Professional Documents
Culture Documents
Crine - 01038657
Crine - 01038657
Crine - 01038657
5, O c t o b e r 2 0 0 2 697
ABSTRACT
The influence of high electrical dc fields (>20 kVlmm) on aging, polarization and on the mor-
phology of polyethylene (PE),isdiscussed. Infrared and positron annihilation spectroscopy
measurements as well as capacitance measurements tend to suggest that the polymermorphol-
ogy is modified by high fields. We show that the accelerated electrical aging characteristics of
PE are linked directly to the morphology changes induced by the field. Below a so-called crit-
ical field, the activation volume of the aging process is dependent on the field-induced strain.
Above the critical field, the amorphous phase is deformed significantly, and weak van der
Waals bonds are broken, leading to another, faster, aging regime. There is an excellent agree-
ment between the proposed model and experimental data obtained with various PE samples.
The possible relation between the submicrocavity formation proposed in our aging model and
various polarization measurements is discussed. It is our contention that strong charge injec-
tion occurs only after submicrocavity formation, Le. after weak bond breakage. As is well
known, the polarization currents obtained under high fields are controlled by space charges. It
seems that the wave packets and the negative resistance observed at >lo0 kV/mm in PE are as-
sociated with a steady state in field-induced defect formation. This suggests that space charges
are related to the formation of submicrocavitiesand, therefore, are a consequence, not a cause,
of high field aging.
nros the long t i e (low field) regime cannot be well described assuming a
constant value for the activation volume. We have therefore explored
the possibility that AV could vary with F at low field. Note that we
assumed for the sake of simplicity that the field was constant within the
insulation. This could be correct, as long as the sample is not too thick.
2.2 INFLUENCE OF FIELD ON THE
i$ ,
ACTIVATION VOLUME
We propose that aging occurs above a given critical field F, with a
typical value in the 10 to 20 kV/mm range for PE. Its precise value can
be estimated by supposing that above F, submicrocavities are formed.
lw 200 1w cw Lewis et 01. [4,5] have shown that the mechanical stresses induced by
Field (LVimm)
electric field can lead to weak bonds breaking and, thus, to microcrack
Figure 1. Current density of PE samples as a function of dc field at formation. Obviously, the low strains generated by fields in the IO to
22°C by van Roggen [7] and Fallou et RI. [8]showing a 'negative resis- 50 kV/mm range cannot break backbone bonds whose strength is in
tance' &me >SO to 100 kV/mm. The results obtained at lower fields the 1 to 3 eV range. The weaker bonds in a polymer are the van der
by Montanari et nl. [I31on unaged and aged samples are in agreement Waals bonds with strength as low as 0.1 eV (1.6x10~-'@ J). Eyring 191
with [7,8]. and Wunderlich [IO]have shown long ago that a precursor step ~ ~ o u l d
be what Eyring called 'hole' formation, which is equivalent to the 'sub-
activated process. Thus, going from the original (unaged) state to the microcavities' detected by Zhtukov 1111during the mechanical aging of
final (aged) state requires a jump in energy over an activated energy many polymers. In all cases, weak molecular bonds are stretched under
barrier AG = A H - T A S , where A H and A S are the activation the application of a stress up to a point where they are broken, and free
enthalpy and entropy, respectively, and T is the absolute temperature. radicals are formed at the submicrocavity sites, initiating irreversible
We have recently modified the model [2] to include a square-field de- aging of the material. According to Eyring 191 the energy E,, required
-
pendence for AG, in agreement with Lewis et al. [4,5] who proposed to generate a 'hole' is related to the energy of cohesion of the polymer
that the mechanical stress induced by the field may break weak bonds E, 1.6 to 1 . 8 ~ 1 0 - ~J "for PE, to the 'hole' volume
when its value is larger than the Griffith criterion for crack formation. molar volume 1' by
and to its
0 3s
(7)
We have shown elsewhere the good agreement at low fields between
calculations (Equation (7)) and experiments for XLPE cables aged under
ac fields [12]. There is very little data published at low dc fields and
we were unable to verify the validity of Equation (7) under this sort of
electrical stress. However, high dc field results, obtained by Montanari
et ai. (131, Kitani [I41 and Chen and Davies [IS] can be described very
well by the model, as shown in Figure 2. The three different set of re-
sults have nearly identical AG values (from 2.01 to 2 . 0 6 ~ 1 0 - ' J)
~ but e
very different A V values, as can be seen from the slopes in Figure 2. 0 28
The Chen and Davies results must be treated with some care since only 0 2 I B 8 10 12 I4 16
Field (UVImm)
their 100 kV/mm result is an actual data point, the other values being
calculations made as per 1161. Figure 3. Positron annihilation measurements 1161 showing the re-
duction of the amorphous phase fraction of PE as the dc field increases.
