Oxidation: Why Good Oil Turns Bad

Keith Spoonmore, Noria Corporation

Oxidation could be described as the degradation of good oil gone bad. What was once a
stable lubricant is now just sludge and varnish causing havoc in your equipment’s
system. How does this happen?
What was true when your mother said hanging around the wrong crowd was bad is also
true with your lubricants. A bad environment can have devastating effects on the quality
and life of a lubricant. To keep your lubricant in optimum condition, the bad environment
must be identified and steps taken to prevent its destruction.
Lubricants are vulnerable to attack. Most non-synthetic lubricants are comprised of two
components: mineral oil and additives. The oil is a group of molecules made of hydrogen
and carbon atoms.
These atoms have a positive attraction for each other, connecting by a method called
bonding. If the right amount of hydrogen and carbon is available, the molecules are said
to be saturated. This means they are stable and will not attempt to react with other
potentially bad elements.
The problem arises when some hydrogen atoms are not present. The molecule
becomes unsaturated and is quite reactive. This can be the beginning of the end for the
lubricating oil.

Oxygen
The bad environment comes from an unlikely source: oxygen. Oxygen is the third most
abundant element on earth. It is in the air you breathe and the water you drink as well as
countless other substances. Oxygen as an element is actually two atoms which bond
together and generally are not a major source of problems.
If, however these atoms separate, they go looking for another element to bond with and
produce a reaction. This separation of the oxygen element is caused by an increase in
energy. The separated oxygen atom encounters an unsaturated hydrocarbon, they
bond, and the reaction is devastating. Acids are created which attack the oil, resulting in
oxidation. Air is the major source of oxygen needed to make the good oil turn bad.

Heat
The energy needed to separate the oxygen atoms, and to some extent the
hydrocarbons, comes in the form of heat. Heat can originate from a myriad of sources,
including the mechanical process, the external environment, friction, etc.
For the oxygen element to separate, only a small amount of energy is required
(approximately 495 kilojoules). This is equivalent to 120 calories, which is about the
same amount as a half slice of birthday cake. Hydrocarbons are a bit worse and require
less energy. Any increase in heat creates a volatile environment, adding to the potential
of oxidation and varnish formation.
Other Bad Environments
Other environments may also affect the life of a lubricant. For instance, water can
impede lubricant life. However, this generally is accomplished by degrading additives
that attempt to deter oxidation. Water requires a lot of energy to break apart, so oxygen
availability is limited. In addition, metals can react with mineral oils, causing sludge.
Process fluids may be damaging as well. Process acids can lead to major destruction.
Ultraviolet light is another source of energy that can result in oil degradation.

Controlling Oxidation
Preventing the lubricant from a life of oxidation requires minimizing the availability of air
and controlling heat. It is important to remember that heat alone will not lead to
oxidation. It can only expedite the reaction process between two unstable elements.
Since heat reduction or control may be difficult to achieve, controlling air availability is a
better option. Following are some actions to better control air and heat in your systems.

Air Control
In circulating lubrication systems, ensure the fittings and connections are tight. Air can
be sucked into the lubricant through loose connections. Once inside, there is plenty of
agitation to allow the oxygen and hydrocarbons to react. Also, keep your bearing seals in
good shape. Air can infiltrate through defective seals, enabling the oxygen and
hydrocarbons to react and form oxidation products.

On reservoir systems, maintain a positive pressure. Using an inert gas such as nitrogen
prevents air from entering the system. Finally, consider oil mist. Although oil mist is
mostly air, the temperatures are low enough to prevent the oxygen atoms from
separating. It also provides positive pressure to keep external contaminants at a
minimum.

of lubrication professionals say oil

degradation products such as oxidation and
78% varnish have caused problems for their
plant's machines, based on a recent survey at
MachineryLubrication.com

Heat Control
Always use the correct viscosity grade. Low-viscosity lubricants allow metal-to-metal
contact, which generates friction and results in excess energy from the heat produced. A
high viscosity can cause internal friction and lead to similar problems. Your lubricant and
equipment manufacturer can help you determine the right viscosity for your application.
Equipment vibration should also be kept at a minimum. Excess vibration can occur for a
multitude of reasons and cause increased metal-to-metal contact and heat. Additionally,
try to restrict external heat where possible. Use fin fans or covers to inhibit the heat
absorbed from the environment. Consider adding coolers to reduce heat buildup in the
lubricant.

