Development of LTC Monitoring Technique Coking

Development of Load Tap Changer
Monitoring Technique
Mechanism of Coking
Technical Report
Development of Load Tap Changer

Monitoring Technique
Mechanism of Coking
1001946
Technical Progress, December 2001
Cosponsor
Consolidated Edison Company of New York
4 Irving Place
New York, NY 10003
Principal Investigator
D. Chu
EPRI Project Manager

B. Ward
EPRI 3412 Hillview Avenue, Palo Alto, California 94304 PO Box 10412, Palo Alto, California 94303 USA
800.313.3774 650.855.2121 askepri@epri.com www.epri.com
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ORGANIZATION(S) THAT PREPARED THIS DOCUMENT
TJ|H2b Analytical Services Incorporated
Microlab Northwest
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Copyright 2001 Electric Power Research Institute, Inc. All rights reserved.
CITATIONS
This report was prepared by
TJ|H2b Analytical Services Incorporated
3123 Fite Circle
Sacramento, CA 95827
Principal Investigators
D. Hanson
T. Haupert
L. Savio
Microlab Northwest
Principal Investigator
R. Crutcher
This report describes research sponsored by EPRI and Consolidated Edison Company of New
York.
The report is a corporate document that should be cited in the literature in the following manner:
Development of Load Tap Changer Monitoring Technique: Mechanism of Coking, EPRI, Palo
Alto, CA, and Consolidated Edison Company of New York, New York, NY: 2001. 1001946.
iii
REPORT SUMMARY
On-load tap changers (LTC) play a major role in the reliable delivery of electric power. They are
the single biggest contributors to transformer outages. To improve reliability and extend their
service interval, utilities are adopting proactive maintenance practices using monitoring devices
and seeking new diagnostic techniques. As part of an ongoing EPRI project, EPRI and cosponsor
Consolidated Edison Co. of New York, Inc. engaged in a study of contact coking, one of the
biggest problems in LTCs. This EPRI report presents research results into the mechanism of
coke growth and suggests ways to reduce or eliminate coke formation in LTCs.
Background
Formation of carbonaceous depositscommonly referred to as cokesignificantly increases
maintenance costs and efforts on LTC components. These coke deposits cause LTCs to operate
abnormally and ultimately lead to equipment failure. Historically, most coking problems have
been managed through maintenance efforts. These efforts have traditionally included internal
inspections, cleaning, and replacement of parts. More recently, to help reduce coking costs,
monitoring and filtration schemes have been incorporated into maintenance practices. Some
design work also has been done to prevent or eliminate coking problems. Using information
supplied by end users, both original-equipment and after-market manufacturers have made
efforts to redesign LTC components. Anecdotal information indicates that design changes
intended to alleviate coking have had varied successes. Phase 1 of this study included a
preliminary evaluation of coked LTC contacts. This evaluation indicated it is possible to reveal
coke formation processes through a detailed study of deposit layers and the species found in
surrounding material. The combination of optical microscopy, electron microscopy, x-ray
diffraction, energy dispersive x-ray fluorescence, wavelength dispersive x-ray fluorescence, and
infrared spectroscopy provides the capability to identify the chemical structure of the layers, the
materials from which they were formed, and the conditions under which they were formed. This
elucidation of the stratigraphy of coke deposits could help explain how they are formed and
subsequently lead to techniques for eliminating them in LTCs.
Objective
To postulate mechanisms of coking in LTCs
To design controlled studies for verifying proposed coking mechanisms
To formulate a plan that addresses maintenance modes, monitoring techniques, operating

practices, and design specifications for reducing coke formation.
Approach
The project team examined and tested coked samples from operating LTCs to discern the
sequence of physical and chemical events that occurred to them. The team evaluated LTC
components from the component surface through the deposit to the surface of the coke
formation. They evaluated insulating fluid samples for starting materials, intermediate species,
and products that are converted to coke at the surface of coke formations. The team also
examined interactions between the fluid components and the coking surface by testing in small
cells.
Results
The samples evaluated to date indicate four basic causes for increased heating and contact
resistance. These are:
1.
2.
3.
4.
Misalignment of contacts
Design defects or use beyond design limits
Wear of components resulting in increased contact resistance
Chemical processes degrading contact performance.
EPRI Perspective
Transformer management is one of the most critical issues facing todays substation engineers.
LTCs are responsible for approximately forty percent of all transformer failures and are the
biggest single maintenance item in a substation. EPRI will continue to research new technologies
that improve LTC reliability and, at the same time, reduce LTC maintenance. This investigation
has contributed to our previously limited knowledge on coke formation in LTCs. It will be used
for further studies on reducing coking and for developing early warning monitoring techniques.
Keywords
Transformer
Load Tap Changer
Coking
Contact
Carbon
Monitoring
vi
ABSTRACT
The presence of black deposits on and around contacts in load tap changers (LTC's) has been
associated with their failure. This contract was issued to improve our understanding of the
failure mechanisms in LTC's through an analysis of the components exhibiting symptoms
suggesting degraded or degrading performance. Typically this involves the formation of black
deposits known as coke.
Thirteen parts consisting of one hundred and six individual components have been examined.
Twenty-three parts consisting of an additional four hundred and thirty-six individual components
are on hand.
The trends supported by the available evidence include the following:
1. Overheating and increases in contact resistance drives all coking in LTCs. Arcing is
important from the standpoint of creating chemical compounds that form resistive films and
add to heating problem. Multiple chemical processes cause the resistive film or the final
carbon deposit on the contact and other LTC components.
2. Coked parts can continue to function for some time.
The samples evaluated to date indicate four basic causes for increased heating and contact
resistance. These are:
1.
Misalignment of contacts,
2.
Design defects or use beyond design limits,
3.
Wear of components resulting in increased contact resistance, and,
4.
Chemical processes degrading contact performance.
Each of these mechanisms has a characteristic pattern of carbon deposition and composition.
The only one of these not adequately understood is the chemical aspect of the growth of resistive
films, item 4. This is the focus of the continuing investigation.
vii
CONTENTS
1 EVALUATION OF FAILED LTC COMPONENTS AND OIL ................................................ 1-1

Methods and Equipment..................................................................................................... 1-2
Evaluations......................................................................................................................... 1-4
UZD Reversing Switch Main Movable Contacts ............................................................. 1-4
Penn. 996 Main Stationary Contacts.............................................................................1-13
Stationary Switches ......................................................................................................1-21
UZD Bow-Tie Or Bridging Contact ................................................................................1-27
UZD Reversing Switch Stationary Contacts ..................................................................1-30
TLH Contacts................................................................................................................1-31
Analysis.............................................................................................................................1-41
Misalignment of Contacts..............................................................................................1-43
Design Defects or Design Limit Problems .....................................................................1-43
Wear of Components....................................................................................................1-43
Chemical Processes .....................................................................................................1-44
Conclusion ........................................................................................................................1-45
Analysis of Oil ...................................................................................................................1-46
Recommendations ............................................................................................................1-48
2 TEST CELLS ....................................................................................................................... 2-1
Test Method ....................................................................................................................... 2-1
3 CELL TEST RESULTS........................................................................................................ 3-1
INTRODUCTION................................................................................................................ 3-1
Conditions Selected for Test .......................................................................................... 3-3
RESULTS........................................................................................................................... 3-5
Thermal Effects ............................................................................................................. 3-6
Effects of Additives .......................................................................................................3-11
Inorganic Additives .......................................................................................................3-12
ix
Furan Additives.............................................................................................................3-13
Effects of Aromatic Compounds....................................................................................3-14
DISCUSSION....................................................................................................................3-15
CONCLUSIONS ................................................................................................................3-16
4 REFERENCES .................................................................................................................... 4-1
LIST OF FIGURES
Figure 1-1 UZD Movable Contact............................................................................................ 1-4
Figure 1-2 Finger contact from UZD LTC movable contact ..................................................... 1-5
Figure 1-3 Cross-Section of a Finger Contact from the Movable Contact of the Right
Phase of a UZD LTC ....................................................................................................... 1-7
Figure 1-4 Coke Deposit associated with the Part, 40X Magnification..................................... 1-8
Figure 1-5 Coke Deposit associated with the Part, 100X Magnification................................... 1-9
Figure 1-6 Joint Between the Silver Contact Surface and the Copper Part, 80X
Magnification ..................................................................................................................1-10
Figure 1-7 Copper Alloy Constituting the Main Body of the Part, 800X Magnification .............1-11
Figure 1-8 Cross-Section through the Center Steel Band.......................................................1-12
Figure 1-9 Carbon Deposit Near Middle of Part, Magnification 40X........................................1-13
Figure 1-10 Pennsylvania 996 Load Tap Changer (LTC) Main Stationary Contact.................1-15
Figure 1-11 Pennsylvania 996 LTC Main Stationary Contact End Plate .................................1-16
Figure 1-12 Finger Contact From a Pennsylvania 996 LTC....................................................1-17
Figure 1-13 Bar Contact Point on a Finger Contact of a Pennsylvania 996 LTC Main
Stationary Contact..........................................................................................................1-18
Figure 1-14 Knife Contact Surface on a Finger Contact of a Pennsylvania 996 LTC Main
Figure 1-15 Finger Contact From a Pennsylvania 996 LTC....................................................1-19
Figure 1-16 Bar Contact Point on a Finger Contact of a Pennsylvania 996 LTC Main
Figure 1-17 Knife Contact Surface on a Finger Contact of a Pennsylvania 996 LTC Main
Figure 1-18 Cross-Section of Contact Housing, Log 534-99 D ...............................................1-20
Figure 1-19 Cross-Section of Contact Housing, Log 534-99 D ...............................................1-21
Figure 1-20 LTC Switch Showing Metals Present ..................................................................1-22
Figure 1-21 One of the Shorter Finger Contacts Showing the Black Coating of all
Materials.........................................................................................................................1-23
Figure 1-22 Melted Tungsten at Arc Guard Surface, Magnification 400X ...............................1-24
Figure 1-23 Cross-Section of Arc Guard Showing Rough Surface, Copper, and Tungsten
Phases, Magnification 400X ...........................................................................................1-24
Figure 1-24 Transferred Tungsten, Copper Oxides, and Carbonaceous Deposits on
Contact Surface, Magnification 400X..............................................................................1-25
Figure 1-25 Black Deposit on Copper Surface, Magnification 400X .......................................1-25
xi
Figure 1-26 Cross-Section of Black Deposit on Copper Surface, Magnification 1600X ..........1-26
Figure 1-27 Cross-Section of Contact Showing Interface Between Arc Guard and
Copper Contact ..............................................................................................................1-26
Figure 1-28 Coked UZD Contact ............................................................................................1-27
Figure 1-29 Tangential Section of a UZD Contact ..................................................................1-28
Figure 1-30 Cross-Section of the Long Arm of a Coked UZD Bridge Contact.........................1-28
Figure 1-31 Cross-Section of the Short Arm of a Coked UZD Bridge Contact ........................1-29
Figure 1-32 Cross-Section of the Center Connection Fastener Location of a Coked UZD
Bridge Contact ...............................................................................................................1-29
Figure 1-33 Stationary Contact from a UZD LTC Reversing Switch Exposed to Reactive
Sulfur Present in the Oil of a Failed Unit .........................................................................1-30
Figure 1-34 Stationary Contact Exposed to Hydrogen Sulfide in a Laboratory
Environment ...................................................................................................................1-31
Figure 1-35 Coked TLH Reversing Switch Movable Contact ..................................................1-32
Figure 1-38 Cross-Section of a Coked TLH Reversing Switch Movable Contact ....................1-34
Figure 1-39 Carbon and Copper Sulfide Deposits in the Coke Layer, Magnification 400X .....1-34
Figure 1-40 Carbon and Copper Sulfide Deposits in the Coke Layer, Magnification 800X .....1-35
Figure 1-41 The Copper Surface of the Contact Showing Carbon and Sulfide Structures,
Magnification 800X.........................................................................................................1-35
Figure 1-42 Contact Alloy Showing the Copper Sulfide Phase, Magnification 400X ...............1-36
Figure 1-44 Cross-Section of a Coked TLH Reversing Switch Movable Contact ....................1-38
Figure 1-45 Pyrolytic Carbon Deposits in the Coke Layer at the Face of the Contact
Using Polarized Light, Magnification 100X......................................................................1-39
Figure 1-46 Pyrolytic Carbon, Copper Oxide, Copper Sulfide, and Copper Deposits in
the Coke Layer at the Face of the Contact Using Polarized Light, Magnification
400X...............................................................................................................................1-40
Figure 1-47 Carbon, Copper Oxide, Copper Sulfide, and Copper Deposits in the Coke
Layer at the Back Surface of the Contact, Magnification 200X .......................................1-41
Figure 2-1 One of four test cells fabricated for the project ....................................................... 2-2
Figure 2-2 Electrical grade 5/8" copper rods simulate copper LTC load carrying contact
material. A cartridge heater is used to vary the temperature of the copper. Copper
rod length increased after the first test............................................................................. 2-2
Figure 2-3 "Thumper" electrode and feed-through bushing. Used to simulate arcing in
oil. ................................................................................................................................... 2-3
Figure 2-4 "Thumper" in action. The "thumper" is activated at 15 kV and carbon starts to
develop in the oil immediately.......................................................................................... 2-3
Figure 2-5 Test cell and copper rod under oil during heating................................................... 2-4
Figure 2-6 Copper Rod Shown With Carbon Deposit. ............................................................. 2-4
Figure 3-1 A Three Dimensional Sub-Space of an N-Dimensional Study Space. .................... 3-2
xii
Figure 3-2 Test Rod ................................................................................................................ 3-4