-
was shown by Brandt and Wilkenfeld [16], Figure 3, that the amorphous
phase fraction decreases with field and levels off at 15 to 25 kV/mm,
i.e. for a very moderate strain. When the amorphous phase has been
and Shi [20] have shown that the thickness dependence of the dielectric
strength of TeflonrM(PTFE) is due to a variation of the Young modulus
with samples thickness. Since the Young and bulk moduli are related,
deformed completely, bond breaking will occur because the crystalline
this possibly could explain the thickness (or volume) effect"Kim and
phase is much tougher. Further evidence for the deformation of PE by Shi associated the decrease of the Young modulus with thickness in-
an electric field is provided by the change of capacitance C (ie.change
crease to a change in morphology, especially an increase of the lamellar
of sample thickness). A C measured by Sakamoto and Yahagi 1171, size for thicker samples.
which varies with F 2 . In addition, an hysteresis effect was observed
when fields 2 20 kV/nim where applied, i.e. A C never gets back to However, there is no equivalent data for PE and much more work is
zero when the field is lowered to zero after reaching these high fields. needed to determine the exact cause of the thichess/volume effect on
This implies that permanent deformation of the polymer has occurred aging and on breakdown strength of PE.
under the action of the high field. We may conclude that the proposed model describes very r\rell all
700 Crine: Aging and Polarization Phenomena in J'E
- J = Joexp 1- '1.
L
E - aFT
kT
1
(9)
,c
1e.a
.
3-7
I
arc 4w 6.w ax,* todo'
10'. 10'4 10.' IO" IO'D ?e
Square Ron of Field (Whnm)'"
VInl IVInl~l
Figure 5. Current density as a function of U21L3 (Equation (8)). Figure 6. log J us. fi,according to Equation (9) for the results
The expected slope of 1 is not respected for three different measure- shown in Figure 5 (22-231
ments ([U]for the unaged and aged samples, and [231).
Below Fc, there are few (if any) submicrocavitiesgenerated by the
If there is space charge, there must have been strong injection. Other field, but defects are already present, which means that the concentra-
models used to validate this assumption are the Poole-Frenkel and the tion N of 'polaiizable defects' is independent of F . For the sake of
IEEE Transactions on Dielectrics and Electrical Insulation VOl. 9 No. 5,OctoberZOOZ 701
simp1icity;we assume that it is constant and its value is then equal to with the measured values in Figure 9. The agreement is excellent in-
the N value at F,. This value may be empirically determined from the dicating that it is possible to estimate the polarization properties of PE
charge measurements performed by Montanari et d. (22) on the same from the aging results (and vice versa), provided we take into account
samples used for the current measuements shown in Figures 5 and 6. the capacitance and volume of the sample. It should be stressed that we
-
The low-field measurements gave a charge of 0.2 to 0.25 Cnr3, which did not need any space-charge field to attain these results, and we only
seems fairly typical of the residual charges always detected in PE, what- assumed that the density of injected charges was equal to thenumber of
ever the measurement technique [26-291. If we compare the measured free radicals (broken bonds) associated with submicrocavity formation.
charge to the maximum static charge.Q,,,
15kV/mm, the ratio of the measured Q over Q, is in the 2.5xlO-.'
-
= CU, we see that at 10 to This supports our contention that space charges are a consequence of
aging (they appear after bond breaking), and not a cause.
range (Figure 7). We have assumed that the concentration of defects per
10,
unit volume N , present at F, in PE at 22°C is then
N, - 2.5~10-'-
V3
cu
(11)
where V, is the stressed volume, C the sample capacitance, and U the
applied voltage.
008 ,
. . 0
.
0
L----
J 0
0.m
. 10 100
Field (kVlolm)
It is quite obvious that the high field results shown in Figures 5 and 6
are somehow associated with space charges, and we intend to show that
they are associated with submicrocavity formation. Above Fc, submi-
crocavities are formed and their concentration increases exponentially
with the square ofthe field and with time t according to J
101 ' (0' 1Y
Field IkVlmm)
levels off (see Figure 1) in the 100 kV/mm range. In addition, maxi-
mum charge concentration near breakdown are in the 200 to 400 Cni3
range 1301, which means that at very high fields Equation (13) should
be modified. Our assumption is that the current saturation shown in
Figure 1 occurs when the energy spent by the field is equal to the c o h e z
sion energy E, of the polymer ( 1 . 5 ~ 1 0 -J ~for~ PE at 22T),i.e. for a
saturation field F, given by
\\ ./" z-
,/'
I - 1
The expected saturation above Fsfor the samples used by [13-15] >I m am ua
FlWid ,*"A"
is represented on Figure 10 by dashed lines. This has to be confirmed
by more experimental work. We have applied Equation (14) to Fallou's Figure 11. Positronium yield [31]and current density [8] in PE as a
results [SI by assuming that a AV value of Z X ~ O -m3 ~ could
~ be de- function of electric field.
duced from Figure 4 and the experimental [8] V' value of Z X ~ O -m3~
The calculated saturation field is then 87 kV/mm, which is very close temperature although the influence of sample size on the activation
-
to the experimental value of 90 kV/mm (Figure 1). volume is still unclear.
