Lubrication Excellence 2007 May 15-17, 2007 Louisville, KY

Practical Approaches to Controlling Sludge and Varnish in

Turbine Oils

William Moehle and Vincent Gatto, Albemarle Corporation, Baton Rouge, Louisiana, USA

Greg Livingstone, EPT, Inc., Tucson, Arizona, USA

David Wooton, Wooton-Consulting, Richmond, Virginia, USA

Abstract

Free radicals formed by oxidation or spark discharge are frequently the root cause for varnish
and deposit formation in turbines. Traditional methods of analyzing used oils, such as viscosity
measurement, acidity or carbonyl oxidation, were originally developed for turbine oils based on
Group I base oils and are usually inadequate to predict eminent field problems for turbine oils
using Group II, III and IV base stocks. This paper discusses why different behavior is observed
in the field for turbine oils based on different base stocks and why there is a range in the
performance of turbine oils depending on the types of antioxidant systems that are used. Key
criteria for selection of the antioxidant systems in general, and phenolic antioxidants in
particular, are discussed. A more suitable method for monitoring turbine oil acceptability in the
field, particularly for the newer Group II and higher base stocks, is to measure depletion of the
various antioxidant types present in the system. This approach allows one to more accurately
estimate when field problems may occur and provide sufficient time to protect the overall system
and extend the lubricants useful life. Also critical is the availability of new tests that allow
varnish problems to be identified. All of this data must be assessed and used with an appropriate
oil monitoring approach in order to minimize the chance for developing varnish and deposit
problems in power turbines. This paper examines this issue from a well-rounded perspective and
provides a multi-faceted approach to controlling sludge and varnish in turbine oils.

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Introduction

Varnish occurrences are frequently reported and are among the top O&M concerns for some
turbine oil users. The biggest problem with varnish is valve performance in critical control
systems. An example of a varnished spool from a liquid fuel pilot valve can be viewed in FIG. 1.
Other problems reported from turbine oil varnish include premature bearing wear, decreased
filter life and performance, impedance in tight clearance flow paths such as lift oil lines, blocked
oil orifices such as pencil filters and reduced heat exchanger performance.

FIG. 1: Varnish spool from a liquid fuel pilot valve.

How big is this varnish problem? In a recent study of 119 turbine oil systems by the authors,
75% of gas turbine lubes were found to have varnish potential ratings above normal while
steam turbines scored at only 13%. In fact, the highest steam turbine varnish potential rating in
the survey was a 50 out of a 0-100 scale, which was the average for all of the gas turbines in the
study. When one examines the gas turbine data more carefully (data covering 85 discrete
turbines) the units with a common lube and hydraulic reservoir had higher varnish ratings.
Furthermore, units that operate in peaking or cycling modes are more susceptible to performance
problems due to varnish. Finally, it became evident that certain turbine oil formulations are
more prone to varnish formation than others. Paradoxically, turbine oils with high RPVOT

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values did not necessarily perform better in terms of varnish potential, and more often than not
had higher varnish potentials. Clearly, not all turbine oils are created equally.

It is easy to get advice on how to solve lubricant varnish. Companies selling conditioning
systems often claim that installing their technology will solve all varnish problems. The
prescription sometimes offered by oil companies is to use their brand of oil to eradicate the
issues.

This paper offers a rounded perspective at controlling sludge and varnish in turbine oils. For the
purposes of this paper, we will focus on large frame industrial gas turbines with combined lube
and hydraulic systems that are operated in a peaking or cycling fashion. These are the most
extreme environments, thus a good example to allow the user to gauge where potential for
varnish formation might exist in their systems. This segment represents an installed base of over
7,000 such units around the world with tens of millions of gallons of turbine oils.

