IEEE Transactions on Dielectrics and Electrical Insulation Vol. 12, No.

3; June 2005 595

Tracking and Erosion Resistance of Polymeric Materials in

Oxygen Deficient Conditions
S. Venkataraman, R. S. Gorur
Department of Electrical Engineering
Arizona State University
Tempe, 85287, AZ, USA

R. Bass and C. Rhodes

Shell International and Exploration, Inc.
Houston, Texas, USA

ABSTRACT
This paper describes two alternate procedures for evaluating the arc tracking and
erosion resistance of polymeric materials used for insulation in electrically heated
high-pressure pipes by the oil industry. The materials are subjected to electrical
stress in a high-pressure gaseous medium that can have little or no oxygen, and
conductive contaminants such as seawater. Presently, there is no procedure for
evaluating the electrical tracking performance of materials under these conditions.
A series of laboratory tests were performed using the ASTM D 2303 inclined plane
(IP) testing arrangement under ambient as well as high-pressure conditions pro-
duced by nitrogen and methane. The results indicate that the tracking and erosion
resistance of materials obtained under ambient conditions can be significantly dif-
ferent from those obtained in an oxygen deficient high-pressure media. Factors
contributing to this difference are listed and analyzed.
Index Terms Polymeric materials, tracking, erosion, liner, high-pressure,
wetting agent, hydrocarbon vapors, ambient conditions.

1 INTRODUCTION liquids, seawater and water vapor mostly as impurities.

T HE use of electrically heated pipes for oil
exploration, recovery and transport is fairly recent.
Polymeric materials are used as liners and for electrical
insulation in these pipes. Heating is one of the flow as-
surance techniques employed, especially for pipelines that
are under deep water. An electric heating system that
uses the pipe itself as a heating element is one method
that has been utilized recently, and is shown schematically
in Figure 1. Insulating materials are needed to electri-
cally isolate the energized sections from the grounded
parts. Polymers are the materials of choice for such appli-
cations due to the advantages such as cost, ease of pro-
cessing, shaping, handling and installation.
Power frequency 50r60 Hz ac supply is used to supply
the current. Source voltage that is in the range of
6001200 V is a distinct possibility. There are times when
the heater is turned off causing the temperature to re-
duce. The temperature change could produce condensa-
tion of moisture in the pipe. In addition to electric stress,
these materials are exposed to hydrocarbon vapors and
Manuscript receied on 20 September 2003, in final form 13 September 2004.
and emulsification of these components. It is estimated
that pressures up to 13.8 MPa 2000 psi. can be generated
internally in the pipes. Methane is a common gas that is
associated with oil exploration.
Insulating materials that are used in oil exploration ap-
plication are expected to possess low thermal expansion,
high chemical resistance combined with heat resistance,
high strength and dimensional stability over temperature.
Some of the materials used by the oil industry include
Polyetheretherketone PEEK., PolyamideImide PAI.,
Polyvinylidene Fluoride Kynar., polyamide Nylon. and
polyoxymethylene Delrin.. Other materials being ex-
plored for such applications include Halar Ethylene-chlo-
rotrifluoroethylene . and Natural rubber Polyisoprene..
In the combined presence of electric stress and a wet
contaminant, leakage current is promoted that results in
dry-band arcing. This can cause two modes of degrada-
tion for polymer materials. In the first mode, a track is
formed which is a partially conducting carbonaceous path
on the surface. In the second mode of degradation, there
is a progressive material loss due to formation of degrada-
tion byproducts, causing erosion of the insulating surface.

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596 Venkataraman et al.: Tracking and Erosion Resistance of Polymeric Materials in Oxygen Deficient Conditions

serve as a logical starting point. Modifications may be

needed in the testing procedure to make it suitable for
the oil industry.
It is simpler to change the experimental conditions and
perform the test under ambient conditions, provided there
is good correlation with field experience. Another alter-
native is to expose the material to a similar environment
that is high-pressure hydrocarbon gas. Both these ap-
proaches have been investigated in the present study. The
test sample and electrode geometry requirements have not
been changed from the standard procedure.

