Professional Documents
Culture Documents
Mark Barnes
corresponding test for gasoline is ASTM D3525. In both cases, calibration mixtures of known
dilution factors are used to calibrate the GC instrument, prior to running the test sample.
While other physical tests such as changes in viscosity, FTIR and reduced flash point are all used
to determine the presence of fuel in a lubricating oil; GC offers a more precise and reliable means of
determining fuel dilution. This is particularly true for changes in viscosity, which can be offset by
soot loading, and FTIR, which at best is capable of detecting fuel dilution only when it reaches two
percent due to new oil reference mismatches and variable aromatic content in diesel and gasoline
fuels.
Ethylene Glycol in Used Engine Oil
Just like fuel dilution, ASTM D4291 covers the use of GC to detect trace amounts of ethylene glycol
due to coolant leaks; another method specifically developed for used oil analysis. In the case of
ethylene glycol, the method works by first extracting the glycol using water (because ethylene glycol
is a polar molecule, it is easily extracted using water) and injecting it into a calibrated GC column.
GC offers a simpler, more convenient means of determining a reduction in boiling point range. In
this method, the GC instrument is used in the temperature programmable mode. In this mode, the
sample is slowly heated by increasing the temperature linearly over time. As the temperature rises,
the boiling point range of the sample can be determined by ...
... measuring the sample as it elutes, often using a flame ionization source, as a function of the
temperature. This method, which is commonly used in petroleum research and QA labs, is often
referred to as a simulated distillation. The simulated distillation of a petroleum oil, appropriate to
determining cracking of used oil sample is covered under ASTM D2887.
References
1. Reygaerts, Anne (2002). Transformer Oil Analysis. Practicing Oil Analysis magazine.
2. ASTM D3524-90. Standard Test Method for Diesel Fuel Diluent in Used Diesel Engine Oils
By Gas Chromatography - (Reapproved in 1999).
3. ASTM D3525-93. Standard Test Method for Gasoline Diluent in Used Gasoline Engine Oils
By Gas Chromatography - (Reapproved in 1997).
4. ASTM D4291-93. Standard Test Method for Trace Ethylene Glycol in Used Engine Oil
(Reapproved in 1998).
5. ASTM D2887-99. Standard Test Method for Boiling Range of Petroleum Fractions by Gas
Chromatography.
Further Reading
Oil Analysis 101: Fourier Transform Infrared Spectroscopy, Practicing Oil Analysis magazine,
March-April, 2002.
It is well known that regular oil analysis is useful in monitoring the condition of engines, turbines and
other oil lubricated equipment. The same can be said for transformer oils used to insulate many
transformers and other electrical distribution equipment. The analysis of insulating oils provides
information about the oil, but also enables the detection of other possible problems, including
contact arcing, aging insulating paper and other latent faults and is an indispensable part of a costefficient electrical maintenance program.
Dielectric Strength
The dielectric strength (ASTM D300-00) of a transformer oil is defined as the maximum voltage that
can be applied across the fluid without electrical breakdown. Because transformer oils are designed
to provide electrical insulation under high electrical fields, any significant reduction in the dielectric
strength may indicate that the oil is no longer capable of performing this vital function. Some of the
things that can result in a reduction in dielectric strength include polar contaminants, such as water,
oil degradation by-products and cellulose paper breakdown.
Power Factor
The power factor (ASTM D924) of an insulating oil is the ratio of true power to apparent power. In a
transformer, a high power factor is an indication of significant power loss in the insulating oil, usually
as a result of polar contaminants such as water, oxidized oil and cellulose paper degradation.
Dissolved Gas Analysis (DGA)
Dissolved gas analysis (often referred to as DGA), is used to determine the concentrations of
certain gases in the oil such as nitrogen, oxygen, carbon monoxide, carbon dioxide, hydrogen,
methane, ethane, ethylene and acetylene (ASTM D3612). The concentrations and relative ratios of
these gases can be used to diagnose certain operational problems with the transformer, which may
or may not be associated with a change in a physical or chemical property of the insulating oil.
For example, high levels of carbon monoxide relative to the other gases may indicate thermal
breakdown of cellulose paper, while high hydrogen, in conjunction with methane may indicate a
corona discharge within the transformer. Some of the more common key gas analysis fault
conditions can be seen in Figure 2.