Causes of Sludge and Varnish

There are numerous reasons why varnish occurrences are more common today than in the recent
past. These reasons are associated with system operational conditions (elevated temperatures,
reduced dwell times, increased flow rates and tighter mechanical filters), turbine oil formulations
(all aminic versus mixed phenolic and aminic), as well as fluid maintenance (FIG. 2). Todays
turbine fleet undergoes significantly higher fluid operating temperatures which promotes
oxidation and additive depletion. This is combined with fluid formulation changes that may not
be optimized for the equipment. As seen in FIG. 2, the problem is initiated by higher thermal
and mechanical stress from modern turbine engine design. This is compounded by the poor duty
cycle associated with increased flow rates and filtration conditions to produce more varnish.

Factors that Increase Varnish Occurrence in Gas Turbines

Less Tolerant of
Cooler temperatures Increased Rates Cooler temperatures More Air Bubbles =
Insolubles and/or Increased Rate of
encourage varnish of Oxidation encourage varnish increased rate of oxidation
not optimized to Spark Discharge
formation formation and micro-dieseling
prevent varnish.

New Oil
Formulations

Increased Cycling/
Hotter Increased Less Dwell Increased Major Varnish
Output/ Peaking
Temperatures Flow Rates Time Filtration Problem
Production duty cycle

Cooler
placed on
outlet of
reservoir

Causes More Causes More Causes More Causes More

Varnish Varnish Varnish Varnish

FIG. 2: Simplified representation of some of the causes of gas turbine varnish

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Preventing varnish can be viewed like links to a chain. The critical links are:

1. Turbine Oil Formulation Chemistry

2. Thermal Degradation
3. Additive Depletion
4. Fluid Maintenance

FIG. 3: The key criteria in preventing varnish

The ideal system has strong links in all areas to prevent varnish. Conversely, even if the turbine
oil in use has excellent formulation chemistry and minimal amounts of thermal degradation and
additive depletion, varnish may still be a problem if the end-user does not properly maintain the
fluid.

Turbine Oil Formulation Chemistry

Most end-users believe that if an oil meets the OEM specification, then it will provide years of
reliable service in their application. With turbine oils, this is simply not the case. There is a
wide range of fluid performance based on the products formulation.

OEM Selling
Specifications Points

Formulation

Product Cost

FIG. 4: The balance required in oil formulation.

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The three primary guidelines for formulators in creating turbine oils are the OEM specifications,
competitive selling points and product cost. Until very recently, no OEM had demanded turbine
oil meet sludge limits. (As of this writing, only one OEM has included sludge tendency as part
of their specifications.) This is partly due to the fact that adequate varnish tendency tests
established by the international standard committees havent been in place. Regardless of
standards, modern turbine oils do not have to be optimized for low varnish production in order to
meet OEM specifications. The key competitive selling point that has been used for turbine oils
over the last couple of decades is the fluids oxidative stability as measured by RPVOT (D2272)
and TOST (D943). Utilizing Group II and higher basestocks make it easier to create extremely
high oxidative values for these tests. Unfortunately, good test results with this test criterion are
not related to low sludge forming characteristics. Also, cost factors play a significant role in
determining formulation chemistry. An example of how these factors may not produce a turbine
oil optimized for sludge formation is the use of phenyl-alpha-naphthyl-amine (PANA) an
antioxidant used in some turbine oils. This product provides among the best bang-for-your-buck
chemistries for very high RPVOT values and also produces considerable sludge upon depletion.

A Disconnect Between Laboratory Oxidation & Varnish Tests and Field Experience

Field experience suggests that there is a higher degree of varnish problems in modern
formulated, API Group II+ oils. End-users often comment that they wish that Group I turbine
oils were still available because varnish problems were not significant 20 years ago. This
sentiment is opposite of what the laboratory oxidation tests reveal. It is often suggested that
varnish occurs more readily in Group II and above oils because the fluids have lower solvency
and therefore a lower tolerance for degradation by-products. If reduced fluid solvency was the
primary reason for varnish problems, then one would expect to observe similar results from the
laboratory oxidation tests. There are at least three possible explanations for the differences
observed between laboratory tests and field experience.