The detection of submicrocavities under various fields and after var-
ious times would be extremely helpful to validate the fundamental as-
pects of the model.
The influence of morphology on XLPE aging and its evolution with
time, field and temperature requires much more work.
There is no need to calculate and use a so-called space charge field;
the applied field combined with our model gives an excellent agreement
to the existing experimental data.
Polarization seems to be related to the same physical processes than
those describing aging and at fields above the critical field the concen-
tration of charges appears to be directly related to the concentration of
0 100 zoo 300 Iw
F8eId (kVlmm)
submicrocavities.
Polarization and aging are sensitive to the sample size via the re-
Figure 10. Concentrationof radicals (or submicrocavities or charges)
lation between the activation energy and the sample size. This may
calculated as a function of field for samples used in [1?-15]. The
dashed lines represent the estimated saturation concentration value possibly explain the thickness effect on breakdown strength.
for each case. Our model predicts that the wave packets and current saturation
observed at very high fields occur when the energy spent by the field is
The assumption that no more defects are created above F, is sup- equal to the cohesion energy of the polymer.
ported by the positron annihilation spectroscopy performed on PE un- The relation between charges and defect concentration (formed be-
der high fields [31], which also indicates a saturation in the positronium fore injection) suggests that space charges are more a consequence than
yield (i.e. a saturation in the formation of defects) in the 100 kV/mm a cause of aging under high fields.
range (Figure 11). The saturation of the positronium yield corresponds
very well with the current saturation measured by Fallou and also with ACKNOWLEDGMENT
the~wavepackets observed in space charge measurements [6]. Hence,
This work was partially funded by EPRI, and we thank W. Zenger
we suggest that wave packets and 'negative resistance' occur in the 60 for his support,
to 100 kV/mm ranee. because there are no more defects created. which
Y .
implies that charge injection reaches a constant state. Since more and REFERENCES
more electrons are available with increasing fields, this leads to charge
[I] C. Dang,J. L. Parpal and 1. P. Crine, "Electrical Aging of Extruded Dielectric Cables
pile-up at the electrode/polymer interface with eventual flows (it. cur- . A physical M ~ ~ IEEEY T, ~Diel.~ E I ~~hSul.,
~ .. v0i.4, pp. i97-202,197.
rent oscillation) similar to powder flow in a bel. Obviously, much 121 J. P trine, "Comparison of the Lwis and Crhe Models on Eiectrical Agng of D i ~
more work is needed to confirm this sunnestion.
"" .. 50bl1, Oct. 1999.
electria", CElDP Coni., DD.
131 L. A. Dissado, G. Marzanti and G. C. Montanari, "The Role of Space Charge; in the
4 CONCLUSIONS Electrical Ache of Insulation Materials". EEE Trans. DEI, Vol. 4. OD. 496505.1997.
Y Y . 1 1
[4] T.J. Lewis, I. P Llewelin, M.I.van der Sluijs, I.Freestone and N. Hampton, "A New
The Proposed model for the dry electrical aging of PE under dc field Model for Electrical Aging and Breakdown in Dielectrics", Proc. 7th IEE Coni. Diel.
describes very well accelerated aging results obtained under constant Meas. Appl., pp. 220-5,1996 and in Froc. 1996 CEiDP. pp. 328-33.1996.
IEEE Transactionson Dielectrics and Electrical Insulation Vol. 9 No. 5,OctoberZOOZ 703
(51 C. L. Giiffiths, 1. F. Freestone and R. N. Hamptan, "Thermaelectric'Aging of Cable- [20] H. K. Kim and F. G. Shi, "Thickness Dependent Dielectric Strength a Law-
Grade XLPE, IEEE Int. Symp. Electr. h u l . , pp. 57682,1998. Pennittivity Dielectric Film", IEEE Trans. DEI, Vol. 8, pp. 248-52,2001.
161 N. Hozumi, Y. Muramoto and hl. Nagau, "Estimation of Carrier Mobility Using 1211 S. H. Lee, I. K. Park, C. R. Lee and K. S. Suh, "The Effect of Low-molecular-weight
Space Charge Measurement Technique", Roc. 19% CEIDP, pp. 35&3,1999. Species on Space Charge and Conduction in LDPE, IEEE Trans. DEI, Vol. 4, pp.
