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Tcnicas

experimentais

A interao entre ondas eletromagnticas e materiais


dieltricos pode ser determinada por tcnicas de
medio de banda larga.

Espectroscopia de relaxamento dieltrica permite o


estudo da estrutura molecular, atravs da orientao
dos dipolos sob0 a ao de um campo
eltrico.
-4
4
8

10

10
1012
experimental

10

10

The
devices cover the frequency range
-4 -1011 Hz.de domnio do tempo
Espectrmetro
10
Analisador de resposta de frequncia
Pontes AC
Reflectmetros
Circuitos de ressonncia

Cavidades e guias de onda

MEASUREMENT SYSTEMS IN THE


TIME DOMAIN

In linear systems the time-dependent response to a step


function field and the frequency-dependent response to a
sinusoidal electric field are related through Fourier
transforms.

For this reason, from a mathematical point of view, there is


no essential difference between these two types of
measurement.

Over a long period of time the equipment for


measurements in the time domain has been far less
developed than that used in the frequency domain.

As a result, available experimental data in the time domain


are much less abundant than those in the frequency
domain.

Time domain spectroscopy

To cover the lowest


Vo
frequency range (from 10-4
to 101 Hz), time domain
spectrometers have
recently been developed.

In these devices, a
voltage step Vo is applied
to the sample placed
between the plates of a
plane parallel capacitor,
and the current I(t) is
recorded.

I(t)

I (t )
d (t )
Co
Vo
dt
eo S eo R 2
Co

d
d

d (t )
I (t )

dt
eo S Eo

1
(t )
I (t ')dt '

Co Vo 0

d (t ) 1

dt
2

( ) exp(it )d

*()
(t)

d (t )
( )
exp(it ) dt
dt
0
*

Complex Dielectric
Function

Time Dependent
Dielectric Functio

The main item in the equipment is the


electrometer, which must be able to measure
currents as low as 10-16A.
In many cases the applied voltage can be taken
from the internal voltage source of the
electrometer.
Also low-noise cables with high insulation
resistance must be used.

MEASUREMENT SYSTEMS IN THE


FREQUENCY DOMAIN

In the intermediate frequency range 10-1- 106


Hz, capacitance bridges have been the common
tools used to measure dielectric permittivities.

The devices are based on the Wheatstone


bridge principle where the arms are
capacitance-resistance networks.

The

principle of measurement of capacitance


bridges is based on the balance of the bridge
placing the test sample in one of the arms.

The sample is represented by an RC network in parallel or series.

When the null detector of the bridge is at its minimum value (as
close as possible to zero), the equations of the balanced bridge
provide the values of the capacitance and loss factor (or
conductivity) for the test sample

Frequency response analyzers have proved to be very useful in


measuring dielectric permittivities in the frequency range 10 -2 - 106
Hz,.

An a.c. voltage V1 is applied to the sample, and then a resistor R,


or alternatively a current-to-voltage converter for low frequencies,
converts the sample current Is, into a voltage V2 .

By comparing the amplitude and the phase angle between these


two voltages, the complex impedance of the sample Zs can be

V
V

V
1
2
1
2
calculated as
Zs

R
Is
V2

V1 V2 V1 V2
Zs

R
Is
V2

Conductivity

Owing to parasitic inductances, the highfrequency limit is about 1 MHz,

It is necessary to be very careful with the


temperature control, and for this purpose
it is advisable to measure the
temperature as close as possible to the
sample.

At frequencies ranging from 1 MHz to 10


GHz, the inductance of the connecting
cables contributes to the measured
impedance.

At frequencies above 1 GHz the


technique often used to obtain dielectric
spectra is reflectometry.

The technique is based on the reflection


of an electric wave, transported through a
coaxial line, in a dielectric sample cell
attached at the end of the line.

In this case, the reflective coefficient is a


function of the complex permittivity of
the sample, and the electric and
geometric cell lengths.