1. Although there have been considerable oxidative studies on Group II versus Group I
turbine oils, little of this research focused on varnish production. One reason is that there
is not a standardized varnish test suitable for Group II and above oils established by the
standard bodies. As a result, turbine oil formulations have focused on oxidative stability
and have not necessarily been optimized for resisting deposit formation. There is often
an assumption that the more oxidatively robust a turbine oil is, the more resilient to
varnish formation it is. This assumption is incorrect as some of the additive components
that best enhance the fluids performance in oxidative tests are significant contributors to
deposit formation.
2. There are operating conditions in the field that cannot be simulated in a laboratory
oxidation experiment, such as spark events from mechanical filters.
3. There is evidence to suggest that topping off used Group I turbine oils with new Group II
fluid encourages the transition of soluble degradation by-products to insoluble and
varnish causing degradation by-products.

Several new turbine oil formulations with properly balanced additive systems are showing
excellent performance and lower varnish problems in high stress environments (Reference 1).

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The data shows that turbine oils with mixed antioxidant systems that have been optimized for
minimal varnish production perform better than their Group I ancestors.

There is also strong evidence to support the use of Group III and IV base stocks, provided that
they too are intelligently formulated.

The Importance of a Mixed Antioxidant System

A practical approach to preventing the formation of the undesired oxidation products and
minimizing varnish formation is to control the free radicals that are produced during lubricant
oxidation. Antioxidants are designed to control free radicals by donating a hydrogen atom to the
free radicals in the base stock so that a more stable molecule is formed. The antioxidant then
becomes a free radical, but is a much more stable radical. Depending on the antioxidant used,
the free radical form of the antioxidant may also react with another free radical from the base
stock leading to two relatively stable materials. Some antioxidants can even go through complex
chemical reaction schemes that allow them to regenerate themselves (Reference 2).

The two most commonly used chemical classes of antioxidants are amines and phenols. Table 1
shows the relative advantages of amines and phenols in stabilizing lubricants.

Table 1: Relative advantages of different antioxidant systems.

Antioxidant Varnish Deposit Oxidation Viscosity Low Temp High Temp

Control Control Control Control Control Control
Amine + + +
Phenolic + + +
Both + + + + + +

Note that if the right combination of phenols and amines are chosen, its possible to produce an
antioxidant system that has good performance in all areas. These aminic/phenolic systems work
to protect the lubricant by the mechanism shown in FIG. 5. Here the amine efficiently reacts with
the free radicals from the oil oxidation, but it is then regenerated by the phenolic, which is a good
free radical trap. The phenol radical is stable and does not react further to degrade the lubricant.
FIG. 6 is a comparison of the amine degradation process in an all amine system versus an
aminic/phenolic system at the same total antioxidant treat rate. Note that the amine depletes
from the lubricant more rapidly when the phenol is not present. FIGs. 5 and 6 illustrate the
importance of the phenolic to both re-generate the amine and prevent it from degrading. FIG. 7
shows that oxidation control, as measured by PAI (FTIR Peak Area Increase of the carbonyl
oxidation peaks), is improved when a mixed antioxidant system composed of amine and phenolic
is used. FIG. 8 shows that in a mixed system it is also possible to obtain superior varnish control
as long as sufficient phenolic levels are maintained (Reference 3). When phenolic levels fall
below a critical level varnish levels start to increase. Thus the life of the turbine oil can be related
to the level of phenolics in the system.

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Phenol Radical - STABLE

Peroxy Free Amine Radical

Radical

ROO . R
.
N R
.O
H2
C OH

H
ROOH R N R H2
HO C OH
Stable
Hydroperoxide Amine Antioxidant (e.g. NDPA)

Phenol Antioxidant (e.g. MBDTBP)

FIG. 5: How an amine and phenol interact synergistically to quench free radicals.

0.04
Rapid decline indicates
0.035
Diphenylamine degradation
NH Peak Intensity

0.03
Gradual decline indicates
0.025
Diphenylamine regeneration
0.02

0.015

0.01

0.005
0 10 20 30 40 50 60 70
Time (Days)

0.25% Aminic 0.125% Aminic & 0.125% Phenolic

FIG. 6: Amine depletion, as measured by FTIR, of an all amine system versus a mixed
phenolic/amine system in Group II turbine oil at 95oC.