171 A. van Roggen, "Electronic Conduction of Polymer Crystals", Phys. Re,,. Letters,.. 42532,1997.
Vol. 9, pp. 3W70, 1962. 1221 G. C. Monlamri, D. Fabiani, L. Bencivenni, B. Garros and C. Audq: "Spare Charge
181 B. Fallnu, "Etude des charges d'espare dans le polyethylene pour cables haute ten- and Conduction Current measuzements far the Evaluation of Aging of Insulating
sion", Rev. GenCraIe lec., Vol. 81, pp. 761.7. 1972. Materials far DC Applications", Jicable 99 Coni., pp. 1416, 1999; also in REE, Vol.
[91 N. Hirai and H. Eying, "Bulk Wrcosity of Liquids", J. Appl. Phys., Val. 29, pp. 1,pp. 44-48.1999.
XIM, 1958. 1231 J. L. Aug6, C. Laurent, D. Fabiani and G. C. Montanan, "Investigating dc Polyeth-
ll01 8. Wunderlich, "Motions in Polyethylene- The Amorphous Polymer". J. Chrm. ylene Threshold by Space Charge", IEEE Trans. DEI, Val. 7, pp. 797-803.2000.
Phys., Vol. 37, ..
DO.242932,1962, 1241 See for example: I. 1. ODwyer, The Tiimry ofElectrica1 Conductionand Birddoion in
Ill] S. N. Zhurkov, \! A. Zakrevskyi, V. E. Karsukov and V. S. Kuksenko, "Mechanism Solid Did&cs, Clarendon Press, 1973.
of Submicrocrack Generation in Stressed Polymers", 1. Polymer Sci. A2, Val. 10, pp. [UlJ. Frenkel, Phys. Rev., 54Vol.,pp. 6 5 7 4 1938
150~20,1972. [tal J. I? Crine, "Charge Injection and Transport in Polymers: Myths and Reality", 1986
[12l 1. P. Crinc, "lntluence of high Electrical Fields on Aging and Polarization Properties CEIDF, pp. 9596,1986.
of PE", to be published, Polymers Intemational, 2002. 1271 K. Suh, H. G Y w n , C. R. Lee, T Okamoto and T Takada, "Space Charge Behavior of
[I31 G. C. Montanari and D. Fabiani, "Evaluation of Insulation Degradation of Stressed Acrylic Monomer-grafted Polyethylene", IEEE Trans. DEI, Vol. 6, pp. 282-7,1999.
XLPE Cables", EEE Trans. DEI, Vol. 7, pp. 322-8.2000, 1281 Y. Zhang, 1. Lewiner, C. AlquiC and N. Hampton, ''Evidence of Strong Correlation
1141 I. Kitani and K. AIll, "Long lime Range Breakdown in Polymefic insulating Film Between Space Charge Buildup and Breakdown in Cable Insulation", IEEE Trans.
Subjected to Step Voltage", IEEE Int. Symp. Electr. Insul., pp. 3558,1988. DEI, Val. 3, pp. 77H3.1996.
[E] G. Chen and A. E. Davies, "The Influence of Defects on the Short-Term Breakdown 1291 G. Chen, H. M. Baniard and A. E. D a h , "Space Charge Formation in y-irradiated
Characteristics and Long-Term dr Performance of LDPE hulation", EEE Trans. LDPE, lEEE Trans. DEI, Voi. 5, pp. 51-7.1998.
DEI..Vnl. 7..,, .~~
OD. 401-7.2000. 1301 M. Abou Dakka, A. T. Bulinski and S. S. Bamji, "Space Charge Distribution Mea-
W. Brandt and J. Wilkenfeld, "Electric Field Dependence of Positronium Formation surements in XLPE and EPR Subjected to Uniform ac and dc Fields", REE, Vol. 3,
in Condensed Matter", Phys. Rev. 8, Vol. 12, pp. 257947,1975. pp. 3742,1998.
M. Sakamoto and K. Yahagi, "Muence of tiigh Electric Fields an Capacitance Mea- 1311 M. Fukuma, K. Fukunaga and T. Maeno, "Space Charge Dynamics in LDPE Films
surements in PE", Japanese I. ApplLPhys., Vol. 19, pp. 253-9. 1980. Immediately Before Breakdown", IEEE Trans. DEI, Vol. E, pp. 3044,2001,
M. Meimier and I. P. Crine, "In S i b Infra Rod Spectroscopy of Electric Field lnduccd 1321 A. Camar, "Electric-Field Dependence of Positron Annihilation in P E , World Sci-
Micr+Structwal Changes in Polyethylene", 1985 Coni. Elec. Insul. Diel. Phenam., entific Conf., Singapore, pp. 7935.1989.
pp. 37741,1985.
1191 \! K. Agamal and V. K Srivastava, "Thickness Dependence of Breakdown Field in
Manuscript was received on 2 December 2001
Thin Films': Thin %lid Films, Vol. 8, pp. 37741,1971.