Reflection coefficient

r *( x)

*
refl
*
inc

( x)

U ( x)

reflected voltage
Incoming voltage

2
r (l ) r (0) exp

i
*

Reflection
at the beginning
of the line

2 n "
2 n '

; =

Propagati
on
coefficient
Attenuation
coefficient

1 r (l )
Z ( ) Z 0
*
1 r (l )
*
s

IMMITTANCE ANALYSIS
Basic Immittance Functions

In many cases, it is possible to reproduce the electric


properties of a dipolar system by means of passive elements
such as resistors, capacitors or combined elements.

One of the advantages of the models is that they often easily


describe the response of a system to polarization processes.

However, it is necessary to stress that the models in general


only provide an approximate way to represent the actual
behavior of the system.

The analysis of dielectric materials is commonly made in


terms of the complex permittivity function * or its inverse,
the electric modulus M*

electrical

impedance and
admittance are the
appropriate functions to
represent the response of
the corresponding
equivalent circuits.

As a consequence, the four


basic immittance functions
are permittivity, electric
modulus, impedance and
admittance.
They are related by the
following formulae:

M ( )
*

Y Z
*

* 1

* 1

Y * i
Co *
M i
Co Z
*


tan=/

Mixed Circuit. Debye Equations

C 1 = C o

= RC2
C2 = (o-) Co

As shown before, Debye equation can be obtained in


three different ways:
(1) on the grounds of some simplifying assumptions
concerning rotational Brownian motion,
(2) assuming time-dependent orientational
depolarization of a material governed by first order
kinetics, and
(3) from the linear response theory assuming the time
dipole correlation function described by a simple
decreasing exponential.
The actual expressions are given by

Under certain circumstances, the admittance is


increased on account of hopping conductivity
processes. Then, a conductivity term must be included

o is a d.c. conductivity.

However, the presence of interactions leads to the


inclusion of a frequency dependent term in the
conductivity in such a way that

EMPIRICAL MODELS TO REPRESENT


DIELECTRIC DATA - Retardation Time Spectra

The assumptions upon which the Debye equations are


based imply, in practice, that very few systems display
Debye behavior

In fact, relaxations in complex and disordered systems


deviate from this simple behavior.

An alternative way to extend the scope of the Debye


dispersion relations is to include more than one
relaxation time in the physical description of relaxation
phenomena.

The term N() represents the distribution of relaxation


(or better retardation) times representing the fraction of
the total dispersion that has a retardation time between
and +d

The real and imaginary parts of the complex


permittivity are given in terms of the retardation times
by:

Alternatively, the retardation spectrum can be defined


as

Retardation time spectra


Advantages:

Disadvantages:

Better

Require

separation of
processes

Processes

are
narrower than in
frequency domain

numerical
evaluation of the
spectrum.

No

physical sense

'

"

4
3

10

-1

10

-2

2
10

-2

10

10

10

10

f, Hz

1,0
0,8

L(ln )

0,6
0,4
0,2
0,0
-6

-4

-2

log

Cole - Cole Equation

Experimental data ( vs )rarely fit to a Debye semicircle.

Studying several organic crystalline compounds, Cole and Cole


found that the centers of the experimental arcs were displaced
below the real axis, the experimental data thus having the shape of
a depressed arc.

1-={0,5 1}

high frequencies

Low frequencie

The corresponding
equivalent circuit is:

The admittance is given


by:

Note that the circuit


contains a new element,
namely a constant phase
element (CPE), the
admittance of which is
given by

The admittance reduces


to R-1 when = 0

When we can use Cole Cole


equation
Symmetric relaxations.
In general all Secondary relaxations can
be fitted by Cole Cole equation.
The (1-) parameter, give us an idea
about how distributed is the relaxation
(how broad it is).
In general the (1-) parameter, must
increase with the temperature.

Fuoss- Kirkwood Equation



"( )
sec h ln Debye
"
max
o


"( )
sec h mln FK
"
max
o

"( ) 2 max

"

1 o

2m

1941 - Fuoss and Kirkwood


propose to extend the Debye
equation, in order to fit
symmetric functions.