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180
160
140
120 Synergism when
100 a mixed amine and
PAI

Phenolic system
80
Is used
60
40
20
0
0 20 40 60 80
Time(Days)
0.125% P henolic & 0.125% Aminic
0.25% Aminic alone

FIG. 7: Oxidation for an all amine system antioxidant system versus a mixed
amine/phenolic antioxidant system in Group II turbine oil at 95oC.

140 100
aminic
90

Varnish Potential Rating

120
% AO Versus New Oil

phenolic
80
Varnish
100 70

80 60
50
60 Critical level of phenolic 40
needed to suppress varnish
40 30

Varnish formation tracks phenolic depletion 20

20
10
0 0
0 1 2 3 4 5 6 7
Time (days)
FIG. 8: Varnish control in a mixed amine/phenolic system can be maintained as long as
the phenolic level does not dip below a critical level (Reference 3).

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In all the base stocks, the antioxidants deplete during the oxidation process. For Groups II, III
and IV base stocks, this depletion is occurring before there is any change in the traditional
measures of oxidation and is therefore an early indicator of potential oxidation related problems.
This additive depletion can be monitored by traditional FTIR techniques (Reference 4) or by use
of a relatively new instrument, the RULER (Reference 5), which works on the principle of cyclic
voltammetry (see section on antioxidant depletion and fluid maintenance).

Choosing A Phenolic

We have given consideration on how to choose an acceptable phenolic antioxidant considering

the complexities of the turbine environment. Recent data indicates that the presence of a
phenolic is important for deposit and varnish control - but which phenolic? FIG. 9 shows the
structures of several common phenolic antioxidants. References 1 and 5 indicate that MBDTBP
is a high performance phenolic, but it is a solid and has limited solubility in some base stocks.
DTBP and BHT are effective antioxidants, but their relatively low molecular weight makes them
too volatile for many gas turbine applications or for extended drain use. HPE has low volatility,
good solubility and reasonable performance, which makes it an excellent candidate for this
application. Its drawback is its relatively low phenolic content per unit weight which increases
the relative amount of phenolic needed.

Phenolics with good overall Phenolic with excellent

combination of Properties performance, but low solubility.

O
H2
HO CH2CH2COC8H17 HO C OH

HPE MBDTBP

Phenolics with high volatility

OH OH

BHT DTBP

FIG. 9: Selecting the proper phenolic for turbine oils.

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Thermal Degradation

Thermal degradation is the high temperature breakdown of a lubricant due to the cracking of the
hydrocarbon structure. Temperatures in excess of 300oC are required to do this. The hottest
known bearing temperatures in a large frame gas turbine are 262oC, found in the middle bearing
of a particular turbine design. However, from the authors experience, thermal degradation is a
primary degradation mechanism in gas turbine oils. FIG. 10 shows two FTIR spectra of used
turbine fluid. Used Oil 2 shows some oxidation, but minimal thermal breakdown, while Used
Oil 1 shows considerable thermal decomposition of the fluid. As one would expect, thermal
breakdown is always accompanied by additional oxidative breakdown. The type of
decomposition observed in Used Oil 1 is commonly observed in fluids where thermal breakdown
has been reported by additional evidence.

Used Oil 2 Evidence of Thermal degradation

59.
58
56
54 Used Oil 1
52
%T
50 1666 1632
1697 1659
48
46
44 Evidence of Oxidation

42 1601
40
39.
1887 1860 1840 1820 1800 1780 1760 1740 1720 1700 1680 1660 1640 1620 1600 1580 1560 1538.
cm-1

FIG. 10: FTIR Spectra of two Used Turbine Fluids

Based on dozens of filter inspections from gas turbines, it is clear that static-generated sparks are
a common occurrence. This is a phenomena of molecular friction occurring as the oil flows
through small clearances. The smallest clearance zones in most lubrication systems are the
mechanical filters exactly where the sparks tend to discharge.

Spark evidence has been found in the main lube filters, where the flow rates are extremely high,
and in last chance filters where the flow rates can be very low. Evidence of sparking can be from
microscopic inspection of the filter media, filter core, filter meshes and from debris carried away
from the filter. An example of evidence from sparking can be seen in FIG. 11.