Avoid Bad Environments

How do you keep a good oil from turning bad? Analyze your lubricant systems, looking
for air-entry avenues. Remove these points of entry wherever possible. Find the sources
of heat and engineer methods to reduce or control that energy.
Lubricants can have long lives free of oxidation. Equipment optimized in this manner will
provide high production rates and minimal downtime. Just stay away from those bad
environments.

Sludge and Varnish in Turbine Systems

Jim Fitch, Noria Corporation
A wide range of fluid degradation issues can affect lube oil systems.
One growing concern is the presence of sludge and varnish. This
condition can occur in even the most well-maintained machines.
Surprisingly, it can also arise when oils are not particularly old or
contaminated, as well as in thermally robust synthetic lubricants
and hydraulic fluids.

Figure 1. Varnish Formation on Inlet Guide

Vane (IGV) Valve from a Gas Turbine

Sludge and Varnish Defined

The products of lubricant degradation are called sludge and
varnish. These products are generally unstable in the oil and, as
such, are prone to form deposits or separate from the bulk oil. In
certain instances, deposits form on machine surfaces at the exact
location where the oil has degraded. In other cases, the oil
degrades in one location but the insoluble degradation products are
carried elsewhere by the moving fluid forming deposits on surfaces.

Figure 2. Varnish Formation on Plain Bearing and

Shaft (Courtesy Cerestar Deutschland)
Over time, some deposits can thermally cure to a tough enamel-like
coating. Other types of deposits, generally in cooler zones, remain
soft or gummy, and may in some cases appear clear and grease-
like. The following are examples of where sludge and varnish might
occur in turbine lube oil and electrohydraulic control systems:

 black crusty deposits on mechanical seals

 gold adherent films on valves
 charcoal-like deposits on babbitt sleeve bearings
 gooey-brown accumulations on oil filters
 black scabby deposits on mechanical seal surfaces thrust-
bearing pads
 carbonaceous residue on mechanical surfaces

The deposits that form on sensitive machine surfaces interfere with

the flow of fluid and the machine’s mechanical movements,
contribute to wear and corrosion or may simply just cling to surfaces
and impair heat transfer. For example, deposits on the spool and
bore of a servo control valve can tighten the interference fit.
Other types of sludge and varnish-induced failures include silt lock
valve failures, plugged orifices, damaged mechanical seals,
plugged discharged ports, journal-bearing wear (disrupted
hydrodynamic film production), premature plugging of oil filters and
impaired oil cooler performance.

Turbine Systems
In turbine systems, few failure conditions can disrupt operation as
quickly and completely as a varnished and seized-up control valve
operation. Sludge can gum up flow controls, strainers and critical oil
pathways. In recent years, there has been an increasing number of
reported cases associated with varnish and sludge formation in
turbine-generator applications.
In turbine applications where reliability is essential and operating
conditions are stressful, there is a need for incipient advisories that
report developing varnish potential. The risks are especially
pronounced in high-pressure, servo-controlled hydraulic systems
operating in continuous and high-duty service.
Degradation Methods and Analysis
Before discussing the methods for analyzing sludge and varnish in
turbine systems, it is helpful to understand the lubricant degradation
methods in turbine lube oil and hydraulic systems.

Bulk Oil Oxidation

Oxidation causes degradation of the bulk oil over time. Under mild
machine operating conditions and clean environment, oxidation will
occur gradually once the oxidation inhibitor additives have depleted.
However, elevated temperatures accelerate the oxidation process –
the general rule of thumb is that for every 10°C (18°F) increase in
operating temperature, the rate of oxidation doubles (Arrhenius
Rate Rule).
Water, metals (such as iron or copper particles) and aeration also
act as catalysts to speed up this process. Oxidation by-products
develop and coalesce into suspended insolubles in the oil as the
rate of oxidation increases, resulting in progressive formation of
sludge and varnish in the system.

