30
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Aging of Polyolefin Electrical Insulation K. D. KISS, H. C. DOEPKEN, JR., and N. SRINIVAS Phelps Dodge Cable and Wire Company, Yonkers, NY 10702 B. S. BERNSTEIN Electric Power Research Institute, Washington, DC 20006
Polyolefins are the preferred insulating materials due to a fortuitous combination of their properties: high resistivity and dielectric strength, low dielec t r i c constant and dissipation factor, low specific gravity, moderate melting range and good processability, adaptability to stabilization and compatability with additives and f i l l e r s and economy and availability on large scale. In power transmission and distribution cables rated 5 kV and above low density polyethylene (ΡΕ), crosslinked low density polyethylene (XLPE) and ethylene -propylene rubbers (EPR) are used in large quantities. A recent survey (1) shows that the combined length of underground power cables exceeds 190,000 miles in the U.S.A. Field data covering over 25% of this total re veals dielectric failures attributable to premature ageing beginning approximately 3 to 8 years after the installation (Figure 1). This is considered a serious indicator of potential hazard and has precipitated a major effort to define the problem areas, understand the causes with a view of eliminating or at least mini mizing them. Background Ageing Process i n S o l i d D i e l e c t r i c s . "Ageing" and l i f e time" are terms based on b i o l o g i c a l analogies, and, though widely used describe the investigated phenomena with limited accuracy. Kelen ( 2 ) suggests the use of the term "endurance", which i s the opposite though not the exact reverse of ageing. 0-8412-0485-3/79/47-095-433$08.50/0 ©
1979 A m e r i c a n C h e m i c a l Society
Eby; Durability of Macromolecular Materials ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
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DURABILITY O F M A C R O M O L E C U L A R M A T E R I A L S
1962
1965
1970
1975 Time, years
Figure 1.
Field performance of high voltage cables
Annealing Tree Formation
Figure 2.
Schematic life curve
Eby; Durability of Macromolecular Materials ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
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30.
KISS E T A L .
Polyolefin
Electrical
Insulation
435
The inherent d i e l e c t r i c strength of polyethylene measured on t h i n f i l m s i s estimated as 600 to 800 kV/=
Whelan l o i d a l
(12)
presents
the
equation
for
two
hyperbo-
points: E max ^
V r t a n h l
x /
(fiTT j
( )
r
5
where:
This
correlation
calculation electrodes oratories at
the
the
of in
in
t i p
turn
may
t i a t e
adopted
stress
fold
(14).
gradual
Aschcraft
needle
studies.
protrusion
the
by
enhancement
double
the
trigger
Though
was
the
hundred
surface
= point to point dist.
treeing
of
free
= radius conductive point
stress
e l l i p s o i d ,
several
r C
the
test
used
or
on
the
enhancement to
level
immediate
the
of
of
in on
ratio may
d i e l e c t r i c
some of
breakdown
polymers
made
s p e c i f i c a l l y
for
high
occasional
ants
and
contribute
to
deterioration
properties. as
gels
Some or
of
the
these
prematurely
ethylene
particles
which
in
depending
on
color
in
or
i n i -
deterioration. clean,
such
in
to
protrusion
remarkably
nature
axes
increase
are
occur
lab-
radius
amount
insulation e l e c t r i c
the
the
the
smooth,
stress
for
(JL3) t i p
Depending
compared This
at
may
heat
appear
history.
are
voltage
contaminof
polymeric
corsslinked amber
to
Figure
in
poly-
dark 5
d i -
brown
shows
Eby; Durability of Macromolecular Materials ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
one
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30.
KISS E T A L .
Polyolefin
Figure 5.