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Regardless of the basestock or additive chemistry employed in turbine oil, significant spark
events have been observed and will cause thermal degradation and varnish problems.

There is evidence of methods to minimize the amount of spark events occuring in an operating
gas turbine. Efforts such as heat tracing lines, lowering filter flux, using larger sized filter pores
and employing different filtration mediums have been shown to have a positive impact on
minimizing spark events.

Spark Crater caused

by multiple spark events.

FIG. 11: Damage on a last chance filter core from a spark event.

Additive Depletion

There is constant oxidative stress on turbine lubricants. Antioxidants are designed to react
before the base oil, sacrificing themselves to protect the fluid. There are two primary problems
created as additives deplete. First, when antioxidant levels become low the fluid is in danger of
rapid degradation resulting in the formation of soft contaminants and varnish. Second, several
amine antioxidants form deposits when depleted.

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As discussed in the oil formulation section, amines will react first, especially in the higher
temperature zones, but then are regenerated by the phenols. This regeneration process can not be
viewed in a condition monitoring program. The observations are that the phenols deplete first, as
can be seen in FIG. 12. This figure is the output from a RULER test and shows two samples: the
new fluid (the upper curve in green) and the used fluid (the lower curve in red).

Amines Phenols
100% of new 55% of new

FIG. 12: Amine versus Phenol Degradation as measured by the RULER.

The area under the first peak represents the amount of amines. The area under the second peak
represents the amount of phenols. The results from this test show that the amine level is 100% of
new and the phenols have depleted to 55% of new. As the level of phenols continues to drop,
one should expect performance problems.

A test six months later showed even more depletion of the phenolic antioxidant, as seen in FIG.
13. During this same time period, the analytical varnish potentials increased and unit trips and
fail-to-start conditions occurred due to valve sticking. While amines still had minimal depletion
(92% of new), phenols were almost completely depleted (14% of new). It should also be noted
in this example that the relative ratio of amines to phenols show that there are considerably more
amines in the product formula. The time before significant fluid degradation and varnish
problems might have been extended had this formulation contained higher levels of phenols.

This example demonstrates the importance of having phenols formulated into turbine oil
products and the effectiveness of the RULER for predicting fluid degradation.

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FIG. 13: Six months later, almost all of the phenols had been depleted.

Fluid Maintenance

There are many field examples of the same vintage gas turbines being installed in similar
locations and with similar operating conditions. Yet, one turbine is plagued with varnish
problems and the other is not. Often this comes down to how the fluid is maintained. There are
many proactive maintenance practices that should be incorporated to extend fluid life and
performance that are outside the scope of this paper. However, the use of contamination control
technologies and continual diligence in following good maintenance practices is extremely
important. One technology that has had a positive impact on removing soft contaminants leading
to varnish formation is electrostatic oil cleaning (FIG. 14). This technology removes insoluble
contaminants from turbine fluids and has been shown to decrease the varnish problem in these
systems.

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FIG. 14: Electrostatic oil cleaner for gas turbine installations

Condition Monitoring

A key part of fluid maintenance is condition monitoring. In order to design an effective method
to monitor turbine oils, one must understand the failure mode of the fluid. This has become
complicated in recent years with the introduction of Group II and higher base oils. The more
highly refined Group II and higher basestocks are more oxidatively stable, but when they fail,
there is little warning from the normal oxidation tests (viscosity change, total acid number,
peroxide value, PAI, etc.). This phenomenon is discussed more thoroughly in several papers
(reference 2 and 6).

Comparing the mode of degradation of a Group I fluid versus a Group II and above fluid shows
considerable difference, as can be seen in FIG. 15. It is reasonable to expect that the methods of
monitoring turbine oil condition would be significantly different in Group II and higher oils
compared to older Group I oils. Fortunately, there is an early predictor of lubricant failure
involving the close monitoring of phenolic and aminic antioxidant depletion as has been
discussed above.