Thermal and Compressive Base Oil Degradation

Thermal degradation occurs due to adiabatic compression from
entrained bubbles or when oil comes in contact with a hot surface.
When the machine surface is greater than 200°C (400°F),
depending on oil type, thermal degradation can start.
Such heat can come from gas combustion, steam and highly loaded
frictional surfaces. Often the aeration occurs due to tank agitation,
plunging oil returns or surface lapping. Suction line leaks, pump
seal leaks and venturi zones (vena contracta regions) can also
introduce air into circulating fluids.
Regardless of the means of entrainment, the forcing function that
leads to sludge and varnish is in place. The failure will now proceed
along one of two pathways. Both involve adiabatic compression in
either the load zone of a lubrication system or the pressured zone
of a hydraulic control system.
Adiabatic compression occurs when air bubbles travel from low
pressure to high pressure. The air bubble compresses rapidly
(implosion), resulting in the entrapment and concentration of heat
and extreme rise in the oil’s temperature. The temperatures
reached (typically greater than 1,000°F) are often more than
sufficient to thermally degrade the oil.

Electrostatic Discharge
Studies have been conducted on the effects of static discharge in
hydraulic systems since the 1970s. Static discharge is a form of
localized thermal degradation, which has been discussed
previously. Recently, attention has been directed to fluid
electrification and static discharge as a prominent contributor to
sludge and varnish formation in turbine systems.
Electrostatic charge generation occurs in fluid systems as a result
of internal molecular friction and electric potential between the fluid
and machine surfaces (particularly where no boundary films
develop, such as the interstices of an oil filter). Many factors
contribute toward the magnitude of the static charge within the oil;
however, grounding of the machine itself has little impact toward
mitigating charge propagation.
This is due to the oil being nonconductive, which effectively self-
insulates the charged fluid zones from grounded surfaces. Once
these charges build up in the working fluid zones, including
reservoirs, the subsequent static discharging, similar to lightning
strikes through the fluid, may cause localized thermal-oxidative oil
degradation.
 Figure 3. Acid Number (AN) for Turbine Oil Exposed to Static
Charges
after Zero, Six and Nine Months in Storage
According to research conducted by Dr. Sasaki, spark discharges
can reach temperatures as high as 20,000°C. Additionally, he has
found that although the initial failure is localized, the chemical
degradation process is autocatalytic. In one study, a turbine oil
sample was exposed to spark discharges. Acid number (AN) was
measured on the oil samples just after initial exposure and after six
and nine months of oil storage.
Results of this test are shown in Figure 3. AN was measured
immediately after the tests and were the same, regardless of the
number of sparks exposed to the turbine oil, suggesting that the
bulk oil degradation had not yet started. However, there was a
significant change in AN after being stored, indicating that the oil
oxidation process had advanced past the induction period, even
when stored at room temperature in the dark.
Conditions of
Stages of Corresponding
the Fluid to be
Failure Analytical Method
Tested
Stage One Measurable 1. Various
(precursor oxidation root laboratory particle
stage) – Root causes: counting methods
causes that 1. Particle (optical, pore
propel the fluid contamination blockage and
into the next 2. Wear debris microscopic)
stage 3. Water 2. Elemental
contamination analysis,
4. Antioxidant ferrography, ferrous
additive density analysis
depletion 3. Various
laboratory methods
including Karl
Fischer and FTIR
4. Methods include
FTIR, RPVOT,
RULER and
HPDSC
Stage Two The presence 1. FTIR (1,730 cm-
(transitory of soluble 1), AN
stage) – The oxidation 2. Coagulated
beginning of products to oxide insolubles
base oil form: 3.
degradation 1. Carboxylic Spectrophotometry,
and increasing acids, formic patch colorimetry
risk of acids, etc.
varnishing 2. High-density
formation resins,
polymers, etc.
3.
Chromophoric
compounds
(color bodies)
Stage Three The presence 1. Analysis of
(attack stage) of both soluble sludge (bottom
– More and sediment, organic
advanced insoluble filter sediment, etc.)
oxidation oxidation by elemental
phase where products to analysis, FTIR
significant risk form: (1,730 cm-1),
of varnish, 1. Metal GC/MS
corrosion and carboxylate 2. Ultracentrifuge,
impaired soaps and patch test,
lubrication is sludge patch colorimetry
present 2. Suspended 3. Viscometry
oxide
 insolubles
3. Rising oil
viscosity
Table 1. Methods for Analyzing
Oxidation-induced Sludge and Varnish

