Professional Documents
Culture Documents
N
early 10 years ago, GE Factors affecting
reported that approximately
one in three large industrial
lubricant solvency
gas turbines showed signs of The following factors play a major role
oil varnishing. Because this condition in determining the solubility of varnish
affects the availability and reliability precursors in lubricants:
of GTs, the OEM recommended the use Molecular polarity. The polarity
of varnish removal systems. Despite of a molecule refers to the distribution
the recommendation, varnish-related of positive and negative charges within
turbine outages remain a significant it. In some molecules, these charges
issue for the industry. are well separated (like the poles of a
The primary reason varnish is an bar magnet); such molecules are said to
ongoing problem: The mechanism be polar. In others, there is little or no
by which varnishing occurs is poorly 1. Varnish is shown here in its insolu- separation of charge; these molecules
understood by many turbine owner/ ble form are said to be non-polar.
operators. Thus, strategies aimed Molecular polarity is not simply
at correcting or mitigating varnish- to understanding the mechanism by black and white. The polarity scale
related problems often are misdirected, which varnish deposits are formed and, incorporates shades of gray. Because
resulting in less than ideal outcomes. more importantly, the mechanism by polarity depends on the specific struc-
The goal of this article, based on a which they can be removed. ture of every molecule, it is possible for
presentation by the principal author one polar molecule to be more, or less,
at the 2013 Conference of the Frame Lubricant solvency polar than another. The corollary for
6 Users Group, is to improve under- non-polar molecules is also true. The
standing of varnish by discussing its Under normal operating conditions, most basic axiom of solvency is that
specific cause and how various miti- turbine lubricants are subjected “like dissolves like.”
gation alternatives work to minimize to oxidation, which produces polar This accounts for the fact that
operational impacts. molecules (varnish precursors) from polar alcohol will dissolve fully in
non-polar ones (lubricant mineral- polar water while polar water will
Varnish formation oil base stocks). These polar spe- not dissolve in non-polar mineral
cies represent the starting point of oil. Although the varnish precursors
Lubricant varnish generally is defined the varnish life cycle. As a result, produced by oxidative degradation
as a thin, hard, lustrous, oil-insoluble lubricants in service are a complex of mineral oil base stocks are polar,
deposit composed primarily of organic combination of base stocks, additives, they are much less so than water.
residue. It is most readily defined and contaminants. Consequently, these somewhat polar
by color intensity and is not easily A lubricant’s solvency is defined degradation products have some finite
removed by wiping. as its ability to dissolve these distinct solubility in a lubricant’s non-polar
While this definition provides an components. Everything in the oil has mineral-oil matrix. Degradation
adequate description of varnish at a finite solubility, which is affected by products that are more polar will be
the end of its life cycle (Fig 1), it must numerous variables (molecular polar- correspondingly less soluble.
be expanded as follows to account for ity, contaminant levels, temperature, Contaminant levels. A lubricant
the remainder of the varnish cycle: etc). This solubility determines if a has a finite capacity to dissolve other
Varnish begins its life as a soluble particular molecule is soluble in the molecules (additives, contaminants,
degradation product before convert- fluid or if it will precipitate from the varnish precursors, etc). As the oil
ing to an insoluble particulate form. fluid to form a potentially damaging degrades and oxidation products
The process responsible for the deposit. accumulate, the solvency of the fluid
deposition of particulate varnish is When the solubility of a molecule decreases accordingly. Beyond a cer-
reversible. is low, the lubricant cannot dissolve it tain point (known as the saturation
This expanded definition reveals and will actively release it, producing point), the fluid can no longer dissolve
that varnish is a shape-shifter; it can deposits. However, when the solubil- additional varnish precursors formed
be insoluble (conventionally recog- ity of a molecule is high, the lubricant by continuing oxidation and varnish
nized particulate form) or dissolved will have a high capacity to dissolve will begin to precipitate from solution
(soluble) in the fluid. An understand- it, avoiding the formation of varnish in the solid form.