Figure 3-3 Test Rods and Marks Left by Thermocouples ........................................................ 3-4
Figure 3-4 Interference films ................................................................................................... 3-5
Figure 3-5 Polymers................................................................................................................ 3-6
Figure 3-6 High Carbon Coordination...................................................................................... 3-6
Figure 3-7 Thermal Charts of Test Run with New Diala .......................................................... 3-7
Figure 3-8 Thermal Chart and Rod Naphthalene Added to Oil ................................................ 3-8
Figure 3-9 Effect of Temperature Cycling................................................................................ 3-9
Figure 3-10 Test With Used Oil ..............................................................................................3-10
Figure 3-11 High Temperature and New Diala .......................................................................3-10
Figure 3-12 Test Rod Exposed to Arc-conditioned Oil............................................................3-11
Figure 3-13 Film With 39PPM of Sulfur ..................................................................................3-12
Figure 3-14 Oxide Film Under Sulfur Rich Black Powdery Film..............................................3-12
Figure 3-15 Test Rods Exposed to Furfuryl Alcohol ...............................................................3-13
Figure 3-16 Films associated With Furan Test Runs ..............................................................3-14
Figure 3-17 Brittle and Cohesive ...........................................................................................3-15
Figure 3-18 Test Rod Surface Magnified 100X.......................................................................3-15
xiii
LIST OF TABLES
Table 1-1 Polynuclear Aromatic Hydrocarbons by Modified EPA Method 8270 (SIM) ............1-47
xv
EVALUATION OF FAILED LTC COMPONENTS AND

OIL
The presence of black deposits, commonly known as coke, on and around the contacts in load tap
changers (LTC's) has been associated with their failure. This contract was issued to improve our
understanding of the failure mechanisms in LTC's through an analysis of the components
exhibiting symptoms suggesting degraded or degrading performance. Typically this involves the
formation of black deposits.
LTC samples were examined and tested to discern the sequence of physical and chemical events
that has occurred to them. LTC components were evaluated from the component surface through
the deposit to the surface of the coke formation. Insulating fluid samples were evaluated for
starting materials, intermediate species and the products that are converted to coke at the surface
of the coke formations. Interactions between the fluid components and the coking surface were
examined.
A principle objective of this part of the study was to generate data enabling us to postulate a
mechanism for the development of "coke" deposits in LTC's.
The mechanisms producing "coke" have been an area of extensive research for over a hundred
years. With the development of high performance applications of pyrolytic carbon materials
("coke") our ability to assess the nature and history of pyrolytic carbon deposits has progressed
rapidly. The technical definition of coke is given below:
Coke:
Synthetic carbon formed by the rupturing of the carbon-hydrogen bonds and

the removal of hydrogen to produce a plastic or nematic liquid crystalline
mesophase material. On continued heating a pronounced graphitic structure
results1.
The carbon-based materials that are found on LTC components include materials called sludge
(highly viscous deposits), coke (defined above), char (free radical carbon condensation
reactions), and pyrolysis products (aggregated soot). They all share the properties of being black
and of containing carbon. The last three are always associated with the presence of heat or high
energy but sludge can be created in low energy environments over long time periods or in higher
energy environments over shorter intervals of time. Basic background information on these
materials is available in a number of reference materials1, 2,3,4,5,6,7,8,9,10,11. The characterization of
the carbonaceous materials formed in equipment that is part of the electrical power industry can
be approached using the allotropes and combination of allotropes of carbon in the deposit as
suggested by Heimann, Evsyukov, and Koga12 with their 105 references for clarification. At this
1-1
Evaluation of Failed LTC Components and Oil
stage of the study it was sufficient to determine the optimum approach to the analysis of these
materials and to evaluate the deposits on selected samples. This report documents the analytical
approach and the results of applying that approach to the evaluation of coke deposits.
Methods and Equipment

Samples were first examined and photographed as received. Some of these parts were received
with samples of the oil from the LTC collected at the time the component was removed. The
macroscopic photographs were taken using a Polaroid MP4 photographic stand with either a
Polaroid digital camera or a Pentax 35mm single lens reflex camera. The initial examination of
the samples was performed at low magnification under a stereoscopic microscope. After original
photographic documentation and examination under the stereoscopic microscope a sampling plan
was prepared for each part. The sampling plan addressed how materials would be removed, the
order of their removal, the mechanism of their removal, and subsequent processing prior to
analysis.
The principle analytical tool for the evaluation of solid materials has been the light microscope.
Three basic light microscopes have been used. These are:
1. Stereoscopic Microscope:
a) General Use: Nikon SMZ-1B
b) Photographic Stereoscope: Bausch and Lomb Stereozoom 7 with Photographic
attachment.
2. Reflected Light Research Microscope: Nikon Optiphot-Pol optimized for reflected light with
150 Watt Epi-illuminator, full reflected light cross polarization capability with rotating
analyzer and rotating polarizer, compensator plates, reflected Nomarski system, reflected
light brightfield/darkfield objectives, transmission system with brightfield/darkfield and
oblique illumination systems, transmitted polarized light, trinocular head, and
photomicrographic system.
3. Transmitted Light Research Microscope: Nikon Optiphot-Pol optimized for transmitted light
with 150 Watt fiber optic ring epi-illuminator and fiber optic epi-oblique illuminator for top
illumination, full transmitted light cross polarization capability with rotating analyzer,
rotating polarizer, compensator plates, circular polarization system, transmission
brightfield/darkfield and oblique illumination systems, phase contrast system, trinocular
head, and photomicrographic system.
The light microscope is a very powerful analytical tool for the characterization of a wide variety
of materials15. Carbonaceous deposits and the interface between these deposits and the
underlying metal were ultimately characterized and identified using the light
microscope2,4,8,10,16,17,18,19,20. Characterizing metals and surface corrosion films is an extension of
common ore petrography21,22. The characterization of carbon deposits using light microscopy
1-2
and its unique ability to document the nature of these deposits was particularly useful in this
study. All of the light microscopical analysis was performed by E. Russ Crutcher of Microlab
Northwest, Redmond, Washington.
To supplement the analysis of these coke deposits, two additional pieces of equipment were
used. The first was an electron microprobe for elemental analysis. The second was an x-ray
diffractometer for crystallographic analysis. Both of these instruments are owned and operated
by Bart Cannon of Cannon Microprobe in Seattle, Washington. This work was done under the
auspice of E. Russ Crutcher of Microlab Northwest, Redmond, Washington.
The electron microprobe used was a modified ARL SEMQ. It was equipped with six wavelength
dispersive x-ray spectrometers (WDS) and a Kevex energy dispersive x-ray spectrometer (EDS).
This system has a beam coaxial light optical system for the evaluation of cathodoluminescence
and for observation of color contrast in the sample being analyzed. The sample was imaged with
a television rate backscatter electron detector. SEM images were collected using Digisem3
software and hardware. This system was used to characterize structure below the resolution limit
of the light microscope (less than 0.5 micrometers) and to create a deep field view of structure
that was more three dimensional than could be usefully imaged using light microscopy23. The
principle use of the electron microscope was the elemental analysis of phases seen in or
associated with the carbon deposits on various surfaces24. Standard chemical handbooks contain
all of the energy and wavelength signatures for the elements33. A full battery of primary
standards was coloaded into the microprobe for standardization and comparison. Microchemical
tests under the light microscope were used to gain information on more complex organic and
inorganic functional groups as required34,35.
The X-ray diffractometer used was a GE XRD-6 with modernized electronics. X-ray diffraction
analysis was very useful for characterizing the nature of the crystalline units that develop with
exposure to heat25,26,27,28,29. X-ray diffraction was also an excellent tool for the characterization
of corrosion products and other crystalline materials that were present30,31,32. Samples were
examined as intact films and as crushed powders, depending on the nature of the deposit.
The work completed at this point includes a gas chromatography/mass spectrometer (GC/MS)
analysis of an oil and a brown solid precipitate. Infrared spectroscopy has not been fully utilized,
though in other studies it has been demonstrated to provide essential data in the determination of
the reactions leading up to the formation of carbon deposits8,36,37,38. This analysis is being
performed at Oregon Analytical Services in Portland, Oregon under the direction of Stan Cassel
under the auspice of E. Russ Crutcher of Microlab Northwest. Dissolved gases analysis39,40,
furfural analysis, and the basic oil characterization was performed in the laboratories of
TJ|H2bAnalytical Services.
The solid materials in the oil were collected by filtering a portion of the oil or by centrifuging
part of the oil. Particles centrifuged from the oil were mounted directly on a microscope slide
using Cargille 1.605 Melt Mount medium. If the particles were collected by filtration, an
alumina membrane filter was used. This filter medium has a refractive index of about 1.605. By
mounting the filter with its particles in Cargille 1.605 Melt Mount, the filter disappeared and the
particles could be examined without interference.
1-3
Evaluations
In this section the materials are presented by component type. Components of various types
have been received over the last few years. There is no special order in which the different types
of components are presented.
UZD Reversing Switch Main Movable Contacts
Figure 1-1
UZD Movable Contact
A set of main movable contacts from each of three phases was received in December of 1997.
They were designated as Microlab NW Log 1117-97. The right and left phases exhibited the
most coking. . The center phase had only a thin, incomplete layer of soot as can be seen in
Figure 1-1. Visually, the coke consisted of a porous layer of oil soaked char and soot Figure 1-2.
1-4
Figure 1-2
Finger contact from UZD LTC movable contact
The contacts were examined under the stereoscopic microscope to evaluate the distribution of
surface deposits and to assess the condition of the parts. The black layer was very porous and
crumbled on handling. It covered nearly the entire finger contact and the alignment pins. Some
arc scaring was seen on the contact surfaces.
Samples of the black deposit from one of the left phase finger contacts and from one of the
center phase finger contacts were sent for x-ray diffraction analysis. The left phase deposit
exhibited some crystalline structure but the pattern was too complex to attribute to a graphitic
compound. Small, but discernable peaks were seen at 4.58, 4.12, 3.29, 3.08, 3.02, 2.58 and 2.33
angstroms. The sodium azide test for sulfides was positive for the black layer but negative when
the black layer was gently scraped away, exposing a brown layer. This brown layer is discussed
in more detail for the center phase contact because that part didnt have to be handled as much to
expose the layer. Scraping the coke away from the surface on the right and left phase parts
damaged the film in some areas limiting some of the tests that could be performed on the brown
film of these samples.
The surface deposit on the center phase parts was a light brown in color. Interference colors
were evident in thicker areas of the film. A sodium azide test of the film for sulfides was
negative. Concentrated nitric acid had no effect on the film. Had the film been an oxide of
silver, the film would have dissolved. When exposed to dilute hydrochloric acid, the film lifted
from the silver substrate. The refractive index of the film was in the range of 1.55. This
indicates a material without significant amounts of a heavy metal. This is consistent with an
organic, polymeric film. The interference colors indicate a film thickness of from 0.07 to 0.2
micrometers. The interference colors are dominated by thin film interference effects and do not
indicate the color of the chemical forming the film. The center phase black deposit showed no xray diffraction peaks.
One of the right phase contacts was mounted in resin for metallographic analysis. The contact
was cut across the steel band, and then the tapered end was cut longitudinally (Photographs 3 and
9). These sections were polished in order to examine the surface films and the base materials
1-5
(Photographs 4, 5, 6, 7, 8, and 9). The elemental and compound analysis of the base materials
indicated pure silver, a copper/copper oxide alloy, and carbon steel. Examination of the part
under the microscope indicated that the entire copper surface, even under the steel band, had
been silver plated. The silver contact at the tapered end of the part had been brazed into place,
and a layer of copper/silver intermetalic had formed between the copper and the silver.
The carbon deposit consisted of a loose network of flakes and irregular granules forming an
insulative layer around the part. Photographs 4 and 5 illustrate the loose structure of this deposit.
Photograph 9 shows a more consolidated region of carbon deposit but it is still very loose and
full of voids. The temperatures here did not seem to exceed 800 degrees Fahrenheit (F), though
they did exceed 450 F. Reflected polarized light detected no organized crystal structure, but the
reflectivity of some of the granules in the deposit indicated a compact structure as opposed to an
aggregated soot (Photographs 5 and 9). The uniformity of the deposit over the surface of the part
suggests a similar temperature over the entire part. The uniformity of temperature regardless of
the current cross-section and resistance heating locations indicates inadequate cooling of the part
in service. The back of the center phase contacts shows flow lines, which indicate fluid flow
around the parts when it was warm. This apparent higher rate of flow may have kept the part
cooler, which resulted in less coking.
The active area of contact was evident by the clean silver surface on the contact pin of each
contact. The area of contact was different for each contact and never included the entire contact
area. On the center phase contact a horseshoe-shaped area was the active area of contact and
there were arc scars to the inactive part of the contact surface. There was little evidence of
abrasion on the center phase contacts. The right and left phase contacts exhibited significant
amounts of abrasion on the contact surfaces. Carbon had been smeared into the silver of the
right and left phase contact surfaces. In general, the center phase parts appeared to have been
used far less than the other phases.
1-6
Steel Band
Spring Cavity
Photo 4 and 5
Photo 7
Main Body of Contact
Main Body of
Contact
Copper
Rivet
Pin
Cavity
Photo 6
Silver Contact
Figure 1-3
Cross-Section of a Finger Contact from the Movable Contact of the Right Phase of a UZD
LTC
Photo numbers correspond to Figures, example photo 4 is Figure 1-4.
This is a section through the tapered end of one of the right phase contacts. The silver pin
contact is shown in the right part of the contact. The division in the center between the two
copper pieces is the hole through which one of the pin guides fit in the assembled contact. The
larger part of the hole (upper) is for the steel spring. This photograph was taken before final
polish. The carbon layer mixed with the resin when this part was mounted for sectioning. Swirls
of carbon can be seen in the resin. This material became detached as resin was gently added to a
mold containing the part. The areas with the thickest carbon deposits tended to be the most
inaccessible regions, cavities or depressions in the surface of the part. The deposit in one of
these cavities is shown in the next two photographs. The area of the photographs corresponds to
the area in the red rectangle labeled "Figures 1-4 &1-5". There were a number of voids in the
bond between the silver contact and the copper part. Some of these are shown in Figure 1-6.
Figure 1-7 shows some of the copper/copper oxide alloy microstructure for this part.
1-7
Resin
Free Carbon Particles
Voids
Carbon Deposit
Copper
Copper
Brazing Metal
Figure 1-4
Coke Deposit associated with the Part, 40X Magnification
This shows the distribution of the carbon deposit in the cavity designated in Figure 1-3.
Note the carbon particles that have floated free into the resin. Many of the voids in the
carbon deposit can be seen here.
1-8
Carbon
Figure 1-5
Coke Deposit associated with the Part, 100X Magnification
This photograph was optimized to show the structure of the carbon deposit. The lighter
colored pattern is the carbon deposit. It consists of a very lacy network of small flakes
and irregular granules. The smooth areas are voids that have been filled with resin. The
rounded voids are air pockets that were trapped as the resin cured. The irregular voids
are voids that were sealed, and the resin could not enter to fill them.
1-9
Silver Contact
Brazing Metal
Void
Copper
Void
Figure 1-6
Joint Between the Silver Contact Surface and the Copper Part, 80X Magnification
The silver contact was brazed to the copper main body of the part. The braze joint had a
high proportion of voids.
1-10
Copper Oxide
Figure 1-7
Copper Alloy Constituting the Main Body of the Part, 800X Magnification
Reflected cross-polarized light was used here to bring out the red internal reflection of the
copper oxide (Cu2O) phase of this copper/copper oxide alloy.
1-11
Photo 9
Figure 1-8
Cross-Section through the Center Steel Band
The carbon layer can be seen all around the exterior of the steel band as well as on the
exposed copper in the lower part of the photograph. The fact that the carbon layer was
similar everywhere, regardless of substrate material or cross-section area indicated
inefficient cooling as the cause for this deposit. The actual point of contact the carbon
coating was not any thicker nor did it indicate any elevated temperature. This indicates a
slow steady heating during use.
1-12
Copper
Carbon
Resin
Figure 1-9
Carbon Deposit Near Middle of Part, Magnification 40X
This seems to be a region of very poor circulation where the carbon can accumulate. The
carbon layer is more consolidated at this location but it is still full of void and exhibits no
evidence of temperatures higher than those seen anywhere else on the part. No
crystallinity of the carbon deposit was evident.
Penn. 996 Main Stationary Contacts