Analysis Techniques for Monitoring Sludge and

Varnish
Analytical techniques for measuring sludge and varnish vary
depending on the failure mechanism. These methods fall into three
categories, according to the stage of contaminant or degradation
product targeted. The first stage is a precursor condition.
Specifically, it relates to the contaminants that give lubricants a
propensity to form oxides and other oil breakdown products.
Stage two is a transitory stage. Typically, it consists of soluble
oxides and other dissolved impurities that might later synthesize to
form insolubles. The condition that aids the transition from stage
two (oxide soluble) to stage three (oxide insoluble) may be cold oil
temperature or simply a supersaturated state (a concentration of
oxides in excess of the varnish saturation point).
Conditions of
Stages of Corresponding
the Fluid to be
Failure Analytical Method
Tested
Stage One Measurable 1. Air release tests,
(precursor root causes: (ASTM D3427)
stage) – Root 1. Impaired air- 2. FTIR, elemental
causes that release analysis, etc.
propel the fluid properties 3. Various standard
into the next 2. Cross lab tests for such
stage contamination impurities
(mixed
lubricants)
3.
Contamination
with polar
impurities (dirt,
water, oxides,
 etc.)
Stage Two The presence 1. Thick-cell (500
(transitory of soluble µm) FTIR for
stage)- The thermal nitration (1,639 cm-
beginning of degradation 1)
base oil products: 2.
degradation 1. Nitric oxides Spectrophotometry,
and increasing 2. patch colorimetry
risk of Chromophoric 3. Pattern testing
varnishing compounds (combining above
formation (color bodies) tests with RPVOT,
3. Localized AN, viscosity, etc.)
thermal failure to differentiate from
conditions bulk oil degradation
Stage Three The presence 1. Ultracentrifuge,
(attack stage) of both soluble patch test
– More and insoluble colorimetry,
advanced thermal coagulated
degradation degradation insolubles
phase where products to 2. Analysis of
significant risk form: sludge (bottom
of varnish is 1. Suspended sediment, organic
present high molecular- filter sediment, etc.)
weight nitric by elemental
oxides and analysis, FTIR,
similar GC/MS
resinous
insoluble
compounds
2. Sludge and
deposits
Table 2. Methods for Analyzing Thermal
Degradation-induced Sludge and Varnish
Stage three is an attack stage. While conditions in stages one and
two may not damage the machine, stage three contaminants are
surface active, potentially causing deposits, corrosion or
mechanical wear. Stages one and two are more proactive, meaning
that analytical methods detect aberrant conditions before damage
or harm to the machine occurs. Stage three is a predictive
maintenance stage where an incipient or impending machine failure
is already in progress.
Conditions of
Stages of Corresponding
the Fluid to be
Failure Analytical Method
Tested
Stage One Root causes: 1. Karl Fischer,
(precursor 1. Exceedingly dew point meters
stage) – Root dry oil 2. Particle counters
causes that 2. Exceedingly (various), total
propel the fluid clean oil insolubles
into the next 3. Unoxidized 3. AN, RPVOT,
stage oil FTIR (1,730 cm-1)
4. Drop in oil 4. Conductivity
conductivity meters, dielectric
breakdown testers,
dielectric constant
meters, etc.
Stage Two The presence 1.
(transitory of soluble Spectrophotometry,
stage)- The thermal patch colorimetry
beginning of degradation 2. Pattern testing
base oil products: (combining above
degradation 1. tests with RPVOT,
and increasing Chromophoric AN, viscosity, etc.)
risk of compounds to differentiate from
varnishing (color bodies) bulk oil
formation 2. Localized degradation*
thermal failure
conditions
Stage Three The presence 1. Coagulated total
(attack stage) of soluble and insolubles
– More insoluble 2. Analysis of
advanced thermal sludge (bottom
degradation degradation sediment, filter
phase where products: sediment, etc.) by
significant risk 1. Suspended elemental analysis,
of varnish is high molecular- FTIR (1,730 cm-1),
present weight similar GC/MS
resinous 3. Flash point, gas
 insoluble chromatography for
compounds acetylene and
2. Sludge and other gases*
deposits
3. Gas
evolution
*Note: Analytical methods for clearly isolating oil
degradation in conditions to electrification and
static discharge has not been fully developed.
The methods listed here are general in nature and
may aid in the differentiation.
Table 3. Methods for Analyzing Static
Discharge-induced Sludge and Varnish
Oxidation is a well-known oil degradation mechanism and is
relatively simple to monitor with traditional oil analysis methods
compared to other failure mechanisms. Thermal degradation,
although less understood, is also common and can be analyzed
with traditional oil analysis. The effects of static discharge are still
relatively new to the oil analysis field. It is more difficult to analyze
(isolate as the root cause) with traditional oil analysis techniques.
The degradation stages and analytical scheme for oxidation,
thermal and compressive base oil degradation and static discharge
conditions are presented in Tables 1 through 3.
Numerous analytical tests have been identified in Tables 1 through
3. It is of interest to discuss a couple of these tests and how their
results can be used to distinguish the various failure mechanisms.