2 EXPERIMENTAL SETUP
In the present application, the voltage distribution along
Figure 1. Schematic of electric heating used in oil exploration.
the insulating materials is determined by the applied volt-
age, geometry and possibility of contact with conducting
The type of degradation that is encountered depends on fluids, of which the last aspect cannot be definitively es-
the chemical composition of the polymer and the severity tablished. Hence it is difficult to select a fixed voltage for
of discharge activity w1, 2x. evaluation. It would be useful to perform the test over a
None of the above materials are preferred for outdoor voltage range that covers both present practice as well as
high voltage applications due to their high propensity to future projections.
tracking produced by surface discharges w2x. This can be Figure 2 shows the schematic of the test procedure for
easily demonstrated by performing the ASTM D2303 In- testing in ambient conditions. This apparatus is widely
clined plane testing, which serves as a simple screening used by many laboratories and adequately described in w5x.
test to establish the suitability of the material for outdoor The picture and schematic diagram of the high-pressure
use, as well as a means of ranking the tracking and ero- set up are shown in Figures 3 and 4, respectively. The
sion resistance of different materials. liner materials can be subjected to high pressures up to
The poor tracking and erosion resistance under ambi- 20.7 MPa and hence metal containers made for this test
the middle chamber. were designed to withstand 41.4
ent conditions can also be verified by performing a calcu-
lation based on bond energies. Hc pd represents the sum MPa. The top cylinder was used as a container for storing
of all bond energies in the molecule, Hc represents sum the liquid contaminant ammonium chloride with Triton
of bond energies tending to produce carbon and H o l
represents the sum of bond energies tending to remove
carbon as volatile products. The tendency of a molecule
to form carbon is then expressed as ratio of Hc r Hc pd .
Table 1 gives the details of this calculation for a few mate-
rials. It has been observed that materials with ratios higher
than 0.40 tend to track very quickly w3x. Since the tracking
and erosion processes require the formation of arcs, it can
be assumed that the presence of oxygen in the environ-
ment plays an important role in the outcome of the test.
Presently, there is no suitable test available for evaluat-
ing the tracking and erosion performance of materials used
in the oil industry. However, the presence of conducting
contaminant on the surface of an energized insulating ma-
terial suggests that the ASTM D 2303 test method could Figure 2. Schematic of the set-up for testing in ambient conditions.

Table 1. Details of bond energy calculations.

Hc H o l Hc p d
kilocalories kilocalories kilocalories
Material rmole. rmole. rmole. Hcr Hc p d
Polyvinylidene Fluoride PVDF. 376 198 574 0.66
Ethylene-chlorotrifluoroethylene Halar . 725 396 1121 0.65
Polyamide-Imide PAI. 1320 513 1833 0.72
Polyetheretherketone PEEK. 2683 171 2857 0.94
IEEE Transactions on Dielectrics and Electrical Insulation
Figure 3. Picture of High Pressure testing apparatus.
Figure 4. Schematic diagram of the high-pressure set up.
wetting agent.. The purpose of the needle valve is to con-
trol the dripping of liquid contaminant on to the sample
surface. The bottom cylinder not shown in the schematic
drawing. is the one where all the fumes produced during
testing are accumulated and purged at the end of the ex-
periment.
The middle test chamber houses the sample along
with electrodes. The sample is held in the vertical posi-
tion. The entire chamber is tilted to 45 to give the re-
quired orientation as desired by the ASTM D 2303
method. Mounting the sample itself at this inclination in
a vertical chamber would have necessitated a larger cham-
ber. The whole setup was placed inside a cage for safety.
The liquid contaminant is a source of oxygen and it is
possible that this might be adequate to support combus-
tion of the sample. Tests with methane in a high-pressure
Vol. 12, No. 3; June 2005 597
environment need to be conducted with great care as the
gas can be explosive. For the purpose of ranking materi-
als, it may be desirable to perform the laboratory testing
in a relatively inert gas such as nitrogen, provided the re-
sults are not significantly different from those obtained
with methane. In order to investigate this possibility the
high-pressure tests were therefore performed with both
nitrogen and methane.
Field experience with PVDF material has been positive
and it is likely that this will be the material of choice in
the future. The high-pressure tests have been therefore
limited to this material. Different materials were tested
for the experiments performed under ambient conditions.
The materials used in this study are classified as pure
material implying that there are no fillers added. This
was reconfirmed using Fourier transform infrared spec-
troscopy.
3 RESULTS AND DISCUSSION
3.1 TESTS AT AMBIENT CONDITIONS AS
PER ASTM D 2303
The testing was initially performed at atmospheric pres-
sure to get baseline data for comparison. In this test vari-
ous materials were evaluated. There are two methods for
conducting the IP test. The first is the variable voltage
method. In this method the sample is initially subjected
to a value that will not cause tracking, and subsequently
the voltage is raised in 200 V steps, each step duration
being 1 h. The value of the voltage that causes tracking is
noted. The second method is the time to track method,
wherein the sample is subjected to a fixed voltage and the
time to failure is noted w2, 5x. Typically samples are tested
at 2.5 kV in time to track method.
Table 2 shows the results of the test performed under
ambient conditions using the wetting agent Triton X
y100.. Triton X-100 is a standard nonionic surfactant
and its chemical equivalent is octyl phenol ethoxylate and
has no other specific additives. It can be seen all the
samples failed in a very short time, and were charred be-
fore the primary protection system could operate. Since
some of these materials PVDF. tested have been success-
fully used in their application, this suggests that perform-
ing the test as per the recommendations of the ASTM D
2303 would be of little value for this particular applica-
tion.
For the samples that failed in the test with the wetting
agent, additional tests were performed to determine the
initial tracking voltage. The test voltage was lowered to
determine the threshold voltage for which there would be
no failure for 8 hours criteria specified in the ASTM D-
2303.. The value of 1000 V was chosen as the starting
value, based on preliminary trials and also recognizing the
fact that this level of voltage is used in the field applica-
tion. The results are shown in Table 3. Tracking oc-
curred at about 1.4 kV for the PVDF samples.
598 Venkataraman et al.: Tracking and Erosion Resistance of Polymeric Materials in Oxygen Deficient Conditions