Furans
Furan derivatives are a measure of the degradation of cellulose paper. When the paper ages, its
degree of polymerization reduces, so its mechanical strength decreases. The degree of
polymerization can only be determined directly by taking a sample of paper, a very complex
operation and almost never performed in practice. However, the degree of polymerization of the
paper can be directly related to the concentration of furan derivatives in the oil. Furan derivates are
formed as a direct result of the breakdown of the polymeric structure of cellulose paper. The content
of furan derivatives is relatively easy to measure in the oil, using HPLC and is thus a way of
measuring the aging of the paper.
Just like machinery oil analysis, electrical insulating oil analysis can play a vital role in preventing
unscheduled outages in electrical transmission and distribution equipment by determining the
condition of the equipment itself, and other vital components including the condition of the oil and
the cellulose paper insulation. For all critical oil-filled electrical equipment, including transformers,
circuit breakers and voltage regulators, regular, routine oil analysis should be the cornerstone of
any PM program.
Fluids with specific gravity greater then 1.0, such as askarels, should be sampled from the top
because free water will float. For fluids with a specific gravity less than 1.0, such as mineral-based
transformer oils, synthetic fluids and silicone oils, the sample should be taken from the bottom since
water will tend to drop to the bottom in these fluids.
There are a number of environmental variables, such as temperature, precipitation, etc., to consider
before collecting a sample. The ideal situation for collecting a sample from an electrical apparatus is
95F (35C) or higher, zero percent humidity and no wind. Cold conditions, or conditions when
relative humidity is in excess of 70 percent, should be avoided, as this will increase moisture in the
sample. Collecting a sample during windy conditions is also not recommended because dust and
debris enter the clean sample easily and disrupt accurate particle counts. If sampling the oils is
unavoidable when the outside temperatures are at or below 32F (0C), it should not be tested for
water content or any properties that are affected by water such as dielectric breakdown voltage.
For dissolved gas analysis, an elaborate procedure must be followed, including the use of a glass
syringe; with strict adherence to sampling protocol to ensure that the concentration of dissolved
gases is not influenced in any way by sampling procedure. This procedure is described in detail in
ASTM D3613.
The analysis of gases from petroleum products has been performed for decades
using gas chromatography. However, this technique was not applied specifically to
transformer mineral oil until the late 1960s/early 1970s and is now commonly called
dissolved gas-in-oil analysis (DGA). Some of the early developers of the technique
were Dr. James Morgan of Morgan Schaffer Systems, Canada, and researchers J.E.
Dind, R. Daust and J. Regis from the Canadian utility Hydro-Quebec.1
Because the technique was so successful and provided a wealth of diagnostic information to detect
incipient faults, other laboratories such as Doble Engineering in Massachusetts began utilizing the
technique shortly thereafter. DGA has now become a standard in the utility industry throughout the
world and is considered to be the most important oil test for insulating liquids in electrical apparatus.
More importantly, an oil sample can be taken at anytime from most equipment without having to
take it out of service, allowing a window inside the electrical apparatus that helps with diagnosing
and trouble-shooting potential problems.
Insulating fluid analysis is performed using an array of physical, chemical and electrical tests.
Physical tests include analysis for interfacial tension, pour point, relative density, viscosity, color and
others. Tests such as water content, neutralization number, oxidation inhibitor and polychlorinated
biphenyls (PCBs) are considered chemical tests. Electrical tests consist of analyses for dielectric
breakdown voltage and power factor. There are many other tests that can be performed but these
are the main ones executed on a routine basis. Most tests performed in North America are based
on ASTM test methods. In Europe and other parts of the world, similar test methods come under the
auspices of the International Electrotechnical Committee TC10.
Because oil and solid insulation degrade with service in electric apparatus, periodic sampling and
testing are necessary to ensure that deterioration is detected before it becomes excessive. The rate
at which the insulating materials degrade depends on several factors, such as the type of oil
preservation system (amount of oxygen present), operating temperature, water content of the
insulation, and the amounts and types of contaminants. The frequency at which testing is conducted
varies with the test, importance of the equipment, whether an incipient-fault condition is known to be
present or a problem exists, and when a family of transformers has been identified as having a
history of problems.