Fourier Transform Infrared Spectroscopy

As oxidation increases, common reaction by-products are carbon-
oxygen double bonds, also called the carbonyl group. Carbonyl
peaks on FTIR spectra in the 1,740 cm-1 region (Figure 4), easily
identifying oxidation. As oxidation increases, the absorbance peaks
will increase in this region. Additionally, phenol inhibitors used as
antioxidants in the oil show peaks around 3,650. Changes in this
peak are also noteworthy.
 Figure 4. FTIR Spectrum Showing
Oxidation Peak around 1,740 cm-1 Range
Because thermal degradation can occur without significant amounts
of oxygen, different degradation by-products are often observed.
Therefore, the 1,740 cm-1 peak is less likely to be significant.
Instead, the by-products of thermal base oil degradation show up in
the 1,600 to 1,640 cm-1 region – also known as the nitration peak
due to the nitrogenous by-products, which is more pronounced
using a thick-cell (500 µm path length) spectrometer.

Acid Number (ASTM D974 or D664)

As the number of acids increase due to the oxidation process, AN
will increase accordingly. In large turbine systems, an AN change
as low as 0.3 to 0.4 above the new oil baseline is often sufficient to
condemn an oil.

Rotating Pressure Vessel Oxidation Test (ASTM D2272)

RPVOT measures an oil’s resistance to oxidation. This information
indicates the oil’s remaining oxidative useful life (RUL) and is
calculated by dividing the in-service sample result by the new oil
result. RPVOT values are influenced by the type and quantity of
antioxidants present in the oil and the oxidative robustness of the
base oil. Cautionary and critical limits for turbine oils are usually at
60 percent and 40 percent RUL, respectively.

Viscosity (ASTM D445)

During oxidation, cleaved oil molecules recombine to form higher
molecular weight species. An increase in absolute viscosity can
indicate when oxidation becomes advanced. In some cases, oil can
be thermally cracked during degradation, where the oil molecules
are severed into smaller molecules. As a result, a decrease in
viscosity can be detected.

Flash Point (ASTM D92)

Flash point may be used to identify thermal degradation if oil
molecules have been thermally cracked. As the percentage of lower
molecular-weight oil fractions increases due to thermal cracking, the
flash point will drop accordingly.

Gas Chromatography (GC)

One of the advantages of gas chromatography is its ability to
separate similar molecules based on their size. Thermally cracked
oil will show an increased number of light-end molecules compared
to the new oil baseline.