Four lots of Pennsylvania 996 main stationary contacts were received. The first lot consisted of
a single contact mark "Transformer #1 LTC, Z Left, RIGHT". A small steel spring was received
with this contact. The spring was marked "TR-1, W 110th St., Z Switch, Left Upper Stationary
Contact. These two parts were included in Microlab NW sample Log #034-98 and were received
in February of 1998. The finger contacts, spacers, links, insulating panels, pins, and springs had
been removed from the contact. The copper surfaces of this part were a reddish purple as a result
of an interference film on the copper. A sodium azide test was negative indicating that the
coating was not a copper sulfide. The interference color indicates a thickness of about one
hundred nanometers. There were thin black deposits around the rocking position where each
finger contact would have contacted the contact bar. These residual carbon deposits were
heaviest on opposite ends of the opposing bars. This suggests a difference in contact pressure
that may have been due to a slight misalignment of the movable contact blade relative to the
stationary contact. There was a black residue at the ends of each bar contact.
The second lot consisted of three complete main stationary contacts with a sample of oil from the
LTC. These samples were all designated as Microlab NW Log #138-98. The three contacts
were marked as Z Side Center, Y Side Middle (Center), and Y Side Right. The Z Side
Center contact was heavily coked. The Y Side Middle sample showed much less coking with
1-13
selective carbon staining. Some of the finger contacts where black while others where only tan
in color. The Y Side Right sample (see Figure 1-10) had the least amount of carbon deposits.
The end plate was dark with a light tan colored dust (see Figure 1-11). The finger contacts of this
sample were a light tan in color (see Figure 1-12). The bar contact region on the back of the
finger contact showed wear and some light coking (see Figure 1-13). The surface of the finger
contacts that met the knife contact exhibited multiple impact or slippage lines in the silver plated
surface for all of the finger contacts (see Figure 1-14). This pattern suggests that the contact
tension varies as the knife contact engages. This could indicate a wear-induced lack of contact
pressure. Some light coking around this surface was also evident. A sodium azide test of the
finger contact was negative for sulfide.
The third lot consisted of six complete main stationary contacts and a sample of oil. These
samples were all designated as Microlab NW Log #408-98. All of these parts exhibited varying
degrees of moving contact miss-alignment and coking. The most coked part was assigned the
designation of A. The least coked part was assigned the designation F. The part where the
contact striations ran only along one edge of the finger contacts where the most coked. The least
coking was on the part showing contact striations evenly over the entire face of the finger
contact. The sodium azide test was negative for sulfides on all parts.
The fourth lot consisted of six complete main stationary contacts and a sample of oil from the
LTC. These samples were all designated as Microlab NW Log #534-98 and were further
assigned letter designators. The contact D has been examined in detail. Contact D exhibited
the most discoloration on the finger contacts (see Photograph 15). All of the individual finger
contacts of the stationary contact were a light tan color and were showing some wear. The
surface of the finger contact that rocked on the bar contact was worn through to the copper under
the silver plate (see Figure 1-16). Some carbon deposits had developed around this area, and
some of the carbon had been worked into the contact surface. The silver plate of the finger
contacts where they met the knife contact was worn through to the copper (see Figure 1-17).
Closer to the tip of some of the finger contacts was a row of arc pits. The arc pit band had
generated particles that roughened the contact and that were smeared into the scuffing zone and
final contact region. Heating had generated some carbon deposits around the final contact
position. This carbon was also smeared into the contact zone. The tan film responded strongly
positive for sulfides when the sodium azide test was applied. The coating was confirmed to be
silver sulfide. Cross-sections have been prepared of the finger contact housing, the main body of
the stationary contact (see Figures 1-17 and 1-18). Some design differences are indicated. The
basic materials; the bar alloy, the copper alloy, and the brazing compound, are all the same.
More coked parts will be cross-sectioned, and these
Materials were compared to assess evidence of heating.
1-14
Fiberglass/Epoxy
End Plate
Finger Contacts
Pins in
Mounting
Slots
"U" Shaped Housing
Figure 1-10
Pennsylvania 996 Load Tap Changer (LTC) Main Stationary Contact

The main stationary contact consists of a copper U-shaped conductor housing in contact
with twelve individual finger contacts that physically meet the movable knife contact. The
finger contacts rock against a silver alloy bar brazed into the copper housing. Contact
pressure between the finger contacts and the bar is maintained by springs mounted
between opposing sets of finger contacts. The finger contacts are held in position by two
pins each and metal spacers between adjacent fingers and between the fingers and the
end plates. These pins are secured in a slot in the end plates to allow for the rocking of
the finger contacts. The end plates on either side of the housing are fiberglass/epoxy.
1-15
Figure 1-11
Pennsylvania 996 LTC Main Stationary Contact End Plate
This is a removed end plate to show the slot mount for the positioning pins. In this
version of the part, an additional hole has been cut in the center to facilitate the circulation
of oil through the contact region. Note the brown deposit on the surface. The
composition of the end plate has also changed. This is from the parts designated as
Microlab NW Log 534-99.
1-16
Bar Contact Point
Knife Contact Surface
Figure 1-12
Finger Contact From a Pennsylvania 996 LTC
This is a finger contact removed from a Pennsylvania 996 LTC main stationary contact.
The small black lines are fingerprints from handling the part. The reddish tan color of the
part is a thin-film interference effect. The silver plated copper part would appear silver but
for a thin polymer coating. This is from Microlab NW Log 138-98.
1-17
Figure 1-13
Bar Contact Point on a Finger Contact of a Pennsylvania 996 LTC Main Stationary Contact
This is the bar contact point of the finger contact shown in Figure 1-12. The notch is to the
right side in this photograph. Carbon builds up on either side of the contact line. More
carbon collects in the notch, an area of restricted circulation. Carbon can be seen pressed
into the silver of the contact.
Stutter Lines
Final Contact Point
Figure 1-14
Knife Contact Surface on a Finger Contact of a Pennsylvania 996 LTC Main Stationary
Contact
This is the knife contact surface of the finger contact shown in Figure 1-12. The knife
contact would move from the right to the left in this photograph when it engaged the
contact. The stutter lines (vertical white lines) show locations where the knife temporarily
stopped, relative to the finger contact, before sliding forward again. This suggests a worn
stationary contact that was not performing optimally and that tension was not constant.
This could lead to poor contact pressure.
1-18