ing of lubricant solvency is the key deposits. Temperature. Oil temperature
COMBINED CYCLE JOURNAL, Fourth Quarter 2013 34
LUBE-OIL MAINTENANCE
directly affects the solubilities of varnishing, it is imperative that a
all the species dissolved within it. Lubricant lubricant’s propensity to form varnish
As temperature decreases, so does deposits be determined. Most turbine
C
the solubility of varnish and its pre- users test their lubricants for varnish
he
m
cursors. In the sugar industry, hot potential using widely adopted tech-
ic
al
solutions of table sugar are cooled to niques including QSA® (quantitative
decrease the sugar’s solubility. As Step 3: Step 1: spectrophotometric analysis) and the
the sugar’s solubility falls, crystal- Varnish Soluble standardized test MPC (membrane
line table sugar is deposited from deposit varnish patch colorimetry, ASTM 7843). Pro-
the solution. This same process is prietary (non-standardized) varnish
responsible for the precipitation of test methods are not recommended,
varnish deposits in cooler regions of as they are not widely used and can-
Ph
al
ic
ys
a turbine’s lubricant circulation sys- not be readily corroborated. Other
ys
ic
Ph
Step 2:
al
tem. Because metals are more polar collaborative analyses, like patch
Insoluble
than the lubricant’s base stock, the varnish weight, may be helpful in substanti-
precipitated polar varnishes prefer ating oil health.
to adhere to the metal and form Both of the above varnish measure-
potentially damaging deposits. When 2. Varnish formation cycle is sum- ment methods can produce results
the level of varnish precursors in a marized in three steps which vary significantly depending
lubricant is at (or near) the fluid’s upon the length of time during which
saturation point, varnishing in cooler decreases. These precursors begin the oil sample was “aged.” Indeed,
regions is very likely to occur. to precipitate from solution in the longer sample aging periods produce
form of particulates. Like water higher MPC values, suggesting that
The varnish cycle freezing to form ice, this precipita- degradation of lubricants continues
tion of varnish is a physical change in the sample bottle. For this reason,
The typical varnish formation cycle and not a chemical reaction. the ASTM MPC method suggests all
in a gas turbine involves these three 3. Once formed, varnish particles samples be incubated at room tempera-
steps (Fig 2): agglomerate and form deposits, ture for 72 hours after being heated to
1. Oxidation is a chemical reaction preferentially coating metal sur- 140F for 24 hours. This well-defined
between the lubricant base stock and faces. These deposits are often the and standardized aging time has pro-
oxygen present in the air surround- cause of unit trips or fail-to-start vided inter-laboratory consistency and
ing it. Oxidation is unavoidable and conditions. Like precipitation in improved repeatability.
begins to take place the instant that Step 2 above, agglomeration and Increasing MPC and QSA values
a new fluid is exposed to air for the deposition are physical changes. during sample aging occur as a result
first time, regardless of whether or This model of varnish formation is of the continuing propagation of
not the fluid is put into service. Like widely accepted and reasonably well oxidation reactions that were likely
all other chemical reactions, the rate understood. Less well-understood is initiated when the lubricant was in
of oxidation is bound by the Arrhe- the fact that once varnish deposits service. Oils that continue to degrade
nius equation, which states that form, they can be reabsorbed, if the in a sample bottle will also continue
the rate of reaction will double for solvency of the lubricant is increased. to degrade in a lubricant reservoir.
every 10-deg-C (18 deg F) increase While the chemical changes that lead This highlights the necessity of using
in temperature. to the formation of varnish precursors varnish removal equipment on a
Once a new fluid is put in service, (Step 1) are irreversible, the physical continuous basis. In the absence of
it is exposed to higher tempera- changes (Steps 2 and 3) which lead to varnish removal equipment, lube-
tures and experiences a concomitant the formation of varnish deposits are oil reservoirs with accumulations of
increase in the rate at which it oxi- reversible. Successful varnish mitiga- dissolved break-down products can
dizes. Even when operating tempera- tion strategies use this fact to their continue to form varnish when the
tures are a typical 125F, bearings advantage. turbine is not operating.
may reach temperatures in excess
of 300F; the rate of oxidation at the Testing for varnish Strategies to combat
bearing in this instance will be more
than 1000 times greater than that in As a result of the potential for costly varnishing
the cooler regions of the system. As turbine downtime associated with Most modern turbine lubricants
a result, oxidation typi- are made with API (American
cally occurs wherever Petroleum Institute) Group II
hot spots are found. mineral-oil base stocks, which
Oil degradation
Oil degradation