Assuming an Arrhenius
dependency of the relaxation
time with the temperature, it
is possible to express the FK
equation as a T function.

When its possible to use the FK


eq.
Secondary relaxations Symmetric
relaxations.
Advantages: The temperature
dependencies of the loss factor have a
very simple expression.
There are some relation between the m
parameter of the FK equation and the
(1- ) parameter of the CC equation.

a=1-

Davison Cole Equation


The

Cole Cole and Fuoss Kirkwood equations


are very useful for symmetric relaxations.
experimental data obtained from
vs. plots show skewness on the high
frequency side.

However,

For

this reason, Davison and Cole (1950)


proposed to fit the experimental data with the
following equation:

high frequencies

Low frequencie

Characteristic maximum
maximum

max CD

high frequencies

Low frequencie

Havriliak - Negami Equation


The

generalization of the Cole-Cole, and


Davison-Cole equation was proposed by
Havriliak and Negami (1967).
The flexibility of the HN, five-parameter
equation, makes it one of the most widely
used methods of representing dielectric
relaxation data.
The formal expression is

m et
Asym

Depressed
(1-)

ric

high frequencies

Low frequencie

When we can use HN eq.


For

all dielectric processed,


We must use for the main relaxation
process ( - process)
For secondary relaxation we can use,
taking = 1.
Advantages: flexibility
Disadvantages: number of parameters

KWW Model

Williams and Watt proposed to use a stretched


exponential for the decay function (t), in a similar way
to Kohlrausch many years ago.

In this way, the normalized dielectric permittivity can


be written as

KWW - Model
The

resulting expression does not have a


closed form but can be expressed as a
series expansion

where is the gamma function For = 1 the


Debye equations are recovered.

low values of and > 0.25, the


convergence of the series of the KWW eq. is
slow, and the following equation is proposed

For

The

KWW equations are nonsymmetrical in


shape and for this reason it is particularly useful
to describe the nonsymmetrical -relaxations.

Thermostimulated Depolarization and


Polarization

T
T

Due to the fact that the charges are virtually immobile at


low temperatures, it is possible to study the depolarization
as a temperature function

Tp,tp
E=Eo

Tf

Tw,td
E=0

Tf

Tp,tp
E=Eo

h (C/min)
h (C/min)
To

To

Eo

Eo
0

I (A)
-12
10

1E-12

1E-13

10

-13

100

150

200

250

T, K

Poly 3 (Fluor) bencyl-methacrylate

300

350

1E-14

Thermostimulated

depolarization currents is a
complementary technique for the evaluation of
the dielectric properties.

Its

also useful for the following of the chemical


reaction in which the mobility of the dipoles
change due to structural changes.

Could

give information about the fine structure


of the materials

Its

equivalent frequency is lower than the


dielectric spectroscopy

*
*

n
O

"

0.1
F

0.01
10

-1

10

10

10

10

10

f, Hz

10

10

10

10

10

DC

j vac

1 j
1

2
1 j 2

1 2

Summary

Experimental techniques:
Time domain
Frequency domain:
Frequency

Response Analyzer (ac bridges)


RF Analyzer (reflectometry)

Complex

dielectric Function it is related


with the Time Dependant dielectric
function by means of the Fourier Transform

Summary
M ( )

Immitance

Y Z

Electric

* 1

Functions:

Modulus
Permittivity
Impedance
Admitance

Y i
Co
*

M i
Co Z
*

Summary

Fitting of the
experimental data
Symmetric relaxation
broader than Debye
relaxation:
Cole-Cole equation
Fouss Kirkwood

Asymmetric relaxation:
Cole-Davison

Asymmetric and
broader relaxations:
Havriliak-Negami
KWW

Summary
Another

fitting procedures:

Retardation time spectra

Equivalent circuits

Wheaston bridge

Z1=1/Y1

Z2=1/Y2

Z3=1/Y3

Z4=1/Y4

a.c.signal generator

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