 2 )2 F= 3(2 s + )
int 2 g = 2 = 1 + z cos

Internal field Onsager factor Dipole interactions Kirkwood-Froehlich factor

Dielectric dispersion in time domain

Perturbation Electric Field Response Electric Displacement

E(t) (t)

D(t)

E(t)

D(t)
0sE0

D (t ) = 0 (t )E0

(t ) = + ( s ) (t )
(0 ) = 0 ( ) = 1

E0

oo0E0

(t ) = 1 (t )
0
t

Dielectric dispersion in frequency domain

Perturbation Electric Field Response Electric Displacement

E() *()

D*()

E(t)=E0sin(t) D(t)=D0sin(t-)

D * ( ) = D( ) + iD( ) D( ) = D0 cos ( ) D( ) = D0 sin ( )

( ) =

D0 cos ( ) 0 E0 D0 sin ( ) 0 E0

( ) =

Time-frequency domain
Time dependent dielectric function (t) Complex dielectric function *()

d (t) 1 [it]d = *() exp dt 2 0

() =
*

d (t ) [it]dt exp dt 0

Relation between dielectric function and correlation function

(t) = (s )[1 (t )] *() = (s )

d(t ) [it]dt exp dt 0

(t) =

(0) (t) + 2 (0) (t)

i i i j i i i< j 2

i i

(0) =1

(t ) = 0

Dielectric dispersion in frequency domain

Debye relaxation

t (t) = exp D
t (t ) = 1 exp D

4 3 2 1

'

''

* ( ) = +

1 + i D

0 10
-1

10

10

10

10

10

10

10

f(Hz)

Dielectric dispersion in frequency domain

Kolhrauch-Williams-Watts KWW relaxation

t KWW (t) = exp KWW

t (t ) = 1 exp KWW
1
HN

4 3 2 1 0 10
-1

'

KWW

Havrilliak-Negami relaxation

''

HN ( ) =
*

[1 + (i

* ( ) = +

[1 + (i

HN

10

10

10

10

10

10

10

f(Hz)

KWW 1.23

= 1 0.812(1 )0.387

Dielectric dispersion in frequency domain

Dipole moments in polymers

Molecular motions accommodate dipole reorientation in polymers

Decreasing frequency of external field

Dielectric dispersion in frequency domain

3x10
-1

- 60 C
0

- 40 C
2x10
-1

10

dielectric loss, ''

10

-1

10

-1

- 90 C

- 120 C
-1 0 1 2 3 4 5

10

10

10

10

10

10

10

frequency [Hz]

Glassy state (localized motions)

, relaxations
Depends on chemical structure and local molecular environment Motion of groups present in side chain around the main chain or bonds of the side chain Motion of groups in the main chain The relaxation of Johari-Goldstein type

Thermally activated motion between two potential wells separated by a potential barrier

Glassy state (localized motions)

Characteristics of dielectric dispersion
Temperature dependence of relaxation rate (time) is Arrhenius

II

E f = f exp act kT
Dielectric strength, contribute , increases with increasing T, more dipoles

FOnsager g

2 N
kT V

Broad (4-6 decades) symmetric dielectric dispersion, becomes narrower with increasing T as a result of molecular environment homogenization

Glassy state (localized motions)

7 6 5 4 3 logfmax 2 1 0 -1 -2 -3 3 4 5 6 -1 1000/T[K ] 7 8
Liquid/Rubbery State Glassy State

II

Rubbery/liquid state (segmental motions)

relaxation (dynamic glass transition) relaxation time reflects the time involved in the structural rearrangement (glass transition) of the molecules changes by many orders of magnitude from the liquid to the glass The -relaxation in polymers involves cooperative micro-Brownian segmental motions of the chains Segmental motions are associated with conformational transitions taking place about the skeletal bonds

Rubbery/liquid state (segmental motions)

Characteristics of dielectric dispersion

II

Temperature dependence of relaxation rate (time) described by VTF equation B f = f exp T T 0 Dielectric strength, predicted by , decreases with increasing T more strongly than
FOnsager g