The tests mentioned above provide information on the oil quality itself but fail to provide in-depth
diagnostic information on the operating condition or health of the electric apparatus. In addition,
because most transformers in the United States are considered to be sealed systems (equipped
with preservation systems that retard the ingress of moisture and oxygen), oil degradation can
occur quite slowly over many years. Many of the transformers in the United States that have been
in-service for more than 30 years still contain oil that is in good condition. There is one test
however, also performed on the insulating oil of the transformer, which provides a means for
diagnosing the operating condition of the electrical apparatus, namely DGA.
powerful tool for detecting incipient-fault conditions and for root-cause investigations
after failures have occurred. Dissolved gases are detectable in low concentrations
(ppm level), which usually permit early intervention before failure of the electrical
apparatus occurs, and allow for planned maintenance.
The DGA technique involves extracting or stripping the gases from the oil and
injecting them into a gas chromatograph (GC). Detection of gas concentrations
usually involves the use of a flame ionization detector (FID) and a thermal
conductivity detector (TCD). Most systems also employ a methanizer, which converts
any carbon monoxide and carbon dioxide present into methane so that it can be burned and
detected on the FID, a very sensitive sensor.
Removing the gas from the oil is one of the more difficult and critical portions of the procedure. The
original method, now ASTM D3612A, required that the oil be subjected to a high vacuum in an
elaborate glass-sealed system to remove most of the gas from the oil. The gas was then collected
and measured in a graduated tube by breaking the vacuum with a mercury piston. The gas was
removed from the graduated column through a septum with a gas-tight syringe and immediately
injected into a GC. In the present modern day laboratory, however, mercury is not a favorite
material of chemists. For this reason, two additional extraction techniques have been developed to
eliminate mercury.
ASTM D3612B is called the direct injection technique. In this method, the stripping of gases from
the oil and the gas analysis takes place inside the GC. Originally developed in the mid-1980s for
this application, the process involves injecting the oil into a sample loop in the GC. When the GC
run is initiated, the sample loop transfers the oil through a series of valves into a stripper column.
The stripper column is composed of metal spheres in one end in which the oil overlays the surface
of the spheres to increase the surface area. Carrier gas is passed over the spheres and extracts
dissolved gases from the oil, which then pass through a series of columns and on through the
detectors. The oil is back-flushed and purged from the system before the next sample is introduced.
The newest method, ASTM D3612C, was approved about a year ago and is called the headspace
method. Headspace technology was used for DGA analysis for almost a decade. However, it was
never developed into a robust, reliable standard method until several years ago when Jocelyn
Jalbert of Hydro-Quebec developed a headspace method using a Hewlett Packard (now Agilent
Technologies) instrument.2 The technique involves injecting an exact volume of oil into a purged
and pressurized headspace vial. The gas in the oil is then allowed to develop an equilibrium with
the vial headspace under shaking and heating conditions. After a predetermined sample extraction
time, the autosampler removes a portion of the gas from the vial headspace and injects it into the
GC. The advantage of this method is that it can be automated and reduces the risk of operator error
from excessive handling of the sample during preparation and injection.
Of course, each method has its advantages and disadvantages. Method A (ASTM D3612A) is by far
the longest-standing technique and is still widely used today and offers accurate, reliable sample
preparation if followed rigorously. However, the alternative methods, which are more easily
automated, are gaining acceptance as they are shown to be reliable. None of the extraction
techniques completely removes all the gases from the oil. This is due to the solubility coefficient of
each gas, which must be accounted for in the final concentration determination. Laboratories must
also work with commercial suppliers ...
... to develop gas and gas-in-oil standards or they must prepare standards themselves, because
these are not currently available from national standardization bodies such as the NIST.
Repeatability and accuracy are also of the utmost importance as small changes, even several
ppm in some cases, can mean the difference between an active incipient fault condition that
requires immediate attention or one that is stable and requires no attention.
Just like with industrial oil analysis, good sampling practice is important for obtaining accurate DGA
data. Key gases such as hydrogen and carbon monoxide could easily be lost from a sample
because of their low solubilities in oil. In order to minimize the loss of gases, ASTM D3613 requires
samples to be taken using gas-tight glass syringes or metal bulbs; these are available from several
suppliers or from commercial transformer oil analysis labs.