Knife Contact Surface
Bar Contact Point

Figure 1-15
Finger Contact From a Pennsylvania 996 LTC
This is a finger contact removed from a Pennsylvania 996 LTC main stationary contact but
with a slightly different design than that seen in Figure 1-12. The reddish tan color of the
part is a thin film interference effect. The silver-plated copper part would appear silver but
for a thin silver sulfide coating. Although the coating appears the same as that in Figure
1-12 the chemical composition is quite different. The pattern on the left of the part
suggests that the film forms most efficiently when the spring is compressed and the part
is active and warm. This finger contact is from Microlab NW Log 534-99.
Figure 1-16
Bar Contact Point on a Finger Contact of a Pennsylvania 996 LTC Main Stationary Contact
This is the bar contact point of the finger contact shown in Figure 1-15. Carbon builds up
on either side of the contact line. Carbon can be seen pressed into the silver of the contact
on the right side of band, and the silver is worn away on the left side exposing the copper
base metal.
1-19
Figure 1-17
Knife Contact Surface on a Finger Contact of a Pennsylvania 996 LTC Main Stationary
Contact
This is the knife contact surface of the finger contact shown in Figure 1-15. The knife
contact would move from the right to the left in this photograph when it engaged the
contact. The silver-plate layer is completely worn away at the point of final contact. Wear
of the contacts could reduce contact pressure.
Figure 1-18
Cross-Section of Contact Housing, Log 534-99 D
1-20
Figure 1-19
Cross-Section of Contact Housing, Log 534-99 D
The main stationary contacts in this set have a slightly different design. Presumably the
design change was made to improve performance. It has not been determined which was
the earlier design at this time.
Stationary Switches
Two stationary switches were received in March of 1998 and were designated as Microlab NW
Log #075-98. Two of the parts were coated with a dark, loose deposit. Under this loose coating
was a tougher hard dark coating that was very thin (Figure 1-20). The stationary switch offered
an opportunity to examine the effect that different alloys had on the formation of the coke. On
this one unit we had tungsten, copper, silver/zinc/copper brazing alloy, iron, and aluminum.
Each finger of the contact was tipped with a copper/tungsten powder metallurgy arc guard. This
was bonded to the copper contact surface with a silver/zinc/copper brazing alloy. On the back
was an iron support bar. The contact finger was fixed to an aluminum mounting block. An
examination of the arc guard under the stereoscopic microscope showed arc scars and erosion of
the arc guard. At higher magnification local regions of melted tungsten could be seen (see
Figure 1-22). The active surface of the arc guard was very rough (see Figure 1-23). Large grains
of tungsten and copper protruded from this surface and would both abrade the knife contact
and/or could be worn away from the surface of the arc guard. The removal of these large grains
would result in rapid erosion of the arc guard and a degrading of the contact surfaces due to their
displacement into the final contact zone (see Figure 1-24).
The copper surfaces were coated with a layer of dense copper oxide (see Figures 1-25 and 1-26).
X-ray diffraction analysis indicated cuprite and tenorite as the main crystalline phases. Microchemical analysis detected a thin film of copper sulfide under the oxide and sulfides present in
the carbon layer.
1-21
X-ray diffraction analysis of the various carbon layers on the surface of the copper showed early
development of the 100-graphite plane. This would suggest temperatures over 800 degrees
Fahrenheit were reached at times. No crystal structure in the carbon layers was indicated for the
deposits on the aluminum or iron surfaces.
An examination of the brazing compound between the arc guard and the copper conductor
indicated the growth of a silver/copper intermetallic phase. This phase grows slowly at
temperatures above 450 F and practically not at all for lower temperatures. The amount of
growth at any time shows the integrated, time-weighted total exposure of the part to temperatures
over 450 degrees Fahrenheit (see Figure 1-27).
Cu/W
Cu
Fe
Al
Figure 1-20
LTC Switch Showing Metals Present
This switch had been covered with a carbonaceous deposit, much of which was very
fragile and was destroyed in the process of cleaning the oil from the part prior to shipping.
Some of the carbonaceous deposit remains and all of the parts are covered with a black
deposit (see below).
1-22
Iron
Cu
Cu/W
Copper Sheet
(a) Side View of Finger Contact
25, 26
27
22, 23
24
(b) Contact Surface of the Finger Contact

Figure 1-21
One of the Shorter Finger Contacts Showing the Black Coating of all Materials
The location of the following photographs is shown on this view of the contact face of this
finger contact.
1-23
Figure 1-22
Melted Tungsten at Arc Guard Surface, Magnification 400X
The bright white spot in the upper center of this photograph (red circle) is an arc scar on a
tungsten grain on the arc guard. Tungsten melts at 3100 degrees Celsius (6100 degrees
Fahrenheit).
Cu
W
Figure 1-23
Cross-Section of Arc Guard Showing Rough Surface, Copper, and Tungsten Phases,
Magnification 400X
The black area at the top of the photograph is the surface of the arc guard that contacts
the knife contact. It is extremely rough and large grains of metal can be torn from its
surface. Large grains of both copper (Cu) and tungsten (W) are present at this surface.
1-24
Copper Oxides and Carbon
Copper Oxides and Carbon
Figure 1-24
Transferred Tungsten, Copper Oxides, and Carbonaceous Deposits on Contact Surface,
Magnification 400X
The copper contact surface of the finger contact is coated with copper oxides, carbon, and
tungsten particles (red circles). The tungsten particle had been carried by the knife
contact onto and into the surface of the copper conductor.
CuO
Cu2O
Figure 1-25
Black Deposit on Copper Surface, Magnification 400X
The black deposit consists of a dark black carbon layer, a dark gray layer of tenorite
(CuO), and a red layer of cuprite (Cu2O). A sodium azide test for copper sulfide was
positive for both the area below the cuprite layer and for the carbon layer.
1-25

Tenorite
Cuprite
Mounting Resin
Copper
Figure 1-26
Cross-Section of Black Deposit on Copper Surface, Magnification 1600X
The layers always formed in the same sequence; a thin sulfide layer followed by the red
cuprite layer, then the tenorite, followed by a carbon deposit. The sulfide layer was too
thin to be seen in cross-section.
Copper
Intermetallics
Cu/W Arc Guard
Figure 1-27
Cross-Section of Contact Showing Interface Between Arc Guard and Copper Contact
The arc guard was bonded to the copper conductor with a brazing compound of silver,
zinc, and copper. A copper and silver intermetalic compound grew with time when the
1-26

contact temperature exceeded about 450 degrees Fahrenheit. The development of the
intermetalic can be used as an indication of the thermal history of the part.
UZD Bow-Tie Or Bridging Contact

Only one bridging contact was received for evaluation. It was part of the set of samples received
in March of 1998 and was included in the set of materials designated as Microlab NW Log #07598. The bridging contacts from Pennsylvania 996 LTCs have been reported as having severe
coking problems. The design is susceptible to heating problems and contact pressure problems;
both of these result in increased temperature and the subsequent pyrolysis of oil.
The contact is shown in Figure 1-28. Although the coke deposit is thick on this part, it is very
open and easily disturbed (see Figure 1-29). The sample was mounted and sectioned through the
contact points and through the position of the clamping bolt (see Figures 1-30, 1-31 and 1-32).
No crystallinity was evident and the reflectivity of the coke was very low. This indicates a low
temperature soot type deposit. The temperatures indicated are under 400 C (750 F). The
deposit on this part was similar to that seen on the reversing switch main movable contacts (Log
1117-97).
Cross-Sections
Figure 1-28
Coked UZD Contact
The carbon deposit on this part was uniform over the entire surface. Cross-sections were
cut in three areas as indicated. The tangential polish shown below is indicated by the red
circle.
1-27
Figure 1-29
Tangential Section of a UZD Contact
Note how the carbon layer material drifted into the mounting resin as black fragments and
streaks. The carbon layer was very loosely associated with the part and separated easily.
The tangential section exaggerates the boundary layer for closer examination. A thin
layer of a dark orange brown film was seen on the surface of the silver plate. This
appeared to be a silver oxide film. No sulfide was detected, but the material reacted with
iodine in solution. The reflectivity of the carbon is lower than that seen in the movable
contact of Figure 1-5. The thermal exposure appears to be less than 400 degrees
Fahrenheit.
Figure 1-30
Cross-Section of the Long Arm of a Coked UZD Bridge Contact
The carbon coating exhibited characteristics of temperatures that were less than 450
degrees Fahrenheit.
1-28
Figure 1-31
Cross-Section of the Short Arm of a Coked UZD Bridge Contact
degrees Fahrenheit.
Figure 1-32
Cross-Section of the Center Connection Fastener Location of a Coked UZD Bridge Contact
degrees Fahrenheit. The deposit was a bit more reflective in the hole for the fastener
suggesting slightly higher temperatures here than in the areas of open exposure to the oil.
The temperatures were still rather low.
1-29
UZD Reversing Switch Stationary Contacts

These samples were received in August of 1998 and designated as Microlab NW Log #229-98.
One of the contacts had been removed from a UZD LTC (see Figure 1-33). The contact was a
uniform tan color and responded strongly to the sodium azide test for sulfides. The other contact
had been exposed to elevated levels of hydrogen sulfide (see Figure 1-34). The difference in
appearance is typical of a concentration effect. In the LTC oil the exposure to reduced sulfur is a
diffusionally controlled process resulting in low-level exposure over the entire part. More
reactive sites on the part cannot react with the sulfur more strongly because there is so little
sulfur present. The result is a uniform reaction rate over the entire exposed surface. Exposure to
elevated sulfide levels selects for the more reactive sites on the contact. The result is a splotchy,
irregular deposit.
Figure 1-33
Stationary Contact from a UZD LTC Reversing Switch Exposed to Reactive Sulfur Present
in the Oil of a Failed Unit
Sulfur has been used to inhibit coking in the petroleum industry because it interferes with
the lattice fitting of ethylene and acetylene on iron and nickel surfaces. That doesnt work
in LTCs because lattice fitting with gas phase molecules is not a dominant mechanism in
the formation of coke in these environments. Silver is more noble than copper and the
sulfur is transferred to the copper forming copper sulfide. Copper sulfide increases
contact resistance in the same way as copper oxides. The increased heating then
produces coke.
1-30
Figure 1-34
Stationary Contact Exposed to Hydrogen Sulfide in a Laboratory Environment
The form a reaction product takes on the surface of a part is dependent on the way in
which the reactants are introduced. Exposure to low concentrations of the reactant will
tend to produce an even coating as seen above. Exposure to higher concentrations of the
reactants will tend to localize the reactions as seen here. This was a test submitted by
another laboratory for evaluation and is included here to illustrate the difference between
a real world exposure and an attempted laboratory simulation.
TLH Contacts
Four sets of TLH 21 reversing switch movable contacts have been received. The first set was
received in April of 1999 and was designated as Log 475-99. It exhibited a heavy, consolidated
coke build-up (see Figure 1-35). The contact surfaces showed the greatest buildup and
consolidation with the leads following (see Figures 1-36 and 1-37). The coke around this unit
was reportedly much larger than is represented here but much of it consisted of a fragile leafy
structure that didnt survive the cleaning of the part prior to shipping.
The second set of reversing switch movable contacts was also received in April of 1999 and was
designated as Log 487-99. This set had the same outward appearance as the samples received
above (Log 475-99). One of these switch contacts was mounted and cross-sectioned for analysis
(see Figure 1-38). The deposit consisted of a carbon matrix permeated with a copper sulfide
phase (see Figures 1-39 and 1-40). The carbon layer was not well crystallized and varied in
density through the deposit. The copper sulfide appeared to be predominantly chalcocite (Cu2S)
with smaller areas of covelite (CuS). The distribution of the copper sulfide was in a pattern
referred to as Liesegang Rings41. These rings are typical of systems with ions diffusing from
opposite directions, the reaction product forming where the ions meet within the carrier medium.
In this case the carrier medium is carbon and the ions are copper and sulfur. The distribution of
the Liesegang Rings indicates copper ions coming from the copper contact and sulfur ions
1-31
coming from the oil or outer layers of the carbon. An examination of the immediate surface of
the copper, however, indicated a significant amount of sulfur was present at that surface (see
Figure 1-41). The copper itself was a copper/copper sulfide alloy (see Figure 1-42). This
particular alloy, #147, contains about 1.5% copper sulfide as produced. The immediate surface
of the contact is sulfur enriched, but it also contains significant amounts of carbon. At this time
the reactions occurring at the surface of the contact are unclear. Corrosive attack,
oxidation/reduction, dissolution and solution effects, diffusion, and other phenomena all seem to
be involved. There is no convincing evidence for temperatures above 2000 Fahrenheit (1100
Celsius), though temperatures in excess of 800 degrees Fahrenheit are clearly indicated by the
consolidation of the carbon layer.
The third set of reversing switch movable contacts was received in June of 1999 and was
designated as Log 542-99 (see Photograph 43). A cross-section was prepared for one of these
contacts (see Figure 1-44) to compare to the results seen in the Log 487-99 samples. Much of
the carbon layer had been converted to pyrolytic graphene (see Figure 1-45 and 1-46). This
requires temperatures of at least 1800 degrees Fahrenheit. In Figure 1-46, cavities and cracks in
the carbon layer have been back-filled by flowing copper. Copper melts at 1983 degrees
Fahrenheit. There is also evidence of the thermal decomposition of chalcocite to metallic copper
and released sulfur. Chalcocite decomposes at 2052 degrees Fahrenheit. The temperature at the
face of this contact exceeded the melting point of copper. Apparently the only reason this
contact did not melt was that it dissipated thermal energy rapidly enough to keep the main body
of the contact below the melting point. Examination of the other surfaces of the contact, away
from the main contact face, indicated that lower temperature phenomena predominated (see
Figure 1-47).
Figure 1-35
Coked TLH Reversing Switch Movable Contact
1-32
Figure 1-36
The heavy layer of coke is limited to the contact termination and does not progress very
far along the lead. The entire contact set got very warm and was reported to be in a "ball"
of coke. Only the coke on the contact block itself remained after cleaning the part of oil
prior to shipping the part to the laboratory for analysis.
Figure 1-37
This close-up shows the rough texture of the contact surface and seems to show intact
metal. The black fragment of coke seen below the contacts in Figure 1-35 flaked from the
upper right side and corner of this contact. This set of contacts has not been analyzed.
1-33
Figure 1-38
Cross-Section of a Coked TLH Reversing Switch Movable Contact
This is a different coked contact received later in April 1999 and designated as Log 487-99.
Its relationship, if any, to the other contact has not been provided. Note the solid black
layer of carbon deposit around most of the part.
Figure 1-39
Carbon and Copper Sulfide Deposits in the Coke Layer, Magnification 400X
The pattern here is dominated by the lighter colored copper sulfide deposits that form
bands and rings through the predominantly carbon layer at the front contact surface of the
contact. This pattern is similar to deposits that result from the diffusion of reactant
species from different sides of a neutral carrier. The carrier in this case is the carbon
layer. The copper source would be the contact surface, which would suggest that the
sulfur source was the oil. The copper contact surface is out of view just below the gap at
the bottom of this field of view. The gap is the result of differences in the coefficient of
thermal expansion between the copper and the carbon layers.
1-34
Figure 1-40
Carbon and Copper Sulfide Deposits in the Coke Layer, Magnification 800X
This higher magnification view shows the differences in the carbon density in this deposit.
The brown grays are all carbon. The lighter brown grays are more dense layers of carbon.
The light grays and whites are copper sulfide. The pinks are a combination of copper
sulfide and finely divided metallic copper.
Figure 1-41
The Copper Surface of the Contact Showing Carbon and Sulfide Structures, Magnification
800X
The surface of the copper is heavily corroded. Copper sulfide is the green gray material in
this photograph and the carbon is the black material. The reflectivity of the copper metal
is so high that when the camera exposure is reduced to show the copper the other
materials appear much darker than in the earlier photographs. The sulfide layer is in
direct contact with the copper on all exposed copper surfaces. Carbon is intimately
1-35