Patch Colorimetric Test

The patch test has been used for many years in oil analysis as a
qualitative test to assess the condition of oil. Recently, several
commercial laboratories have developed quantifiable scales to
trend the varnish potential of oil. For example, on Analyst Inc.’s
scale from 0 to 100, a varnish potential rating of 0 to 40 is
considered acceptable. The range 41 to 60 is a reportable
condition, meriting the need for frequent oil monitoring. Readings
greater than 60 are considered actionable and should trigger work
plans to quickly remediate the condition.

Conclusion
A number of degradation methods have been discussed in this
article. In order to differentiate between the failure mechanisms and
assess varnish potential severity, turbine owners should consider
an ensemble of tests to monitor the oxidative or chemical
degradation of turbine oils, such as:

 FTIR
  RPVOT
 RULER
 Patch colorimetry
 Ultracentrifuge
 Coagulated insolubles

How the Oxidation Rate Affects Oil

Change Frequency
Noria Corporation
"How much should an oil’s oxidation rate affect the frequency of an oil change?"
Oxidation is a reaction that takes place between the molecules of a lubricant’s base oil
and existing oxygen in the form of foam or entrained air. Once oxidation begins to occur,
it can, and often will, lead to an adverse, permanent chemical change in the molecules.
As this process is initiated, the molecules, which typically are hydrocarbons, are
transformed into proponents that hinder the lubricant’s performance.

Why Oxidation Is a Concern

Oxidation is the leading degradant of any lubricant that is subjected to typical service
and environmental exposure. While performance deprivation is the initial fear with
oxidation, additional concerns include increased component wear through corrosion,
amplified varnish potential and sludge accumulation. Understanding why oxidation
happens within a lubricant is imperative to help prevent and delay this process.

Oxidation’s Effects
Protection against the onset of oxidation can be found in the form of robust, usually
synthetic base oils with higher viscosity indexes, as well as lubricants with antioxidant
additive packages. Of course, even the most resilient lubricants eventually will succumb
to oxidation if the exposure to water, heat, air or metal catalysts is severe enough. As
this unwanted process progresses, numerous complications may arise. Most issues
initially appear with the base oil breaking down as additive depletion begins. Through the
development of this cycle, the oil’s viscosity and acidity will often increase, and the
formation of rust and corrosion will take effect. The increasing presence of moisture and
reactive metals will also factor into the rate of oxidation.

How the Oxidation Rate Impacts Oil Changes

With a better understanding of oxidation, you can see how it might affect the lubricant’s
degradation rate, which can have a direct impact on the frequency at which the oil is
changed out. Two main factors drive this rate. The first aspect is that as degradation
starts to occur with the antioxidant additives, you will begin to see oxidation. If
influencing factors or pro-oxidants such as contaminants, temperature and pressure
remain the same, the rate of additive depletion and oxidation generally will remain linear.
If these factors deviate from the norm, a change in the oxidation rate may result.
The second factor that will impact the oxidation rate is the base oil’s molecular make-up.
The lubricant’s oxidation stability and the equipment’s history should also play a role in
determining the oil change frequency. Oil analysis can help identify both of these factors.

Using Oil Analysis to Check for Oxidation

Much like the human body, a lubricant will show symptoms of an "illness" as
complications begin to take place. The lubrication team and the oil analysis laboratory
must ensure activities are put in place to catch these signals before it is too late.  
Sensory inspections during preventive maintenance (PM) tasks are a great way to start.
Typically, operators and mechanics have already been assigned tasks associated with
the equipment, so this is an ideal time to check for oxidation stress signals. These
inspections might include examining the lubricant through a clean sight glass with a
flashlight to ensure the oil is clear and bright or at least its normal color. Since oxidation
sometimes can cause the lubricant to have a foul odor, consider pulling a small sample
or opening an access port to see if it has the same characteristic scent.
Oil analysis can be divided into routine and exception test slates. Routine test slates
would include viscosity, acid number and Fourier transform infrared spectroscopy, while
exception test slates might consist of sludge and oxidation, linear sweep voltammetry,
and rotating pressure vessel oxidation testing.
Identifying the Stages of Oil Oxidation
Bennett Fitch, Noria Corporation