Electrical discharges or inadequate cooling of the paper insulation cause it to overheat, generating
carbon oxide gases. Examination of the relative composition or ratios of gases present can provide
further refinement of the diagnosis. This typically involves using either Rogers ratio or Dornenberg
ratios.
The severity of an incipient-fault condition is ascertained by the total amount of combustible gases
present (CO, H2, C2H2, C2H4, C2H6, CH4) and their rate of generation. Generally, transformers will
retain a large portion of the gases generated and therefore produce a cumulative history of the
insulating materials degradation. This is an important tool for detecting and trending incipient
problems. However, it also means that care is needed in interpreting values for a first-time analysis
on service-aged transformers (more than several years old), which could contain residual gases
from previous events.
Some gas generation is expected from normal aging of the transformer insulation. Therefore it is
important to differentiate between normal and excessive gassing rates. Normal aging or gas
generation varies with transformer design, loading and type of insulating materials. Routinely,
general gassing rates for all transformers are used to define abnormal behavior. Specific
information for a family of transformers can be used when sufficient dissolved gas-in-oil data are
available.
Acetylene is considered to be the most significant gas generated. An enormous amount of energy is
required to produce acetylene, which is formed from the breakdown of oil at temperatures in excess
of 700C. Excessively high overheating of the oil will produce the gas in low concentrations;
however, higher concentrations are typically symptomatic of sustained arcing, a more serious
operational issue that can cause a transformer failure if left unchecked.
DGA is used not only as a diagnostic tool but also to stem apparatus failure. Failure of a large
power transformer not only results in the loss of very expensive equipment (costs can exceed one
million U.S. dollars) but it can cause significant collateral damage as well. Revenue losses due to
customers outages may be the least worrisome consequence of a failure. Replacement of that
transformer can take up to a year if the failure is not catastrophic and can result in tremendous
revenue losses and fines. If the failure is catastrophic, then additional loses could be realized, such
as adjacent transformers, environmental problems from the release of oil, which could be as much
as 20,000 gallons, and the resulting fire that must be contained and smothered, all of which are a
utilitys worst nightmare. In order to avoid such a failure, the sample frequency of most large power
transformers is between one and three years. However, sampling frequencies will increase as an
incipient fault is detected and monitored. Often times sampling frequencies are dictated by
insurance requirements, which often stipulate that annual transformer oil analysis must be
conducted to ensure continued coverage.
The following examples are extreme but serve to illustrate how the dissolved gas-in-oil test can be
used to highlight active problems.
EXAMPLE 14
The utility suspected that the magnetic shunt pads attached to the inside of this transformer tank
had come loose and were either touching the core (layered steel structure around which the copper
winding is installed) or were coming very close. The result was intermittent unintentional core
grounding and stray flux causing localized overheating of the oil.
EXAMPLE 25 It was suspected that a single line to ground through-fault caused the failure of this
transformer. The fault was of enough energy to destroy one of the windings. Acetylene was a
predominant gas possibly indicating that arcing may have occurred. The acetyleneto-ethylene ratio
indicated the problem could be either high temperature overheating of the oil, arcing or both. The
problem was likely in the winding because it involved cellulosic materials, as witnessed by the
comparatively high carbon monoxide and carbon dioxide concentrations.
EXAMPLE 35 A technician noticed that this transformer was enveloped in a cloud of steam
during a rainstorm. This prompted an investigation where it was found that the temperature indicator
pegged. It was estimated that the temperature in the unit had been greater than 200C. It was
discovered also that the unit became highly overloaded during some switching functions due to
current imbalances in the three phases. The condition probably existed on and off for two years. An
internal investigation found the cellulosic paper used as an insulant was brittle and crumbly. Again,
the key gas indicators for this condition were carbon monoxide and carbon dioxide.
Oil testing is an important part of a utilitys electric apparatus condition assessment. As these cases
illustrate, dissolved gas-in-oil analysis is the most important diagnostic test for detecting a wide
range of problems.
References
1. Dind, J.E., Daoust, R., Regis, J. and Morgan, J., (1971). Analysis of Gases Dissolved in
2.
3.
4.
5.