Table 2. Summary of results of samples tested in ambient conditions with wetting agent 4 samples of each type were tested and the mean time
to failure is listed..
Test
Voltage Duration
Samples kV. minutes. Results
Polyvinylidene Fluoride 2.5 20 Failed by tracking
Ethylene-chlorotrifluoroethylene Halar . 2.5 56 Failed by tracking
Polyelectrolite 1.5 205 Failed by tracking caught fire.
Polyisoprene 2.5 45 Failed by tracking caught fire.

Table 3. Initial tracking voltage test results of PVDF samples Comparing the results in Table 4 to those in Table 2
with wetting agent under ambient conditions.
and 3, it appears that the IP test without the wetting agent
Conductivity Voltage Test Duration
ID mS. kV. minutes. Results could be suggested as a possible screening test for this
2.5 1.0 60 No failure
particular application.
1 2.5 1.2 60 No failure
2.5 1.4 20 Failed by tracking 3.2 HIGH PRESSURE TESTING
2.5 1.0 60 No failure
2 2.5 1.2 60 No failure The testing at higher pressures was limited to PVDF
2.5 1.4 60 Failed by tracking material, as this material is being used in the actual appli-
cation. Table 5 gives the list of few samples tested under
different pressure and gases. Actually six PVDF samples
were tested in high-pressure nitrogen atmosphere and four
In the testing procedure, the wetting agent is used to
PVDF samples were tested in high-pressure methane at-
create a wettable surface regardless of the material sur-
mosphere. Figure 5 shows the samples that failed during
face properties, and arcing activity is quickly established.
the test under ambient and high-pressure conditions. It
This enables us to compare the resistance to tracking and
can be seen that the failure under high pressure is less
erosion of different materials. It is of interest to deter-
severe than obtained under ambient conditions. There
mine the role-played by the wetting agent, as it is not en-
was no charring during the high-pressure test.
countered in this particular field application. The tests
were therefore repeated on a new set of samples without The following observations can be made from Table 5:
the wetting agent. Table 4 shows the results, and it can 1. Samples tested in atmospheric pressures failed in a
be seen that there is a huge difference in the time to fail- shorter time than those tested at higher pressures. The
ure, confirming the significant role played by the wetting main reason is attributed to the lack of free oxygen in the
agent. high-pressure environment.

Table 4. Summary of results of samples tested in ambient conditions without wetting agent.
Test
Conductivity Voltage Duration
Samples mS. kV. minutes. Results
Polyvinylidene Fluoride 2.5 2.5 ) 480 Passed
Ethylene-chlorotrifluoroethylene Halar . 40 2.5 ) 240 Passed
Polyamide 1 2.5 2.5 ) 480 Passed
Polyamide 2 40 2.5 480 Tracked
Polyelectrolite 2.5 1.5 90 No tracking
2.0 112 Tracked

Table 5. Summary of high pressure testing of PVDF samples.