Electrical
Insulation
Gel particle in XLPE (10 ym)
Eby; Durability of Macromolecular Materials ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
441
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442
DURABILITY O F
MACROMOLECULAR
MATERIALS
of these i n the center, the v e r t i c a l r i p p l e s are a r t i f a c t s caused by the c u t t i n g blade f o r c i n g the r e s i s t i n g g e l forward. Inorganic p a r t i c l e s (Fig. 6) such as meta l l i c f i l i n g s contribute to tree i n i t i a t i o n and hence gradual d e t e r i o r a t i o n . Along with contaminant nature, t h e i r shape, d i r e c t i o n and l o c a t i o n may amplify t h e i r detrimental e f f e c t . Those imbedded at the conductor s h i e l d - i n s u l a t i o n i n t e r f a c e (Figure 8) may act as protrusions and cause l o c a l i z e d s t r e s s enhancement. C e l l u l o s i c fibrous p a r t i c l e s (Figure 7) (15-20 mils, 0.38 to 0.51 mm) at about 10 per l i n e a r foot of cable were shown by Bahder (15) to lower the average AC breakdown strength by 40%. E x i s t i n g s p e c i f i c a t i o n s for 5 to 69 kV cables proh i b i t "any translucent material that i s l a r g e r than 50 m i l (2 mm) i n i t s r a d i a l vector p r o j e c t i o n " and "any contaminant larger than 10 mils (0.4 mm) i n i t s largest dimension" and l i m i t s those 2 to 5 mils (0.08 to 0.2 mm) to 15 per cubic inch (0.92 per ccm) (9.). Part of the contaminants may be present i n the p e l l e t i z e d raw materials, another part o r i g i n a t e s from m a t e r i a l handling and processing. The extrusion process and the a p p l i c a t i o n of screens removes the larger p a r t i c l e s or breaks them down. Ionic contamination may occur during the service l i f e due to corrosion products of the conductor or of the m e t a l l i c s h i e l d s entering the i n s u l a t i o n . Voids or c a v i t i e s are the most numerous of the imp e r f e c t i o n s . Their number i n steam cured XLPE i s e s t i mated as 10^ per cubic cm. (16) Their combined volume amounts to l e s s than 1% of the t o t a l , which computes as about 30 jam average diameter assuming s p h e r i c a l shape. This s p h e r i c a l shape probably applies to the majority of them though ovaloid shapes, roundish ones with i r regular corners, polygonals with s l i g h t l y rounded corners and long, narrow cracks have also been found ( F i g . 9); the l a t t e r ones may o r i g i n a t e from round voids. Void d i s t r i b u t i o n i s not uniform (15, 17). In the r a d i a l d i r e c t i o n of the cable r e l a t i v e l y few are l o c a t ed at the conductor side and at the outside surface, and the d i s t r i b u t i o n curve peaks between the midpoint and the outer surface (18). This d i s t r i b u t i o n i s associated with the e f f e c t of steam used to cure XLPE. The s o l u b i l i t y of water i s very low (50 to 70 ppm)
Eby; Durability of Macromolecular Materials ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
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30.
KISS E T A L .
Polyolefin
Figure 6.
Figure 7.
Electrical
Insulation
Contamination in XLPE (600 fim)
Fibrous contamination (25 ym)
Eby; Durability of Macromolecular Materials ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
443
DURABILITY O F M A C R O M O L E C U L A R
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444
Figure 8.
MATERIALS
Contamination at conductor shield-insulation interface (15 fim)
Figure 9.
Void (5 fim) and cracks
Eby; Durability of Macromolecular Materials ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
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30.
KISS E T
AL.