associated with this layer of copper sulfide. This may be the result of oil entering into the
gap between the coke layer and the copper contact as it cools. This oil is then burned
when the contact is placed back into service.
Figure 1-42
Contact Alloy Showing the Copper Sulfide Phase, Magnification 400X
The alloy used in this contact is Copper #147, a copper sulfide hardened alloy. The
greenish phase in this photograph is the copper sulfide phase that is part of this alloy.
The presence of the copper sulfide phase in the copper adds a little complexity in
determining the events that result in an apparent sulfide corrosion at the surface of the
contact. The surface is significantly sulfur enhanced, but some of that sulfur comes from
the alloy itself.
1-36
Figure 1-43
This part was received in June 1999 and designated as Log 542-99. The part is severely
coked. The coke deposit is hard and covers the contact.
1-37
Figure 1-44
Cross-Section of a Coked TLH Reversing Switch Movable Contact
This is a different coked contact received in June 1999 and designated as Log 542-99. Its
relationship, if any, to the other contacts has not been provided. Note the solid black layer
of carbon deposit around most of the part.
1-38
Figure 1-45
Pyrolytic Carbon Deposits in the Coke Layer at the Face of the Contact Using Polarized
Light, Magnification 100X
Pyrolytic coke has secondarily filled a crack in the original carbon layer. The growth
pattern indicates vapor phase deposition.
1-39
Figure 1-46
Pyrolytic Carbon, Copper Oxide, Copper Sulfide, and Copper Deposits in the Coke Layer
at the Face of the Contact Using Polarized Light, Magnification 400X
The sulfide phases in the deposit are being reduced to molten copper in this deposit. The
temperature required for this reaction to occur is over 2066 degrees Fahrenheit.
1-40
Figure 1-47
Carbon, Copper Oxide, Copper Sulfide, and Copper Deposits in the Coke Layer at the Back
Surface of the Contact, Magnification 200X
The deposit at this location indicates a temperature exposure hundreds of degrees less
than on the face of the contact.
Analysis
Coking is a problem in many different environments across many different industries. In each
industry the causes tend to be unique, as are the precursors that ultimately form the coke. Within
an industry there may be a number of environmental conditions that lead to coking. Each set of
conditions has a characteristic signature in the deposit produced. Substrate materials are also
part of that environment and can effect the structure and the rate at which a carbon deposit forms.
The variety of ways in which coke can form is remarkably diverse. This makes the comparison
between the coke produced in a laboratory and real world environment very difficult. The
number of variables active at any given time and the results in terms of the end product are very
difficult to control.
It is not surprising that the coke deposits seen in this study are so diverse. The ethylene model of
coke formation is not representative of the LTC coking mechanism. In LTC's, coke grows on the
very surfaces that prevent the growth of coke in the production of ethylene. Surface preparations
that stop coke growth in ethylene production promote coke growth in LTC's. There are some
useful models in the literature but ethylene production is by far the least useful.
1-41
Some of the variables that are active in an LTC at any given time are:
Temperature
Time
Metal activation
Oil flow volume
Oxygen availability
Oxygen form
Sulfur availability
Sulfur form
Cyclic carbon compound concentration and form
Aromatic carbon compound concentration and form
Dissolved gases
Moisture
Particle concentration and form
Condition of the contacts.
Coke can form in any number of ways. Making coke experimentally will be beneficial only if
the final product, the coke, has the same chemical, morphological, and crystallographic signature
as that produce in an active LTC under similar conditions. We are getting closer to defining
what that real world signature is and to understanding the variables well enough to suggest
relevant models.
One clear set of observations is that coking occurs on only certain components of an LTC. It is
also clear that an increase in heating and contact resistance drives all of the coking processes in
an LTC. Controlling the increase in heating and contact resistance will control or minimize
coking. This has been demonstrated by the design changes to abandon bridge contacts in new
LTC designs. It has also been shown in the improved electrical connection between main
stationary contact fingers and the contact housing. Both of these design changes significantly
reduced contact resistance and the subsequent reduction in component heating and coking.
Controlling contact resistance is not always so easy. In each of the two cases cited, the problem
was a design susceptibility. There are other situations where the design is a compromise
between two different mechanisms that degrade the contact. The use of arc guard alloys (sintered
copper-tungsten alloy) is an example. The arc guard protects the contact from the damaging arc
but exposes it to entrainment of high resistance materials at the contact surface. There is also the
issue of reactive compounds present in the oil that can increase contact resistance by depositing
of the contact face. These issues need to be fully understood before they can be controlled.
The samples evaluated to date indicate four basic causes for increased heating and consequent
increases in contact resistance and coking. These are:
1-42
1. Misalignment of contacts,
2. Design defects or design limit problems due to use beyond design limits,
3. Wear of components resulting in increased contact resistance, and,
4. Chemical processes degrading contact performance.
Misalignment of Contacts
Misalignment of contacts has been indicated as the cause for some of the coking around main
stationary contacts in LTC's. The best example seems to be in the Log 408-99 parts, page
number ( ). This involves workmanship or improper procedures but can also occur as a result of
a mechanical failure or other operational problem.
Design Defects or Design Limit Problems
Design defects or use beyond design limits are indicated both by the reverse switch movable
contacts (Log 1117-97) and the bridging contact (Log 075-98). In each of these cases excessive
temperature of the component was the main issue. This may have caused by insufficient coolant
flow, (design defect) or due to over loading (use beyond design limits) or both.
In case of the reversing switch movable contacts, the heat moved beyond the contact area and
spread throughout the entire part. The coking was general in nature with no indications of
localized hot spots or elevated temperatures. This suggests that with adequate cooling or with
lower power flow the part may not have coked as quickly as it did.
In the case of the bridging contact it is susceptible to resistance heating by its design. Contact
pressure is hard to maintain as the part ages and the part acts as a funnel, directing any available
contaminants into the contact region. The movable contacts seem to function well in the center
phase position but not as well in the left and right phase positions. This may be due to more
efficient cooling of the center phase making it less susceptible to resistance heating. In any case,
the center phase is being used within the operational envelope of the "system" design, and the
other phases are not.
Wear of Components
Component wear degrades performance in two ways. In the case of the contact surface itself,
wear processes degrade the quality of the contact surface. The introduction of less conductive
phases into the contact region has been documented in all the samples examined. This is a
normal result of use. These less conductive phases include tungsten from arc guard materials in
the case of Log 075-98 and carbon in every case. The contact surface is also degraded by
becoming rougher. Initially, wear improves the mating efficiency of the contact by
"conforming" the two contacting surfaces. With age, the surfaces become rougher, and it is less
likely that the contacts will mate exactly. The result is gaps in the contact and a smaller contact
1-43
area. This increases contact resistance and promotes the development of less conductive
chemical species at the contact face.
The second way wear degrades performance is in the physical loss of material. The result is less
tension in the contact, which reduces contact pressure and makes the contact more susceptible to
misalignment or to the introduction of foreign materials into the contact region. The finger
contacts of the main stationary contacts in Log 138-98 seem to be an example of this problem.
Wear is an inevitable result of use and component aging. It can be minimized by design, but it is
inevitably a process of optimizing component performance with component durability. All
systems fail eventually and component wear is one of the most common causes.
Chemical Processes
The final coking mechanism, chemical processes degrading contact performance, is the most
complex. The stationary switches of Log 075-98 and the movable switches of Log 475-99, 48799, 542-99, and 589-99 are all examples of these processes. These mechanisms in LTCs
involve the deposition of a high-resistance material on the contact surface as a result of a
chemical reaction at the surface of the contact with reactive species in the oil. There are nonconductive films on all of the parts received, but those listed here show the most contact
degradation resulting from these processes. Both organic and inorganic films are involved.
The inorganic films include sulfides and oxides of copper predominantly. Two forms of each
have been identified in these samples. The oxides are both tenorite (CuO) and cuprite (Cu2O).
The sulfides are both covelite (CuS) and chalcocite (Cu2S). Silver sulfide film was also detected.
Oxygen is available in the oil for the formation of oxides but it appears that sulfur may be an
intermediary. Copper reacts readily with sulfur at ambient temperatures and more rapidly at
elevated temperature. Sulfur also has an affinity for carbon. In at least three samples, Log
numbers 075-98, 487-99, and 542-99 carbon seems to be involved in the reduction of the copper
sulfide to copper metal or the conversion of copper sulfide to copper oxide. Sulfur in the system
seems to facilitate corrosion of the copper even when the final product is copper oxide.
The organic films are from a variety of sources. Some of the precursors to these films are
created in the arcing events that occur on a regular basis in an LTC. The arc is a very high
temperature plasma that instantly vaporizes the oil in its path. The vapors created intensify the
arc. It decomposes some of the oil, forming coke, and releases a variety of gas phase
compounds such as hydrogen, ethylene, acetylene, aromatic species and the acrylates. Aromatic
ring structured compounds are common. Other materials are generated from degrading
components to which the oil has been exposed, furans for example, from paper or wood
products. The cyclic structured compounds tend to form deposits in the LTC's. The known
deposits include the polyacrylates and the polyfurans. These ring structured compounds form
polymer films and, given sufficient temperature, pyrolytic graphite. The organic films that had
formed in service on the LTC parts.
1-44
Materials such as ethyl acrylate polymerize in response to heat. The contacts area tends to be the
hottest surface as the LTC loading is reduced and ambient temperature falls or when a system is
taken out of service or. These heat sensitive compounds would tend to polymerize and be
deposited on the exposed surface of the contact. The small quantity of these materials in the oil
near the contact would be rapidly depleted, but convective flow keeps new oil flowing over the
part. The result is that the warm contact scours the polymerizing chemicals from a significant
volume of oil.
A second deposition mechanism is active when the system has cooled. During the unloading
cycle all dissolved compounds in oil including oxidized organic and the furfurals in oil, begin to
cool and precipitate, forming sludge. The sludge formations coat all exposed parts of the LTC
indiscriminately. Furfurals easily form graphene cokes at relatively low temperatures38. The
other components of this sludge are expected to be similar to any other oxidized oil sludge and
are susceptible to the formation of durable carbon films when heated. The behavior of these
materials in oil during cyclic heating and cooling has been documented to some extent. The cold
filtration of the oil to remove these materials is one example of making good use of this effect.
There does seem to be some preferential deposition of materials during cooling based on
analyses of oil before and after filtration or following a complete oil change, but the compound
analyzed has been very limited.
One of the interesting discoveries to date is the degree of degradation that can occur at a contact
surface and yet allow the contact to continue to function. A number of the reversing switch
movable contacts had been functioning at temperature exceeding 2100 degrees Fahrenheit for
some considerable time, at least hours over multiple cycles. At these temperatures a number of
very complex chemical changes occur in the oil and in the material deposited on the contacts
involved. Some of the changes may tend to mask the events that lead to this final condition.
Thirteen LTC parts consisting of one hundred and six individual components have been
examined at this stage of the study. The original literature survey has been significantly
expanded. There are three technical journals dedicated to coke specifically and about fifteen
others that regularly carry articles on coke.
Conclusion
The samples analyzed to date represent about half of what we had original considered the
minimum required sample population. Based on this limited population a few facts seem to
stand out. One of these is that increase in contact resistance drives all of the coking processes in
an LTC. The samples evaluated to date indicate four basic causes for increase in heating and
contact resistance. These are:
1. Misalignment of contacts,
2. Design defects or use beyond design limits,
3. Wear of components resulting in increased contact resistance, and,
1-45
4. Chemical processes degrading contact performance.