Test
Sample Voltage Pressure Duration
numbers kV. Medium psi. minutes. Results
1 1.2 Nitrogen 2000 ) 480 Passed
2 1.25 Nitrogen 2200 480 Failed by tracking
3 1.5 Nitrogen 1000 90 Failed by tracking
4 1.5 Nitrogen 2200 ) 480 Failed by tracking
5 1.5 Methane 500 240 Passed
6 1.5 Methane 1400 ) 480 Passed
7 1.25 Methane 2200 ) 480 Passed
8 1.5 Methane 2200 ) 480 Passed
IEEE Transactions on Dielectrics and Electrical Insulation
Figure 5. PVDF sample that failed under ambient left. and high-
pressure conditions right..
2. The effect of voltage is to increase the intensity of
arcing and cause failure in a short time. This is evident
from the results of samples 2 and 3.
3. The effect of pressure on cooling of the arc can be
observed from the results of samples 3 and 4. The in-
crease in pressure from 6.9 to 15.2 MPa at the same volt-
age of 1.5 kV has increased the time of failure from 90 to
480 minutes w7, 8x.
4. The difference in the performance with different
gases can be explained in terms of electronegativity.
Methane is a more electronegative gas than nitrogen and
could be responsible for the better tracking resistance seen
with this gas. However, as there are no remarkable differ-
ences, it may be safer to perform the screening tests in the
presence of nitrogen. Testing with nitrogen is also seen to
provide conservative results the performance of the same
material can be expected to be better with methane..
Comparing the data in Table 5 with those in Table 4, it
can be seen that the results at higher pressure with wet-
ting agent are similar to those obtained under ambient
conditions without the wetting agent. It therefore ap-
pears that both these methods could be used for the pur-
pose of ranking of materials. Testing in ambient condi-
tions is obviously more convenient.
3.3 NEED FOR EARLY FAILURE
INDICATION
In actual field applications liner materials are used in-
side metal pipes and hence are not visible. Failure of the
liner and insulating material can result in a short-circuit
Vol. 12, No. 3; June 2005 599
Figure 6. Typical variation of peak of leakage current vs time for
PVDF samples that failed under ambient conditions.
Figure 7. Variation of peak of leakage current vs time for two Halar
samples that failed.
andror fire. The samples that failed under ambient con-
ditions caught fire, yet the current drawn from the supply
was not sufficient to operate the circuit breaker. It is im-
portant to be able to shut the power off in a timely man-
ner to prevent catastrophic events. If the onset of degra-
dation can be detected early enough, then it might be pos-
sible to take corrective actions. From this point of view it
is appropriate to investigate different methods of data
monitoring and analysis. A common method used for pre-
diction of degradation is the monitoring of the leakage
current pattern andror its integral, the cumulative charge
w1x. In this work, a program developed using a graphical
programming package Lab VIEW has been used to moni-
tor the peak of leakage current.
It is observed that the leakage current value is almost
the same throughout the test until before failure where
the value is observed to suddenly increase. Figures 6 and
7 substantiate this point. There was not much of intermit-
tent discharge activity observed in these samples resulting
in a pretty smooth variation of leakage current until about
failure no specific smoothing technique used.. The test
conditions for samples identified as PVDF 1 and PVDF
2 in Figure 6 have been mentioned in Table 3. The test
conditions for samples identified as Halar 1 and Halar
600 Venkataraman et al.: Tracking and Erosion Resistance of Polymeric Materials in Oxygen Deficient Conditions

2 in Figure 7 were 2.5 kV, 2.5 mS with wetting agent

using time to track method.
Hence it can be stated that mere leakage current moni-
toring may not provide sufficient time for prediction of
onset of degradation. Presently, work is performed to ex-
plore other possibilities like performing wavelet transfor-
mation of leakage current as a possible method for pre-
diction of degradation.

CONCLUSIONS
1. The standard ASTM D-2303 Inclined plane test can
be suitably modified in order to evaluate the arc tracking
resistance of materials used in the oil industry. Two mod-
ifications have been investigated in this study, and both
show promise.
2. The results indicate that the tracking and erosion
resistance of materials obtained under ambient conditions
is significantly different from those obtained in oxygen de-
ficient high-pressure media. The fact that excessive dam-
age is caused in atmospheric conditions is clearly evident
from Figure 5.
3. The arc tracking resistance of polymeric materials is
superior in a high-pressure methane environment than a
high-pressure nitrogen atmosphere.
4. There is a need for developing suitable diagnostic
tools to indicate impending failures. The use of leakage
current alone as the monitoring parameter does not yield
satisfactory results.

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