Polyolefin
Electrical
Insulation
445
(19) i n polyethylene at room temperature, but reaches 4000 - 5000 ppm under the conditions p r e v a i l i n g i n the steam tube. Thus, most of t h i s absorbed water forms a d i s t i n c t separate phase when the crosslinked cable i s cooled and i s probably responsible f o r the majority of the voids. E s p e c i a l l y harmful are the voids at the conductor s h i e l d - i n s u l a t i o n i n t e r f a c e (Figure 10) which, when f i l l e d with a conductive l i q u i d , may act as protrusions. Even i n XLPE cables cured under dry conditions some voids e x i s t . These are thought to be due to the c o a l escence of c a t a l y s t by-products or i n t e r s p h e r u l i t i c space caused by c r y s t a l l i z a t i o n of the cooling polyethylene. Relative to the morphological structure, the larger voids were shown by P h i l l i p s (17) to occur at the i n t e r s t i c e s of spherulites, and the smaller ones along the s p h e r u l i t i c d i v i d e r s . S i m i l a r views were presented by Patsch (20). An opposing view (16, 21) places them i n the center of the spherulite l i k e structures (Figure 11) . In the f r e s h l y made XLPE cable the c a v i t i e s are f i l l e d with e i t h e r a gas (water vapor, a i r , nitrogen, methane, low molecular weight hydrocarbons) or a l i q u i d (water or organic l i q u i d s from the by-products of the decomposed curing agent). Even r a d i a t i o n crosslinked polyethylene contains voids, presumably caused by the evolution of hydrogen or low molecular weight hydrocarbons (22) (Figure 12). Both the gaseous and the l i q u i d by-products may escape gradually. Thermal treatment was shown to diminish void number and s i z e (18). This would necessitate an increase i n density and such an increase was reported by N i t t a and a l (6_) . E l e c t r i c stress and d i e l e c t r i c heating among other factors could r e s u l t i n a rearrangement of void d i s t r i b u t i o n , shape, s i z e and number, and i s a p o s s i b l e cause of some slowly occurring changes during s e r v i c e . Ageing Parameters Several of the t y p i c a l factors e f f e c t i n g service l i f e or ageing of polymers i n other a p p l i c a t i o n s can be eliminated on the basis that e i t h e r by themselves or i n combination they appear to cause less damage than
Eby; Durability of Macromolecular Materials ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
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DURABILITY O F M A C R O M O L E C U L A R
Figure 10. Void at conductor shield-insulation interface (4 fim)
Figure 11. Voids in center of spherulitic structures (5 fim)
Eby; Durability of Macromolecular Materials ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
MATERIALS
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30.
KISS E T A L .
Polyolefin
Electrical
Insulation
Figure 12. Voids in radiation cross-linked polyethylene (1-8 fim)
Eby; Durability of Macromolecular Materials ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
447
DURABILITY O F M A C R O M O L E C U L A R
448 others, ageing
therefore
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of
Environment.
ultraviolet
whelming et
tection carbon
in
this
black
of
commonly
at
XLPE
a
oxygen
linking
of
e l e c t r i c a l
treeing
The a
fact
major
thermal dealing or
parent
to
concern
or
of
treatment
heat
Mangaraj
(16)
parameters frequency
the
such
as
and
in
in
per
a
the
of
factor
a n t i -
the
crosssystems
the on
reported preventing
limitation
the
with and
was
temperature
potential
concern. by
effect
with
in
compreeffect and
(6)
work
in
that
concentration
ap-
conductor
or
Nitta the
stabil-
is
this
of
(24)
other or
(26).
E l e c t r i c a l
of
by
a
investigations
emergency
of
to
was
performance,
effect
antioxidant
stress,
of
Beneficial
noted
comwould
due
temperature
performance
Most
is
temperature
deleterious
f i e l d
se
insulation
variety
others.
mechanical
prevented
on
operating
to
largely
t e l e -
satisfactory
is
amines
potential
major
acceleration
Mechanical
de-
in
during
provide
investigations.
among
combines
most
the
stabilizer
conductor
indirectly
either
laboratory
area
for
No
allowed
hensive
The
complicating
interest
Obviously,
considered
temperatures,
to
on
thiophenols,
interaction
aromatic
elevated
endurance. up
of
a v a i l -
(14).
of
directly
on
generated
temperature
degradation.
variable
on
out-
enhanced
efficient
A
oxidative
appear
the
of
is
based
or
highly
potential
point
jackpro-
data
years
limited
are
(25).
radicals
effect of
32
application.
diamine
found
and
over-
outer
presented
the
systems
Specific
beneficial
plex.
underground
the
employed
effect
(23)
insulation
A
ity
the
insulation the
adequate
by
(24).
