Thermally Stimulated

Depolarization Current
Technique
TSDC

TSDC technique

Method

1 Polarization Process
2 Depolarization Process

1
2

TSDC technique

Theory
Bucci-Fieschi Theory (Debye)
Polarization Process

t
P (t ) = Pe 1 exp

2
aNp E p
Pe =
kT p

a = 1 ,dipoles free to rotate

3

Depolarization Process
t
P (t ) = Pe exp

J (t ) =

dP (t )
dt

t dt
P (t ) = Pe exp
0

TSDC technique
t dt
P (t ) = Pe exp
0

Theory

J D (T ) =

T = T0 + qt

P (T0 ) = Pe (T p )

dP (t )
J (t ) =
dt

J D (T ) =

Pe (T p )

Pe (T p )

Eyring Equation

1 T dT
exp

(
)
q

T0

kT

(T ) = 0 exp

1 T
E
E
exp
exp
exp
dT

q
k
T
kT

0 T0

T<Tm

T>Tm

H
S
E h
exp

exp
=
kT
kT
k
kT

(T ) = 0T 1 exp

Tm =
VFT Equation

T T

(T ) = 0 exp

qE
k (T p )

TSDC technique

Example

relaxation

PPMA
relaxation
-12

[]

10

relaxation

-13

10

-140

-120

-100

-80

-60
T[C]

-40

-20

20

TSDC technique
In reality relaxation processes deviate considerably from the Debye behaviour!!
Dipole-dipole interactions
Variation in size and shape of the rotating dipolar entities
Anisotropy of internal field in which dipoles reorient

Relaxation processes are described in terms of:

distribution of Debye-like processes with different relaxation times
distribution of relaxation times of Arrhenius behaviour
distribution of pre exponential factor or/and of activation energy
Valid for secondary processes, for the relaxation??

Non exponential process (KWW)

TSDC technique
Effect of experiment conditions on TSDC peaks
Polarization field
Pe =

aNp 2 E p
kT p

Heating rate
q

Tm, Jm

Cooling rate

P (T0 ) = Pe (T p )H (T , t )

tp

t
1 0 dT
exp 0
H (T , t ) = 1 exp

(T p ) q T p (T )
(T0 )

Jm

TSDC technique
Effect of experiment conditions on TSDC peaks
As a result of relaxation time distribution
Position , shape and intensity of peaks are affected by:
Polarization temperature Tp

Storage temperature T0

TSDC technique
Correlation between dipolar TSDC and conventional dielectric measurements

f eq =

1 qE
2 kTm 2

relaxation

relaxation
relaxation

relaxation

-1

10

-12

[]

dielectric loss, ''

10

relaxation

-2

10

relaxation

-13

10

1Hz

-140 -120 -100

-80

-60

-40

-20

20

-140 -120 -100 -80

-60

-40

T[C]

T[C]

kTm
f eq (Tm ), T 1.47
J D (T )
q 0 EE p

-20

20

40

TSDC technique
Correlation between dipolar TSDC and conventional dielectric measurements
Equivalent frequency of TSDC measurement 7
f eq =

1 qE
2 kTm 2

Jeffamine4000

Arrhenius behaviour

5
4

1
qB
VTF behaviour
2 (Tm T )2

logfmax

f eq =

3
2
1
0

For typical values feq10-4-10-1 Hz

Usually f which corresponds to =100s

-1
-2

TSDC

-3
3

5
6
-1
1000/T[K ]

Due to the low equivalent frequency of method location of the peaks correspond to dilatometric
transition temperatures e.g. glass transition temperature


peak

TSDC technique
Determination of dielectric strength

Pe (T p ) = J D (T )dT
0

Pe (T p ) = 0 ( s )T p E p

= ( s ) =

Q
0 AE p

Saturated process, no change in polarization during cooling and storage step

Systematic error depending on the cooling rate

Analysis

TSDC technique
Determination of activation energy and pre exponential factor
Initial rise method
J D (t ) =

Pe (T p )

1 T
E
E
exp
exp
dT
exp

kT
q
k
T

0 T0

T<<Tm
ln J D (T ) const .

E
kT

ln J D (T ) const . + ln T
ln J D (T ) const .

B
T T

E
kT

Analysis

TSDC technique
Determination of activation energy and pre exponential factor
Graphical integration

ln (T ) = ln J (t )dt ln J D (T )
t (T )

= ln 0 +

E
kT

= ln 0 ln T +

= ln 0 +

E
kT

B
T T

Analysis

TSDC technique

Analysis

Determination of activation energy and pre exponential factor

Approximate methods Tm, T1 (<Tm @Jm/2), T2 (>Tm @Jm/2)
E = 2.42

k (T1T2 )
T2 T1

E = 1.51

k (T1Tm )
Tm T1

2
E
kTm

exp
0 =
qE
kT
m

Varying heating rate

2
k (Tm1Tm 2 ) q1Tm 2

ln
E=
2
Tm1 Tm 2 q2Tm1

Tm 2
ln
q

vs

Tm

TSDC technique
Experimental determination of
distribution of relaxation times

Fractional polarization
Thermal sampling technique

TSDC technique

-11

7,0x10

Jeffamine4000

PDMS

-11

6,0x10

-11

5,0x10

I[A]

-11

4,0x10

-11

3,0x10

-11

2,0x10

-11

1,0x10

0,0
-100 -95

-90

-85

-80
T[C]

-75

-70

-65

-60

TSDC technique
Depending on the scenario followed for the non-exponentiality
of the dielectric relaxations especially of the relaxation

Heterogeneous scenario
Each isolated peak is analyzed in terms of single Debye process
T-dependence of relaxation time is assumed
Arrhenius
VTF

Homogeneous scenario
Each isolated peak is analyzed in terms of a KWW process

TSDC technique
Heterogeneous scenario

Q
I
Tf

1
Q = I (T )dT
qT

ln 0i = ln c

E. Laredo, A. Bello, M. C. Hernandez, M. Grimau, Journal of Applied Physics, vol. 90, 11

Ei
kTc

TSDC technique
Homogeneous scenario
t
P (t ) = Pe exp

Q Q0
ln
I Q

Tf

Q=

1 1

Tf

1
I (T )dT
q T

E = k

1
Q0 = I (T )dT
q 0

d [ln ]
d 1
T

[ ]

Journal of Polymer Science: Part B: Polymer Physics, Vol. 38, 21052113 (2000)

TSDC technique
Study of ageing process by TSDC
Increase of ageing time results in
Shift at higher T
Decrease of maximum current, area

C. Alvarez, N.T. Correia, J.J. Moura Ramos, A.C. Fernandes, Polymer 41 (2000) 29072914

TSDC technique
Calculation of fragility index from TSDC curves