Lubricants age and alter chemically by a process called oxidation. In fact, oxidation is
the primary way a lubricant degrades over time from normal service. It typically results in
impaired chemical and physical properties of the base oil and additives. Understanding
why a lubricant oxidizes is essential to prevent, delay and monitor the process.
As oil is used in a machine over time, the oxidation process occurs, typically starting with
the degradation of antioxidant additives. If the driving conditions that stress the oil
remain unchanged, these additives will deplete at a near linear rate.
This is sometimes called the induction period. When the oxidation inhibitors are largely
depleted, the breakpoint of the lubricant is reached, at which time the base oil has lost its
first line of defense against oxidation.
Some base oils are extremely robust and resist oxidation naturally. Examples include
most synthetics. However, if exposures to pro-oxidants such as high temperature,
moisture, metal particles, agitation and oxygen are severe enough, even the most robust
synthetics will give way to oxidize.
This oxidation process has the potential to begin almost spontaneously for even oil
sitting dormant in a storage container. However, the rate of additive depletion and base
oil oxidation generally correlates to the intensity of pro-oxidants existing within the oil.
Ultimately, the consequences of this chemical process will include increased oil viscosity
and organic acids; the formation of sludge, varnish and deposits; additive depletion
(including anti-wear additives, dispersants, corrosion inhibitors, etc.); and the loss of
other vital base oil performance properties.
Once these undesirable lubricant conditions exist, the machine no longer will be
protected effectively against friction, wear and corrosion.

Oxidation Overview
Oxidation is a complex series of chain reactions. To better understand the process,
follow the chart on page 42 as each element is explained.
The oxidation process consists of three key stages: initiation, propagation and
termination.
Initiation describes the mechanisms by which a lubricant’s components can chemically
combine with one or more catalysts to produce a free radical. (Free radicals are highly
reactive molecules that attempt to find other molecules to combine with and create new
products.)
Propagation refers to the complexity of additional reactions of various types of free
radicals and catalysts that result in the production of more free radicals and oxygenated
compounds.
Termination involves the eventual end of the oxidation process, either negatively or
positively. If it is negative, the antioxidants typically have been depleted and the
oxidation process will continue. If it is positive, an antioxidant likely has stunted the
oxidation’s progression.
Keep in mind that antioxidants are sacrificial, which means they become depleted as
they do their job. Therefore, the positive effects of antioxidants will expire, while the
overall oxidation process will not.