The
providing
and
types
free
being
key
in
site.
applications
with
The
covering
paraphenylene
process.
buried.
the
protection
imply
role
the
since
of
of
is
of
surviving
Florida
in
cables
is
Gilroy PE
antioxidant
general
oxidants are
determining
limited,
thus
s t a b i l i t y
communication in
black
used
rivatives same
cables
respect.
protective
a b i l i t y
the
a
Exposure
very
containing
exposure
the
is
of
carbon
Oxidative by
light
majority
contains
door
playing
process.
Effect to
not
MATERIALS
axial
Stress.
and
Excessive the
radial axial
conductor
With
reference
deformations elongation
which
serves
Eby; Durability of Macromolecular Materials ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
as
are is an
30.
KISS E T A L .
internal high ly
the
designed
i a l
The
flow
of
either beyond
i s
with
a
e a r l i e r . fact i s
single
This that
assumptions
questionable kV/mm) l e v e l ,
(8
kv/mm)is other
i n
conclusions. a
applied
type
short
by
are
the
cable
predict
at
the
which term
generating
and i t s stress
v a l i d -
levels
could
present,
result
acceptance at
limit to
and prevent occur
stress,
despite
r e s t r i c t i v e
withstand
operating long
i n
l i f e ,
would
to
I t s conditions
data,
suitable
in
presented
used
set
and
referred
manufacturers.
tests
i n
(2)
basis
voluntary
some
failures
time
A t
5 minute a
by i t s e l f
test
using
voltage
service
controlled
service
no
associated
factors
postulating
project
although
be
parameter.
theoretical
Similarly, to
high
during
stress
widely
l i f e
shows
d i s t i n c t
i n
to
equation
i s
service
limit.
(27)
under
l i f e
without
acceptance
mortality" e s s a r i l y
present
with
stress
Tanaka
accelerated
lacks
deficiencies
areas
contributing
the
include
(6
a t i v e l y
matersuch
(20)
strength
the key ageing
from
c r i t e r i a
of
internal by
variable
(28).
in
and
one
means
during
Patsch
E l e c t r i c a l
by
i t
test
(9.)
or
correlation
as
major
at
inherent
other
95% c o n f i d e n c e
of
questionable
c r i t e r i a
the
poor-
especially
applied
by
at
due t o
i n i t i a l l y
effects.
other
projections
i t y
solved
developed
cusp
the
considered
as
the
i s
are not
whether or
reported
characterized
l i f e
may o c c u r
range
supports
section
d i e l e c t r i c
formation.
combination effect
the
on the
been
with tree above
stress cable
development
has
cross
problems
deleterious
insulation The
at
and can be
made
pattern
l i f e
deformation
temperature
long
these
internal
have
effect
or a
449
Insulation
changes.
freshly
could
is
of
limitations
the
Radial
shields
However,
design
Electrical
allowed
the weight
point.
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support.
end o f
when
as
Polyolefin
but
performance
150
of
V/mil
200
This
V/mil test
pinpoint the
"infant
after
a
r e l -
do n o t
nec-
under
f i e l d
certain
types
conditions. Higher of f u l
frequency
processes tool
to
leading study
testing to
tree
accelerates
premature formation
failure,
and
is
a
use-
(29.) .
Treeing When pated
f i e l d
lifetime
performance i n
solid
indicated
d i e l e c t r i c
lower
than
insulation,
Eby; Durability of Macromolecular Materials ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
a n t i c i close
450
DURABILITY O F M A C R O M O L E C U L A R
inspection of
of
dendritic
the
site
of
d i e l e c t r i c
established trees
and
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cables.
recovered
between
the
to
understand
of
assessing The
the
longest
this
tree
strength
of
p a r t i a l l y
observations the
nature effect
the
i t
only
nearby the
tree
than
the
longest
a
trees
phenomena ageing
is
strength the
be
to
examined
and
caused
the
remaining
level*
excessive
tree-
point
catastrophic the
where
failure.