The first three mechanisms are the most relevant with regard to the LTC main stationary contacts
seen at this time. Chemical processes seem to be secondary and of minor importance in these
components. On the others, chemical processes play a far more significant roll as in all the
reversing switch movable contacts.
The trends that do seem to be supported by the available evidence include the following:
All the factors known to reduce the coking in an ethylene reactor have no effect or increase
coking in an LTC.
The increase in heating and contact resistance drives all coking in LTCs. Arcing is
instrumental in creating the chemical compounds that form resistive films. A variety of
chemical processes create the resistive film and the final carbon deposit on the LTC
components. The degradation of the contact surface, the root cause of increase in resistance,
is due to one or more of the following:
The formation of oxides, sulfides, or polymers on the contact surfaces;
To failures in the cooling system;
To mechanical problems such as contact alignment
Loose contacts.
Coked parts in LTCs continue to function under conditions beyond the design limits for
considerable length of time. The temperature in the contact zone can exceed 2100 degrees
Fahrenheit in an operating LTC contact.
We have only a few examples and very little historical data to construct a set of accurate models
for the development of coke on the surfaces of LTC components. For this study little information
is available about the frequency of failures due to coking by component, and the type of coking
failure with respect to the four mechanisms cited above. The final and lasting solution to the
coking problem will depend on the nature of the cause. Contact misalignment can not be
corrected by removing polymer forming compound from the oil. Multiple mechanisms are
involved, and the most frequent causes should be addressed first.
Analysis of Oil
Six oil samples from four different LTC's have been evaluated in order to develop a
recommended analytical approach. The samples include TJH2b #1035563, #1035564, #1035565
(Microlab NW #229-98), TJH2b #1041951 (Microlab NW #408-98), TJH2b # unk (Microlab
NW #534-99), and TJH2b #1048964 (Microlab NW #589-99). All of the sample oils were from
Pennsylvania 996 LTC's with the exception of the last one, which was from a UZD. The
techniques used to date include extractive polynuclear aromatic hydrocarbon analysis, desolved
gas analysis, furfural analysis, acid acceptance, color, and particle count. Some of the deposits
associated with transformers and with LTC's have been processed for comparison.
1-46
The oils were filtered through a 0.2 mm PFTE membrane filter to separate fluid from solid
materials in the samples. The filtered oil was initially introduced into the GC/MS by simple
dilution with methylene chloride. 0.1 grams of oil was diluted to 10 milliliters with methylene
chloride and a portion of this solution was injected into the GC/MS. The chromatogram was
swamped with alkanes typical of the oil, which obscured all the compounds of interest. The oil
samples were then extracted using acetonitrile. Ten milliliters of oil was shaken with one
milliliter of acetonitrile. The acetonitrile was then collected and diluted to ten milliliters with
methylene chloride. A portion of this sample was then injected into the GC/MS and provided
useful data. The solids on the membrane filter were then similarly extracted with acetonitrile,
diluted and injected into the GC/MS to test for any differences. The results were the same for
both the oil and the filtrate. The compounds detected and their presence in parts per million are
shown in Table 1. Mineral oil spiked with 1,2-dichlorobenzene, nitrobenzene, and 2fluorobiphenyl run along with these samples all exhibited better than 95% recovery in the
extraction. The lower reporting limit was 1 part per million.
Table 1-1
Polynuclear Aromatic Hydrocarbons by Modified EPA Method 8270 (SIM)
Compound
CAS#
563
564
565
951
unk
964
Naphthalene
91-20-3
2-Methylnaphthalene
91-57-6
12
18
26
14
21
1-Methylnaphthalene
91-57-6
12
17
25
15
22
Acenaphthalene
208-96-8
10
11
Acenaphthene
83-32-9
Fluorene
86-73-7
23
29
24
40
19
17
Phenanthrene
85-01-8
26
101
20
284
39
24
Anthracene
120-12-7
30
10
19
36
Fluoranthene
206-44-0
19
Pyrene
129-00-0
11
Benso [a] anthracene
56-55-3
nd
nd
nd
nd
nd
Chrysene
218-01-9
nd
nd
nd
nd
nd
The oils all fluoresced blue to white under ultraviolet light with some showing distinct yellow
fluorescence at the meniscus on top of the liquid layer. This property did not track with the
concentration of any of the compounds detected. An additional concern was that none of the
furans were detected in this analysis and they should have been present. It would seem that there
1-47
were a number of active chemical species present that were not being resolved in the analysis.
The approach did detect differences between the oils and is of value, but additional extractive
methods and solvent systems should be evaluated.
The UZD oil sample (1048964) is within the range of variation of the Pennsylvania 996 samples.
That suggests that the processes that are involved in coking are the same regardless of system
configuration. That is an expected result that would seem to be born out by this single sample.
The possibility that this is an artifact of the procedure, that the differences are simply not
detectable with this extraction sequence, has not been ruled out.
The results for the filtered oil and the particles were not significantly different. That indicates
that the particles were not soluble in acetonitrile. Traces of oil in the filter and with the particles
dominated the filtrate results. The filtrate should have been processed using the standard pitch
and tar techniques of ASTM D-4072 and D-2318, toluene and quinolene extraction respectively.
A sample of a brown deposit from a transformer was analyzed to see if any characteristic PNA's
were present. The result was the identification of ethyl acrylate in the oil of the transformer and
deposited films of polymerized acrylates on some surfaces in transformers. Ethyl acrylate is
generated in arcing environments and so its discovery in these types of environments in not
unexpected. Ethyl acrylate is a rather active compound that will polymerize in the presence of
heat. Once polymerized it becomes very stable. At elevated temperatures it begins to
decompose into graphitic structures referred to as turbostratic graphite or graphenes. It, and its
chemical cousins, are materials of choice for the production of pyrolytic graphite fiber. The oils
that were collected from LTC's have not shown the presence of ethyl acrylate or specifically
related compounds. The presence of ethyl acrylate in this transformer sample is interesting but
the lack of this compound in the LTC oil samples suggests this may have been a special case.
Two coked parts were submitted for extractive analysis. These were both Pennsylvania main
stationary contacts: TJH2b #1031487 (Microlab NW 138-98) and TJH2b #1041951 (Microlab
NW 408-99). The parts were rinsed with ten milliliters of methylene chloride and injected into
the GC/MS. Only alkanes were detected. This test should be rerun using acetonitrile to reduce
the interference from the alkanes (a problem experience before) and the solids should be
processed using the toluene and quinolene procedures. This more rigorous approach is planned
in the next phase of this study.
Recommendations
As a result of the test results on the oil samples and attempts to extract materials for GC/MS
analysis from solid deposits the following recommendations are suggested.
1. The oil and the solids must be extracted differently.
2. Acetonitrile extraction of the oil is effective for many compounds but is far from complete.
3. Solids should be extracted using practices typical of thermally degraded hydrocarbons.
1-48
4. Fluorescence may be a useful qualitative tool.

5. There was a disconnect between the standard tests and the special test that will be corrected.
6. The instability of some of the compounds of interest, specifically the furans, in the oil may be
responsible for some of the results seen in the oil samples. The time from collecting the
sample until it is analyzed should be noted and minimized (days or less, not months).
These recommendations were incorporated and are included in this report.
1-49
TEST CELLS
The next phase of the project builds on the knowledge gained from the analysis of all the
carbonized LTC components and oil obtained from failed or degraded load tap changers. The
objective is to track down the culprit chemical compound or compounds that cause the
development of a film on copper or silver-plated current carrying interfaces which ultimately
results in a high resistance interface.
Test Method
One way to reproduce the LTC environment would have been to use an actual LTC. However,
this was explored and found to be impractical, since an operating load carrying LTC was not
available. Another possibility would be to test a full size LTC at a test facility with the capacity
to pass current through the LTC. This was explored and found too costly.
After evaluating the above options, it was decided to test simulated LTC copper parts in small
(24 inches long by 12 inch diameter) test cells (see Figure 2-1). Each uses about 35 liters of oil
for each experiment. The initial experiments were performed using 4 inch copper rods machined
to accept a cartridge heater, which could be used to heat the part (see Figure 2-2). In order to
simulate the arcing in a load tap changer, a thumper was developed to arc in the oil (see Figure
2-3 and 2-4). The test cells where filled with clean oil and arced with the Thumper in some
experiments. In others clean oil was used. The copper rod was heated using the cartridge heater
inserted into a machined cavity in the rod. The copper rods, deposited film and/or coke and the
oil were then analyzed. The results of these experiments are reported in the following chapters.
2-1
Test Cells
Figure 2-1
One of four test cells fabricated for the project
Figure 2-2
Electrical grade 5/8" copper rods simulate copper LTC load carrying contact material. A
cartridge heater is used to vary the temperature of the copper. Copper rod length
increased after the first test.
2-2
Test Cells
Figure 2-3
"Thumper" electrode and feed-through bushing. Used to simulate arcing in oil.
Figure 2-4
"Thumper" in action. The "thumper" is activated at 15 kV and carbon starts to develop in
the oil immediately.
2-3
Test Cells
Figure 2-5
Test cell and copper rod under oil during heating.
Figure 2-6
Copper Rod Shown With Carbon Deposit.
Four test cells were fabricated and used to conduct experiments, which were planned so as to
expose the copper to conditions found in the failed load tap changers evaluated and reported in
Chapter 1.
2-4
CELL TEST RESULTS
INTRODUCTION
The purpose of the test cells was to create an environment where changes that occur in an LTC
over long periods of time can be created in a much shorter period of time. This accelerated aging
would be the result of using higher temperatures, higher concentrations of challenging agents, or
creating continuous conditions that simulated exposure over several cycles in a functioning LTC.
The number of parameters that may be important to the formations of stable carbon films is
large, and so is the number of parameters that can be controlled in the test cells. A few of these
are listed below and are related to the known active variables in LTCs.
Peak Temperature of Contact
Target Temperature for Contact (150 to 450 Celsius)
Thermal Profile of Contact
Surface Area of Contact per Unit Volume of Chamber
Starting Temperature of Chamber Oil (0 to 50 Celsius)
Ending Temperature of Chamber Oil
Duration of Exposure (Hours to Days)
Duration of Exposure as a Function of Temperature
Base Oil (New Diala, Used LTC Oil, Designer Oil, etc.)
Additive Type (PAH, Alkyne, Carboxyl, Furan, etc.)
Additive Concentration (PPM to Percent)
Precondition of Conductor Surface (Clean, Organic film, Sulfide, ect.)
Precondition of Chamber Oil (Arcing, Soaking, Cycling, etc.)
Conductor Surface Area as a Function of Concentration
Thermal Distribution as a Function of Conductor Surface Area
Sparging (Air, Nitrogen, Fractional Acetylene, etc.)
Volume of Oil in Chamber
Head Space or Blanket Gas (High RH, Inert, Air, etc.)
Contact Metal or Alloy (Copper 147, Silver Plate, Cu-Be, etc.)
Current Cross-section
Beginning Resistance
Cycles
3-1
Cell Test Results
Testing all of these parameters independently would be prohibitive in cost and time. The
approach taken was to test "regions of interest" within the multiple dimensional matrix space
defined by these variables. Figure 3-1 illustrates how this was done. A sub-field of three
dimensions was selected for each set of tests. In theory three parameters are being tested while
all of the other variables are being held constant. Each of the three variables is changed within
the selected space to determine how these three variables interact. In point of fact all of the
other variables are active and are fluctuation over some small range. As long as those
uncontrolled fluctuations are negligible the effects of the three variables of interest can be
determined and test results can be confidently repeated. If the tests cannot be reproduced within
acceptable limits then one or more of the uncontrolled variables is changing in a way that is
significant and must be actively controlled.
Y-axis
Z-axis
X-axis
Figure 3-1: A Three

