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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
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
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
[]
10
relaxation
-2
10
relaxation
-13
10
1Hz
-80
-60
-40
-20
20
-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
-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
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
k (T1T2 )
T2 T1
E = 1.51
k (T1Tm )
Tm T1
2
E
kTm
exp
0 =
qE
kT
m
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
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