Since
breakdown process., i t
failure
nearby
view
and
tolerable
the
in
effort
with a
process
that
of
aged
major
p r a c t i c a l l y view
destroyed
can
that
the
a
was
types
is
assumed
had
to
be
to
be
the
tree
longer f i r s t
f a i l . Types
the
of
Trees.
appearance
16).
Other
terms
like
dendrite,
of
The
some
broccoli, etc
•
(X)
Though
and
overlapping
some
four
types
of
no
The short,
very
which
is
Since
this
cal
tree
unique is
They the
hollow They
are
down.
In
interface lation weeks
corona be
fast
shield or
in
as
the
of
or
tape
to
lined a
fine
within cause
in
they the a
can
at
a
chemi-
without
higher
decomposed high
stain-
initiated
consist
hypodermic
of polymer.
syringe
stress
may
insulation initiated
conductor insulation
failure.
as
shield.
the
stresses
They
be
trees.
tree,
conductor
immediate
with
type
the and
(J5)
discharge
at
by
importance.
with
propagation
exists,
design,
voltage.
is
accepted,
chemical
observe
insulation
through
service
to
a
used
to
delta,
them
Lanctoe
broccoli
e l e c t r i c a l
channels of
and by
of
13
by
e l e c t r i c a l
limited
easy
by
insulation
months
with
frequently
resulting
actual of
colored,
inception
rate
trees,
is
s t i l l
as
described
are
described
nomenclature
water
(Figures
streamer,
controversy
is
descriptive
describe
c l a s s i f i e d
cables a
f i l l e d
Their
extremely
and
caused
connected
can
(14).
to
trees
imperfections
than
t i e ,
considered
E l e c t r i c a l ing.
bow way
dark
to
not
adequately
plume,
are
is
structures
Another
tree
dense, is
are
trees,
chemical
"tree"
the
uniform
trees
electrochemical
word
of
structures
origin.
at
to
causes
usually
these
on
accepted
breakdown
tree
initiated
of
near
Correlation
breakdown
that to
(30).
presence 13)
certain
their
is
failures
the
(Figure
of
minimizing
lowers
revealed
"trees'*
presence
generally
ing
or
the
These
possibly
cables
structures
MATERIALS
shield and
Under
at or
take
be
breakthe insudays,
laboratory
Eby; Durability of Macromolecular Materials ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
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30.
KISS E T A L .
Polyolefin
Electrical
Figure 13.
Figure 14.
Insulation
Dendritic tree
Electrochemical tree
Eby; Durability of Macromolecular Materials ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
451
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DURABILITY O F M A C R O M O L E C U L A R
Figure 15.
Figure 16.
Water tree
Bowtie tree (40 fim)
Eby; Durability of Macromolecular Materials ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
MATERIALS
30.
KISS E T A L .
conditions
Polyolefin
high
Electrical
stress
is
453
Insulation
used
to
accelerate
their
formation. Electrochemical w a t e r - f i l l e d
voids
ed
by
channels.
very
stresses age,
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(or water)
of
fine
s i g n i f i c a n t l y
i . e . ,
charge. a r i l y
i n
the
slowly
(29)
and evidence breakdown They
e l e c t r i c a l
trees.
or
iron
methylene
salts
chemical used
or
t i e at
may s t a i n (31)
have
voids
conductor aligned The
been
do
the in
(5.)
or
alkaline referred
though
the
not
necessnecessarily insulation
appearance such
they as
than
as
copper
can be
solution. to
volt-
d i s -
propagate
f u l l
chemicals
them i n
(not
They
they
diffuse
(Figure
or
stained
Electro-
water
two terms
or
to
to
the
effect
ageing,
failure
on the
service
However,
their
be
the
calculate
trees,
are
often
widely i s
of
place
below
eter.
used
1 2 kv/mm i n
In practice
small
enough
operating
to
i t
avoid
Even which
propagate
i f
weaken
not the
i n
that
less
possible
to
to
17)
is
i n i t i a t e 3.8
kv/mm i n
2 5 jam i n the i n
a
According
discharge
keep
discharges
i n
possi-
discharge
than
when direct-
stress I t
(32).
and no p a r t i a l
p a r t i a l
trees,
f a i l u r e
(Figure
to
insulation
takes
diam-
voids
voids
at
stress.