Dimensional Sub-Space
of an N-Dimensional
Study Space. This is one
three dimensional region of
the ndimensional space
being studied. The other n-3
parameters are being held
constant. By characterizing
the behavior of materials in
this sub-space their behavior
in the larger space can be
considered.
Figure 3-1
A Three Dimensional Sub-Space of an N-Dimensional Study Space.
This is one three dimensional region of the ndimensional space being studied. The
other n-3 parameters are being held constant. By characterizing the behavior of materials
in this sub-space their behavior in the larger space can be considered.
The materials in the test cell are monitored chemically and physically to characterize the changes
that occur as a function of the parameters being tested. The measurements made on these
materials include the list of parameters below.
Output Parameters:
Temperature by Position on the Conductor

Change in the Weight of Conductor (film weight)
Chemical Properties of Film by Position
Crystallographic Properties of Film by Position
Mechanical Properties of Film by Position
3-2
Cell Test Results
Dissolved Gases in the Oil

Sulfur Content of the Oil
Poly-Aromatics Present in the Oil
Furans Present in the Oil
Mechanical Properties of Oil
Temperature of the Oil
These measurements helped to characterize changes in the oil during the test, and to
characterized the changes that occurred on the surface of the test rod
Conditions Selected for Test
In this phase of the study we wanted to evaluate selective sub-populations of the multiple
dimensional matrix space (time, temperature, cycling, furans, arcing, sulfur, aromatics,
oxygenated alphatics, etc.) and generate a model challenge that could be used to evaluate control
methodologies. Our initial intent was to evaluate the effects of temperature and a few additives
at a fixed time of 48 hours but in the process there were some unexpected anomalies in the
behavior of the test equipment. We had the option of disregarding the anomalous runs or, by
virtue of the well-documented thermal history of each run, evaluating these samples as alternate
parameters. We chose the latter. This decision has helped us relate the 48 hour static test to the
more real world conditions of cycling loads and shorter time exposures. Our test configuration
also allowed us to test a range of temperatures in each run. Figure 3-2 illustrates the nature of
the test rod thermal gradient and how it was monitored.
The copper test rod was four inches long and was bored out to contain a two-inch heater unit that
was inserted into the rod. The surface temperature of the copper rod was monitored at three
locations using thermocouples that were fixed to the rod with wire. The heater element was set
for a specific temperature through a feedback loop between the controller and a thermocouple in
the heater itself. The lower thermocouple location on the rod in the test cell was below the
heater position (see Figure 3-2). This location was heated by conduction through the copper by
the heater and was cooled by conduction by the oil in the tank that flowed over its surface. The
rate of oil flow over the surface of the rod was controlled passively by the natural convection
currents created by the test run (Figure 2-5). Under these conditions the gradient range of
temperatures increased with increasing test temperature because of the natural increase in
convection flow at the higher temperature.
3-3
Cell Test Results

Figure 3-2: Test Rod
Upper Thermocouple
Middle Thermocouple
Lower Thermocouple
Copper Test Rod

Heater
Thermocouples
Figure 3-2
Test Rod
Above this thermocouple and over the heater was the second thermocouple. This thermocouple
experienced the highest temperatures by virtue of its proximity to the heater unit itself. The
temperature at this location documented the net cooling effect of the total surface of the test rod.
The final thermocouple was located near the top of the rod beyond the heater. This region
experienced temperatures that were intermediate between the other two thermocouples because
the oil moving along its surface had been heated significantly and was less effective in cooling
the copper. Figure 3-3 shows one of the test rods and the marks left by the thermocouples and
the location of the heater after a test run.
O il L ev el
T h erm o co u p les
H eater
Figure 3-3
Test Rods and Marks Left by Thermocouples
3-4
Cell Test Results
The result of this test configuration was that it provided a range of temperatures for each test.
For any given test the range of temperatures was relatively small, typically 30 to 50 degrees
Celsius, but the differences were often interesting. From test to test the temperature range varied
slightly so that a number of individual temperatures and transitions could be evaluated.
Three basic temperature ranges were evaluated; 60-90 Celsius, 130-200 Celsius, and 250-300
Celsius. The lowest range of temperatures is typical of expected values for new systems. The
second range is a region of interest where the new oil begins to react with the hot copper. The
third range is an area known to be associated with the breakdown of the oil.
The additives that have been used through all of these temperature ranges include elemental
sulfur, furfuryl alcohol, furfuraldahyde, used oil, and arc conditioned oil. A few other specific
additives have been used, such as naphthalene, and more will be used as we identify species of
specific interest.
The used oil contains a variety of poly-aromatic compounds, some of which where presented in
Table 1-1. Naphthalene was one of these compounds and was used by itself as an additive to
new oil in one series of tests. The arc-conditioned oil contained these compounds and others
along with a high population of carbon based particles created by the plasma.
RESULTS
Three basic types of films were created during these tests: inorganic, organic, and carbonized
films. The inorganic films were of two basic chemical types, copper oxides and copper sulfides.
The inorganic films were often complex and dynamic through a series of tests. Low
temperatures tended to create mixed oxide and sulfide films. At higher temperatures the film on
the surface of the rod tended to be an oxide film and the sulfides had moved into the carbon rich
part of the film. These inorganic films ranged from less than 40 nanometers to over a
micrometer in thickness. Often these films generated characteristic interference colors that could
be used to determine film thickness. Figure 3-4 is a photograph showing the interference films
created by an oxide film on one of the copper test rods (Series 1a, Cell, Test).
Figure 3-4
Interference films
The organic films were waxy, non-crystalline polymers (see Figure 3-5). All of them had a
distinct orange to red-orange color. They all exhibited shrinkage cracks. These materials were
3-5
Cell Test Results
highly coordinated carbon ring structures with elevated carbon-carbon bonding, as was indicated
by the high refractive index (>1.80) shown by the film.
Figure 3-5
Polymers
The carbonized films were black films indicating higher carbon coordination (see Figure 3-6).
Some of these films were very tenaciously bonded to the surface of the copper. The tenaciously
bonded carbon films seemed to be always associated with second and third order inorganic films
on the surface of the copper.
Figure 3-6
High Carbon Coordination
Thermal Effects
In the temperature range from 60 to 90 Celsius the copper was a very effective scavenger of
oxygen and sulfur from the system. These films were invariably present at some level after the
test and were not present at detected levels prior to the test runs. Figure 3-7 shows one of the
thermal charts for a test run with new Diala oil and the copper test rod that had been exposed.
The marks on the surface of the test rod are from the machining activity and are not related to the
effects of exposure to the oil. The films on the surface of this rod are about 40 nanometers thick
and include sulfide species as well as oxides of copper.
3-6
Cell Test Results
T e s t S e q u e n c e 1 C e ll # 1 T e s t # 1 H e a t e r T e m p s
1 0 0 .0 0
9 0 .0 0
8 0 .0 0
7 0 .0 0
Temp (C)
6 0 .0 0
113 (C )
5 0 .0 0
114 (C )
115 (C )
4 0 .0 0
3 0 .0 0
2 0 .0 0
1 0 .0 0
0 .0 0
0
10
15
20
25
30
35
40
45
50
E la p s e d T im e ( H r )
Figure 3-7
Thermal Charts of Test Run with New Diala
Organic films didnt form when new oil was used but when used oil or oil with 10 parts per
million added naphthalene was used an orange film would form over the heater. Figure 3-8
shows the thermal chart, the rod, and the tapelifted film generated by the test with added
naphthalene. This film was effectively removed by a tapelift and could be easily flaked from the
surface. At these temperatures the bonds between the film and the underlying copper were weak.
Flakes of the film were removed and tested for their refractive index. The refractive index of the
film was found to exceed 1.80. Refractive indices in this range indicate a significant loss of
hydrogen and the formation of a higher ratio of carbon-to-carbon bonds in the film.
3-7
Cell Test Results
T e s t S e q u e n c e 1 C e ll # 1 T e s t # 1 H e a t e r T e m p s
1 0 0 .0 0
9 0 .0 0
8 0 .0 0
7 0 .0 0
Temp (C)
6 0 .0 0
113 (C )
5 0 .0 0
114 (C )
115 (C )
4 0 .0 0
3 0 .0 0
2 0 .0 0
1 0 .0 0
0 .0 0
0
10
15
20
25
30
35
40
45
50
E l a p s e d T im e ( H r )
Figure 3-8
Thermal Chart and Rod Naphthalene Added to Oil
Carbonized films were never seen in the lower temperature ranges of this test sequence. The
thermal energy available at these temperatures was not sufficient to break down the oil into
predominantly a carbon film.
In the temperature range of 130 to 200 Celsius complex films were always present, even when
new Diala was used. There were often two distinct films, one inorganic film a few tenths of a
micrometer in thickness on the surface of the copper and an organic film above the inorganic
film, which often exceeded ten micrometers in thickness. Sulfides were always present but their
location varied. Test rods that had relatively thin or poorly formed carbon films still had sulfides
in the inorganic layer of film. As the film carbonized and became thicker the sulfur tended to
leave the inorganic film on the surface of the copper and enter the carbonized film. Often sulfur
could not be detected in the inorganic film but was strongly indicated in the carbon film. This
duplicates what has been seen in real world samples (see Figure 1-39 and 1-40) but the
mechanisms involved have not been determined.
3-8
Cell Test Results
T e s t S e q u e n c e 1 a , C e ll 4 , T e s t 1
3 0 0 .00
2 5 0 .00
Te m pe ra ture in C e lsius
2 0 0 .00
1 1 3 (C )
1 5 0 .00
1 1 4 (C )
1 1 5 (C )
1 0 0 .00
5 0 .00
0 .00
0.0 0
5 .00
1 0.0 0
1 5 .00
2 0 .00
2 5 .0 0
3 0 .0 0
35 .0 0
40 .0 0
4 5.0 0
5 0.0 0
T im e in H o u r s
Figure 3-9
Effect of Temperature Cycling
The test runs in this range were the first to present anomalous behavior. Figure 3-9 shows one
example. The temperature registered by the thermocouple on the middle of the test rod went to
nearly 250 before dropping back to near 200. After about 11 hours the temperature dropped
back to ambient for about 7 hours and then cycled between about 170 and ambient four times
over the next 10 hours. The resultant film was poorly defined and weak proximally but was well
bonded to the surface where two conditions were satisfied: first, the film had carbonized, and
second, the film was in contact with an inorganic film on the rod that had a thickness greater than
80 nanometers (Upper Photograph, Proximal on left). The lower photograph shows the oxide
layer under the carbon film. Where the thickness of the oxide film exceeded 80 nanometers
(second order red) the carbon film tended to adhere strongly. The second order red interference
color can be identified as a less intense red following an area of yellow. The second order red
can be seen just before the areas of adhering film in the photograph. The intense red outlined by
blue running diagonally across the photograph is the first order red, a little over 40 nanometers
thickness. These areas were also associated with waxy deposits (dark globular patches).
The organic films covered the test rods as long as the temperature over the entire rod exceeded
130 Celsius. Copper apparently reacts readily with the oil at these temperatures to generate these
films. Below 130 degrees Celsius new Diala was relatively unaffected over the forty-eight hour
duration of the standard test.
Over the heater element the organic films carbonized. The temperature at this location on the
rods always exceeded 160 Celsius. Figure 3-10 show a test run with "used" oil. In this case only
3-9
Cell Test Results
the lower thermocouple recorded. The lower thermocouple recorded the coolest temperatures on
the rod and during this run that temperature well exceeded 130 degrees Celsius. The carbon
films have not been characterized by x-ray diffraction at this time but they will be so
characterized as part of this phase of the project.
T e s t S e q u e n c e 1 a , C e ll 2 , T e s t 2
1 8 0 .00
1 6 0 .00
1 4 0 .00
Te m pe ra ture in C e lsius
1 2 0 .00
1 0 0 .00
1 2 0 (C )
8 0 .00
6 0 .00
4 0 .00
2 0 .00
0 .00
0.0 0
1 0.0 0
2 0 . 00
3 0 .0 0
4 0 .0 0
50 .0 0
6 0. 0 0
T im e in H o u r s
Figure 3-10
Test With Used Oil
At the higher temperatures, 250 to 300 Celsius, carbon films formed over the entire, oil exposed
length of the test rod. The film with new, clean Diala tended to blister and flaked easily (Figure
3-11).
Figure 3-11
High Temperature and New Diala
3-10
Cell Test Results
Most of the copper oxides and sulfides tended to move into the carbon films. Figure 3-12 shows
a rod from one of the tests using arc-conditioned oil. The rod, lower image, is covered with a
thick carbon coating. A cross-section of this film shows the migration of copper compounds into
the carbon layer. The reddish bands are areas rich in copper oxides and sulfides. Oxide layers a
few micrometers thick formed above the oil level.
Figure 3-12
Test Rod Exposed to Arc-conditioned Oil
Effects of Additives
The effects of additives was briefly addressed above but will be considered in more detail here.
There were three basic types of additives considered: inorganic (primarily sulfur), furans, and
aromatics. The effects of sulfur were of interest because it was invariably present in the films
covering failed contacts in the "real" world. Furans were of interest because they are present in
used transformer oils and to varying degrees in new oils exposed in some LTC's believed to be
free of cellulose based products. The aromatic compounds are common in all oil exposed to the
LTC environment. Their source includes arcing events and reactions occurring on the surface of
heated copper or silver. The amount of these chemical challenges added to the cells was
invariably small in terms of the total volume of oil in the cells but it was significant in terms of
the total weigh of film formed during the various tests. Each of the additives exhibited some
characteristic patterns supper-imposed on the thermal patterns discussed above. The additives
will be considered individually below.
3-11
Cell Test Results
Inorganic Additives
The principle inorganic reactants are oxygen and sulfur. The oxygen content was not controlled
in these runs and was considered to be elevated. Sulfur was added as elemental sulfur in
solution. At 30 part per million sulfur the effects were significant. The film that formed at a
temperature of from 170 to 200 Celsius was uniformly black and powdery (Figure 3-13). It had
little cohesion and the tapelift simply removed the top layer of debris, which left the rod still
looking black. The copper beneath the film had a layer of copper oxide nearly a 100 nanometers
thick in places (Figure 3-14).
Figure 3-13
Film With 39PPM of Sulfur
Figure 3-14
Oxide Film Under Sulfur Rich Black Powdery Film
None of the other films examined during this phase of the testing have lacked the cohesion of the
films created by adding elemental sulfur. It was also interesting that all of the sulfur was located
in the black film and that the inorganic film on the surface of the copper was all copper oxide.
3-12
Cell Test Results
Furan Additives
Furfuryl alcohol and 2-furaldahyde have been added as representative furan compounds. They
have been added at 0.25, 1, and 25 parts per million. Figure 3-15 shows the test rods after
exposure to 0.25 and 1 part per million furfuryl alcohol. The total area covered with carbon film
seemed to be greater with the lower concentration of furfuryl alcohol
though the film thickness was less over the heater. This series of tests was run without changing
out the Diala between tests. After the 0.25 ppm run a new rod and an additional 40 microliters of
furfuryl alcohol was added. The decrease in the area of coverage may have been the result of the
depletion of some other component in the new oil. This is being investigated. The film over the
heater is similar in structure for both rods though the higher concentration of furan is associated
with thicker films in each of the three distinct layers present. Figure 3-16 shows these layers in
the two test runs. The lower concentration of furan (left image) was associated with a uniformly
thick oxide layer (about a second order yellow, 70 nanometers), a shinny black film, and finally a
dull black thicker film. The higher concentration of furan (right image) was associated with a
thicker oxide layer (high order white, 500+ nanometers), a shinny bluish-black film, and a layer
of a duller black film. In the image below the shinny film can be seen in only a few very small
areas.
Figure 3-15
Test Rods Exposed to Furfuryl Alcohol
3-13
Cell Test Results
Figure 3-16
Films associated With Furan Test Runs
Effects of Aromatic Compounds