2 N
kT V

Asymmetric dielectric dispersion High f side slope, n: local chain dynamics (n increases as T increases) Low f side slope, m: cooperative dynamics of environment (m increases as T increases)

Rubbery/liquid state (global motions)

7 6 5 4 3 logfmax 2 1 0 -1 -2 -3 3 4 5 6 -1 1000/T[K ] 7 8
Liquid/Rubbery State Glassy State

Rubbery/liquid state (global motions)

Normal mode relaxation (nm)
Observed in polymers containing dipoles type A and AB Motions of the whole chain Observed at frequencies lower than the relaxation The relaxation time of the process is strongly dependent of the molecular weight

Rubbery/liquid state (global motions)

Characteristics of dielectric dispersion
T dependence of relaxation rate (time) 6 same as this of relaxation
5 7

II

Glassy State

logfmax

Dielectric strength proportional to the 4 3 mean end-to-end vector of chain

2 1 0 -1 -2 -3 3 4 5 6 -1 1000/T[K ] 7 8

nm =

4N A p FOnsager
2

3kTM

r2

Liquid/Rubbery State

m=1 and n=0.7 predicted by theory, in practice n considerably smaller

Rubbery/liquid state (charge motions)

Conductivity Motion of charge carriers

* ( ) = ( ) + i ( ) = i 0 ( * ( ) 1)

( ) = 0 ( ) ( ) = 0 ( ( ) 1)
is not affected increases with decreasing f (slope of log vs logf equal to -1) independent of f equal to dc conductivity,
dc

T dependence of dc Arrhenius, VTF or other gives information on the conductivity mechanism

Separation of charges at interfaces

Maxwell-Wagner-Sillars relaxation (MWS)
Blocking of charges at interfaces inside inhomogeneous materials Existence of regions with different characteristics ( , ) Relaxation rate (time) depends on: volume fraction, shape, and values of regions

Electrode Polarization
Blocking of charges at sample/electrode interfaces Observed as a steep increase of Magnitude and frequency position of the process depend on the conductivity of the sample (high values of shift polarization to high f) Time of the process depends on the sample thickness (increase of thickness results in an increase of time of process)

Comparison with other techniques

Understanding the correlation between parameters of the molecular and supermolecular structures and macroscopic properties.

Contribution to open questions regarding the relaxation by covering the widest possible time/frequency scale range by different experimental techniques

Comparison with Mechanical measurements

Material testing method & tool for studying dynamics in polymers Material in an external mechanical field insulator"elastic solid, conductor"viscous liquid Viscoelastic response is analogous to dielectric dispersion Modulus representation is used In order dielectric dispersion be compared to mechanical one electric modulus has to be used for data representation

M * ( ) =

* ( )

Comparison with Mechanical measurements

Extension in broad f range by constructing master plots

Comparison with Mechanical measurements

Comparison of relaxation time temperature dependence

Comparison with Mechanical measurements

Selectivity of dielectric spectroscopy (block copolymers)

Comparison with Quasielastic Neutron Scattering

Observation of the dynamics on a microscopic length and time scale (10-7-10-11s)

S(Q, ) contains not only temporal information but also spatial information of the particle correlation function

Comparison with Quasielastic Neutron Scattering

Different T Different T

Comparison with Quasielastic Neutron Scattering

S (Q, ) = 1

Im * ( )

(Q, T ) = (T ) (Q )

Q = 1A , T

Comparable to

diel (T )

References
A. Broadband dielectric spectroscopy, F. Kremer and A. Schoenhals eds.
Chapter 1 Theory of Dielectric Relaxation A. Schoenhals and F. Kremer Chapter 7 Molecular dynamics in polymer model systems, A. Schoenhals Chapter 16 Dielectric and Mechanical Spectroscopy a Comparison, T. Pakula Chapter 18 Polymer dynamics by dielectric spectroscopy and neutron scattering-a comparison, A. Arbe, J. Colmenero and D. Richter

B. Electrical Properties of Polymers, E. Riande and R. Diaz-Calleja C. Dielectric Spectroscopy of Polymeric materials, J. Runt and J. Fitzgerald