Electrochemical levels,
is
of
level
voids
p a r t i a l
voids
They
direction.
electrochemi-
level.
stress
induce
2 5 0 jam d i a m e t e r ,
and
requires
correlation to
shield.
E l e c t r i c a l
spherical
i n i -
either
contribution
and cause
inception
are to
f i e l d
on the q u a l i t y
t h e minimum
necessary
voids
their
e l e c t r i -
They
insulation
e l e c t r i c a l
formation
i n
either
connected
e l e c t r i c a l
fast
corona
discharges
this
stress
the
of
o r i g i n . not
conditions.
ly.
to
of
depends
void
p a r t i a l
i n
and hence
can propagate
above
can be
contaminants
shield
on
i n i t i a t e d ,
16)
nature
p a r a l l e l
relative
trees
premature
to
that
at
p a r t i a l
phase
bridging
Dissolved
trees
are
ble
when
chemicals,
the
and
exists
consist connect-
inception
measurable
liquid
to be
i n i t i a t e d
corona
prerequisite.
electrochemical
tiated
cal
a
can be
the
of
appear
may n o t
interchangeably. Bow
c a l
They
a r e more
blue
trees
containing
a
even
thickness.
by
of
i s
trees
may o r
below
absence
The presence
water)
cause
which
trees
slowly
immediately insulation
turn
cause
form but
do
causing
at
r e l a t i v e l y
cause the
a n d may s i r e
failures.
The
low
stress
deterioration.
failure
they
e l e c t r i c a l increasing
may
trees rate
Eby; Durability of Macromolecular Materials ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
of
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454
DURABILITY O F M A C R O M O L E C U L A R M A T E R I A L S
V o i d Diameter,
Figure 17.
nm
Calculated partial discharge inception voltage
Eby; Durability of Macromolecular Materials ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
30.
KISS E T A L .
failures slow
with
the
subject
major
l i f e
to
major
from
Institute
chemical
trees
major
ductors iments 300,000
trees
course
of
applied
were
growth. kHz
frequency
maximum
i n i t i a t i o n
of
insulation
surface.
18,
show
t i a l l y
that
with
effect i n
temperature trees, est
trees
trends.
increased
summary a
In
methods
Figure
from
600 t o
actual
fore
i t
i s
ance
of
this
a
3.4,
to
5.0
and
made
8.0 of
70 d a y s .
summarized penetrate PE
as
tree
and a t
were
i n an
60 t o
The
the i n
inner
Figure
exponenthe
appears
0 . 7 5 mm
t o
be
at
accelerating
factor
8000
70°C
the
Hz.
stress
and the
time.
of
of
the
scatter
of
specimens to
i n i t i a t i o n
to
A t
t h e number
length
Large
lengths
about
of
longdata
and
of
establish and the
simultaneously.
various 60
of
propaThe
trees
600 H z ,
but
shows minor
Hz.
the
frequency
contributor
correlation
emerged
correlates
applied
the
8000
the were
scratching
evaluation
service,
not
up
by
i n
for
stress 2,
number
from
during
to
progresses
19
increase
of
a high both
the trees
i n
drastic
effect
with
experOver
methods
temperature
as
of
length
of
Using con-
XLPE.
kv/mm
Obviously, of
rate
range
square
accelerating
length
frequency
average
the use
s t a t i s t i c a l gation
of the
i n
stress
i n
The
the
accelerated
observations
required as
electro-
(29).
conditions.