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As part of proper fluid maintenance practices, a good periodic analyses program is required. The
key analytical tests to monitor the condition of modern turbine oils are:

Cyclic Voltammetry (RULER) for antioxidant depletion

Membrane Patch Colorimetry (Current ASTM draft method) for varnish potential
Fourier Transform Infrared (FTIR) for antioxidant depletion
Oil Degradation

s
I Oil
r oup
G

FIG. 15: Mode of Turbine Oil Degradation

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Overall Recommendations to Controlling Sludge and Varnish in Turbine Oils:

Turbine Oil Formulation

1. Select Group III or IV base oils whenever possible.

2. Utilize a combination of phenolics and aminics with a higher level of phenolic relative to
aminic for maximum aminic protection.
3. Exercise caution when using volatile phenolics such as BHT and DTBP with the less
volatile HPE and MBDTBP being preferred.
4. Avoid or minimize PANA to suppress varnish formation.

Thermal Degradation

1. Inspect filters for signs of spark events and review FTIR analysis for evidence of
oxidation and thermal degradation.
2. If there is evidence of sparking, take proactive measures to minimize this by maintaining
elevated temperatures, decreasing filter flux and investigating different mechanical filter
technologies.

Antioxidant Depletion

1. Closely monitor phenolic and amine antioxidant depletion.

2. When the phenolic antioxidants are close to depletion (below approximately 20 to 30% of
good quality new fluid levels), expect the amine levels to start to deplete and varnish
potential ratings to increase.

Fluid Maintenance

1. Condition monitoring program should consist of RULER, MPC and FTIR.

2. Employ an electrostatic oil cleaning system.

Conclusion
Varnish problems are most severe in peaking or cycling gas turbine applications that share a
common reservoir for hydraulic controls and bearing lubrication. Although a lot of research has
been performed to identify the mechanism of varnish formation in turbine oils, there is still work
to be done. One thing evident from the research is that there is not one cause or one solution to
this problem. Current research on varnish is slowly illuminating the causes and some solutions
to controlling this deposit. It is clear from the research that a multi-pronged approach should be
taken in high-stress turbine oil environments. An important step is selecting turbine oil with a
mixed antioxidant system composed of an amine and phenolic antioxidant optimized for
minimum varnish production. Another step is to minimize thermal stress placed upon the fluid
in service. The turbine oil needs to be closely monitored for additive depletion and soft
contaminant generation during service. Finally, fluid conditioning technologies such as
electrostatic systems should be utilized to help control varnish.

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Rererences

1. Okazaki, M. E.; Militante, S. E., Performance Advantages of Turbine Oils Formulated

with Group II Base Oils. ASTM Special Technical Publication (2001), STP
1407(Turbine Lubrication in the 21st Century), p 79-85.
2. Gatto, V. J.; Moehle, W. E.; Cobb, T. W.; Schneller, E. R., Oxidation Fundamentals and
Its Application to Turbine Oil Testing, Journal of ASTM International, Vol. 3, No. 4,
paper ID JAI13498.
3. Livingstone, G. J.; Thompson, B. T.; Okazaki, M. E., Physical, Performance and
Chemical Changes in Turbine Oils from Oxidation, Journal of ASTM International, Vol.
4, No. 1, paper ID JAI100465.
4. Obiols, J., Lubricant Oxidation Monitoring Using FTIR Analysis Application to the
Development of a Laboratory Bulk Oil Oxidation Test and to In-Service Oil Evaluation,
JSAE Technical Paper No. 20030124, JSAE, Tokyo, Japan, 2003.
5. Ameye, J.; Kauffman, R. E., Antioxidant Analysis For Monitoring Remaining Useful
Life of Turbine Fluids. ASTM Special Technical Publication (2001), STP 1407(Turbine
Lubrication in the 21st Century), p 86-107.
6. Gatto, V. J.: Moehle, W. E.; Schneller, E. R.; Cobb, T. W., The Relationship Between
Oxidation and Antioxidant Depletion in Turbine Oil Formulations with Group II, III and
IV Base Stocks, J. Syn. Lubr., submitted.

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