One of the challenges used consistently in these tests has been the "used" oil. This material is oil
from a variety of sources, both transformers and LTC's. It was shown early in the study to result
in films forming on heated copper long before new oil showed any effect. For that reason we
have repeatedly returned to this material as a target film generator for a procedural or pure
compound additive that could be used as a consistent reference material. The "used" oil contains
a variety of aromatic compounds and includes furans. The effects of adding a pure aromatic
(naphthalene) in the low temperature runs was impressive in that it was similar to the behavior of
the "used" oil. No duplicate comparison as yet been made in the 130 to 200 temperature range.
That test will be made as part of this phase of the study. The used oil tested in this range
produces a multiple layer film in some ways similar to that seen with the furans. This may be the
result of the presence of furans in this oil. That will be evaluated in future tests conducted with
arc-conditioned oil and with pure compound additives.
The "used" oil generated films were consistently dark in color and were thick by comparison to
the furan generated films. Figure 3-17 shows a typical test rod. The film was brittle and
cohesive. It lifted easily with the tapelift but did leave section of film still adhering to the copper
oxide layer. Figure 3-18 shows the surface of the test rod at a magnification of about 100X after
the tapelift was taken. The oxide layer is relatively thick, about 400 nanometers and a shinny
blue film is evident. The duller black film exhibits layering.
3-14
Cell Test Results
Figure 3-17
Brittle and Cohesive
Figure 3-18
Test Rod Surface Magnified 100X
DISCUSSION
We have been able to generate carbon based films on copper heated in new Diala oil, with and
without additives. By modifying temperature, time, and additives in the test cells we have
created films with averaged growth rates spanning four orders of magnitude, from 0.1 milligrams
per hour to 100 milligrams per hour. The films generated exhibit a variety of structures, some
similar, but not identical to the films seen in real world samples. We are now at the point of
more precisely reproducing results so that we can develop a reference procedure against which to
compare alternative materials. This will require more replicate test runs and more analyses of
both the films and the oil used in the tests.
We have seen differences in the properties of films using different additives. Here again repeat
tests will help determine if these differences are characteristic of the additive or were a
coincidence associated with other variables. If the association of specific variables and film
characteristics can be verified then reference films associated with specific conditions in the
equipment could be identified.
All of the above are required to develop a Control Film. A film that can be reproduced with
optimal reliability so that it can be used to evaluate more subtle differences between the behavior
of different oils or different configurations of materials.
3-15
Cell Test Results
CONCLUSIONS
One of the surprises in this study is how easy it is to form organic films on copper. Films form at
lower temperatures than previously expected and with a variety of contaminants that are
commonly encountered in oil with age. There are a variety of different structures in the films
created under different conditions but there are also consistent patterns. At this stage in the
project the knowledge of carbon based films in LTC's has already been greatly increased. The
different types of carbon deposits seen in LTC's have been described and the four basic
mechanisms responsible have been identified. The unique identification of chemically stable
films and their role in the failure of contacts better defined a previously unknown cause of
failure. A procedure for evaluating these films has been developed and is already aiding in the
diagnosis of contact failures.
A number of tasks still need to be accomplished as part of this phase of the study and are in
progress. The project is on schedule and our original goals still seem to be within the scope of
this project. This is still a work in progress but it has already generated information that has
been applied to working systems to prolong their useful life. More cost benefits will be realized
as the project continues.
3-16
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AND PHYSICS OF CARBON: VOLUME V, Philip L. Jr. Walker (ed.), Marcel Dekker,
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5. Taylor, R. (ed.), THE CHEMISTRY OF FULLERENES, World Scientific Publishing,
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ENGINEERING, pp. 101-105, Oct. 4, 1979.
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4-3
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Development of LTC Monitoring Technique Coking

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Development of Load Tap Changer

Development of Load Tap Changer

Technical Progress, December 2001

EPRI Project Manager

DISCLAIMER OF WARRANTIES AND LIMITATION OF LIABILITIES

To design controlled studies for verifying proposed coking mechanisms

To formulate a plan that addresses maintenance modes, monitoring techniques, operating

Design defects or use beyond design limits,

Wear of components resulting in increased contact resistance, and,

Chemical processes degrading contact performance.

1 EVALUATION OF FAILED LTC COMPONENTS AND OIL ................................................ 1-1

Figure 3-2 Test Rod ................................................................................................................ 3-4

EVALUATION OF FAILED LTC COMPONENTS AND

Synthetic carbon formed by the rupturing of the carbon-hydrogen bonds and

Evaluation of Failed LTC Components and Oil

Methods and Equipment

Evaluation of Failed LTC Components and Oil

Evaluation of Failed LTC Components and Oil

Evaluation of Failed LTC Components and Oil

Evaluation of Failed LTC Components and Oil

Evaluation of Failed LTC Components and Oil

Evaluation of Failed LTC Components and Oil

Evaluation of Failed LTC Components and Oil

Evaluation of Failed LTC Components and Oil

Evaluation of Failed LTC Components and Oil

Evaluation of Failed LTC Components and Oil

Evaluation of Failed LTC Components and Oil

Penn. 996 Main Stationary Contacts

Evaluation of Failed LTC Components and Oil

Evaluation of Failed LTC Components and Oil

"U" Shaped Housing

Pennsylvania 996 Load Tap Changer (LTC) Main Stationary Contact

Evaluation of Failed LTC Components and Oil

Evaluation of Failed LTC Components and Oil

Bar Contact Point

Knife Contact Surface

Evaluation of Failed LTC Components and Oil

Final Contact Point

Evaluation of Failed LTC Components and Oil

Bar Contact Point

Evaluation of Failed LTC Components and Oil

Evaluation of Failed LTC Components and Oil

Evaluation of Failed LTC Components and Oil

Evaluation of Failed LTC Components and Oil

(b) Contact Surface of the Finger Contact

Evaluation of Failed LTC Components and Oil

Evaluation of Failed LTC Components and Oil

Copper Oxides and Carbon

Copper Oxides and Carbon

Evaluation of Failed LTC Components and Oil

Cu/W Arc Guard

Evaluation of Failed LTC Components and Oil

UZD Bow-Tie Or Bridging Contact

Evaluation of Failed LTC Components and Oil

Evaluation of Failed LTC Components and Oil

Evaluation of Failed LTC Components and Oil

UZD Reversing Switch Stationary Contacts

Evaluation of Failed LTC Components and Oil

Evaluation of Failed LTC Components and Oil

Evaluation of Failed LTC Components and Oil

Evaluation of Failed LTC Components and Oil

Evaluation of Failed LTC Components and Oil

Evaluation of Failed LTC Components and Oil