Voltage
results,
growth
and 3.4
their
mandated
time
Power
of
obtained.
induced
The
that
formation. or
and measured
tree
was
as high
studied
their
aqueous
70°C
applied
Tree
twice
The was
the
the
insulation. least
trees
the
real
quantify
round
stresses
at
and treeing
and of
was t o
i n f l u e n t i a l
voltage
i n
E l e c t r i c effects
and s t a t i s t i c a l
applied
believed
materials
f o r
Parameters.
Average
kV/mm w e r e
average
under
the data
most
6.8
work
observed
analyze
condition
the
# 1 4 AWG s o l i d
the project,
to
i s
reflect
treeing.
ageing
0 . 7 5 mm i n s u l a t i o n ,
Accelerating the
this
performed
could
treeing.
the
cable
responsible
with
and with were
of
by
evaluate
extruded
objective wires
i t
d i e l e c t r i c
funded
to
i n
parameters
coated
to
electrochemical was
Research primary
l i f e
electrochemical
qualifications,
study
455
Insulation
service
due t o
contribution
results A
Electrical
increasing
deterioration
Though
Downloaded by UNIV OF CALIFORNIA SANTA BARBARA on May 21, 2018 | https://pubs.acs.org Publication Date: April 2, 1979 | doi: 10.1021/bk-1979-0095.ch030
Polyolefin
i s
to i t s
i s
ageing.
constant, The
a p p l i c a b i l i t y
there-
s i g n i f i c to
Eby; Durability of Macromolecular Materials ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
accel-
Downloaded by UNIV OF CALIFORNIA SANTA BARBARA on May 21, 2018 | https://pubs.acs.org Publication Date: April 2, 1979 | doi: 10.1021/bk-1979-0095.ch030
DURABILITY O F M A C R O M O L E C U L A R
Figure 18.
Effect of applied stress on tree growth
Eby; Durability of Macromolecular Materials ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
MATERIALS
Downloaded by UNIV OF CALIFORNIA SANTA BARBARA on May 21, 2018 | https://pubs.acs.org Publication Date: April 2, 1979 | doi: 10.1021/bk-1979-0095.ch030
KISS E T A L .
Polyolefin
Figure 19.
Electrical
Insulation
Effect of frequency on tree growth
Eby; Durability of Macromolecular Materials ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
Downloaded by UNIV OF CALIFORNIA SANTA BARBARA on May 21, 2018 | https://pubs.acs.org Publication Date: April 2, 1979 | doi: 10.1021/bk-1979-0095.ch030
458
DURABILITY
OF MACROMOLECULAR MATERIALS
erate ageing i n laboratory i n v e s t i g a t i o n s , and p o s s i b l y to serve as a q u a l i t y c o n t r o l technique. The e f f e c t of temperature on tree growth i s complex and required s t a t i s t i c a l evaluation of a large number of samples. At 4600 Hz and 30°C, 3.4 kv/mm stress the growth rate was 5 to 8 times higher f o r PE than f o r XLPE. Increasing the temperature to 90°C lowered the rate f o r both i n s u l a t i o n s by a f a c t o r of about 2. In both cases 0.1 NCuSO^ increased the rate obtained with l o c a l (Yonkers) tap water. Figure 20 presents the trend as days to penetrate the 0.75 mm i n s u l a t i o n by the longest t r e e . S i m i l a r trends were found f o r average tree lengths. EPR, on the other hand, shows s l i g h t l y increasing rates with higher temperatures. Organic chemicals as additives to e i t h e r PE or XLPE influence tree growth. The comparison of antioxidants, peroxides, and t h e i r decomposition products was r e v e a l ing. The most commonly used c r o s s l i n k i n g agent, d i cumyl peroxide (dicup), i s t y p i c a l l y applied at about 2% l e v e l i n the c r o s s l i n k a b l e polymer. In the crossl i n k i n g process, decomposition products are generated and amount to the same 2% or s l i g h t l y l e s s . Their r e l a t i v e r a t i o s vary somewhat according to the reported values (33.) . The bulk appear to be cumyl alcohol, with lesser amounts of acetophenone and traces of