Oxidation Stages
The lubricant (a), which is a formulation of hydrocarbon base oil and additives, is
subjected at some point to various catalysts and conditions that allow the initiation of
oxidation to occur. Both the base oil and additives fight against the oxidation process
and are eventually subjected to degradation.
During the initiation stage (b), the hydrocarbon molecules react with various catalysts,
leading to the formation of free radicals. Once this has occurred, further initiations of the
oxidation sequence may continue as the existing free radicals progress to the
propagation stage.
Wear metals (c) have the potential to cause or accelerate oxidation reactions by means
of metal ions in copper, cobalt, chromium, iron and other transition metals. Thus, not
only does oxidation have the ability to create wear debris, but wear debris can cycle
back to promote further oxidation.
Nitro-oxides (d) such as nitrogen dioxide, nitric oxide and nitrous oxide are another form
of pro-oxidants that catalyze the oxidation reaction.
Ultraviolet radiation (e) in the form of sunlight can also initiate oxidation reactions. This is
frequently observed and can often explain the discoloration of unused oil.
Elevated temperatures (f) promote and sometimes are required for certain stages of
oxidation to occur. When in combination with wear metals or oxygen, the effects may be
multiplied. If temperatures are low, the chain reactions are generally slow but will
increase at moderate rates above 100 degrees C.
Oxygen (g) is the major catalyst of oxidation. Whether it exists in the air or in other
molecules such as water, oxygen is integral in the oxidation process at almost every
stage.
Free radicals (h) are among the unwanted results of the intermediate reactions within
oxidation. These highly reactive molecular fragments contain one or more unpaired
electrons that are prone to reactions with hydrocarbons and other molecules. Some free
radicals may exist as molecular fragments of alkyl, hydroperoxide, alkyloxy, hydroxy,
alkylperoxy, etc.
Once free radicals exist, they quickly will react again - propagating (i) the process - with
the hydrocarbons and dissolved or free oxygen to form more free radicals and
oxygenated compounds.
High temperatures also play a role in furthering this reaction at increased levels. Another
example of oxidation propagation would be peroxy radicals reacting with additional
hydrocarbons to produce hydroperoxides and more alkyl radicals.
As a product of several chain reactions during the propagation stage, oxygenated
compounds (j) are formed such as aldehydes, ketones, alcohols and water. These
products are the result of a reaction between the alkyloxy radicals and hydrocarbon.
Alkyl hydroperoxide and alkylperoxy radicals can be neutralized and removed from the
propagation of oxidation when they come in contact with antioxidants (k). The most
common antioxidants will work as chain breakers and decomposers.
Oxidation can move past the propagation stages unfavorably (l) when the oxygenated
compounds continue to react with the hydrocarbons and oxygen. On the other hand,
oxidation may terminate favorably (m) when stabilization of free radicals occurs.
Chain-breaking antioxidants, such as phenolic or aromatic amines, react with the free
radicals to form stable radicals and inert byproducts. Peroxide decomposer types of
antioxidants like phosphates and sulfides react with peroxides to produce alcohols and
water.
Oxygenated compounds (n) will react further with oxygen resulting in carboxylic acid,
esters and water. This process is again increased when subjected to high temperatures.
Carboxylic acids are largely formed by the oxidation of aldehydes and ketones, which
continues through an abstraction of an alpha hydrogen or aldehydic hydrogen from the
hydrocarbon molecules.
Polycondensation and polymerization (o) of the oxygenated compounds describe the
effects of the final stages of oxidation. The increase in weight of the molecular
compounds translates to the formation of sludge, varnish and deposits.
Not only do these insoluble products form, but organic acids corrosively attack the
surfaces along with water. Most of the additives are also negatively affected and in turn
become part of the deposit agglomeration. As aldehydes and ketones increase in the
lubricant due to the condensation reactions, the apparent viscosity will begin to increase.
Insoluble, oxidized oil products (p) like sludge and deposits are significantly different
from the oil molecules that make up the majority of the lubricant. Sludge is the buildup of
insolubles, while deposits are insolubles that attach tightly to metal surfaces.
Corrosion will be promoted as water and acids exist on metal surfaces if the corrosion
inhibitor additives are depleted, which may also be the byproduct of oxidation.
In conclusion, contaminants like water, oxygen and wear metals can have serious
consequences on lubricants and machines. Additives such as antioxidants can help
substantially, but they eventually will become depleted during the induction period. For
your lubricants to last longer and your machines to run longer, you must understand why
oxidation occurs.

Oxidation - The Lubricant's Nemesis

Dave Wooton, Wooton Consulting

Oxidation is the most predominant reaction of a lubricant in service. It is responsible for

numerous lubricant problems - including viscosity increase, varnish, sludge and
sediment formation, additive depletion, base oil breakdown, filter plugging, loss in foam
control, acid number (AN) increase, rust formation and corrosion. Therefore,
understanding and controlling oxidation is a priority of the lubricant chemist.
Many new oil formulation tests (such as ASTM D4310 - the sludge and oxidation test,
turbine oxidation stability test (TOST) D943 and D4485 - the engine oil performance
categories) and used oil analysis tests (such as fourier transform infrared (FTIR)
oxidation ASTM D2412, linear sweep voltammetry (LSV) RULER™ - ASTM 6971,
QSAsm and acid number D664) are used to study this lubricant's nemesis.

Common Oxidation Indicators

Every lubricant is designed with an oxidation controlling method. The formulation of each
lubricant, therefore, contains antioxidants. These antioxidants are designed to be
sacrificial, meaning they react or oxidize before the remainder of the lubricant (the base
oil) to provide protection.
This protection is the only mechanism saving the lubricant from premature failure. To
develop a lubricant, the chemist should know what types and how much of these
antioxidants to incorporate into the formulation. Anyone monitoring the used fluid's life
expedience should also track these additives.
This article discusses oxidation with respect to the tools used for monitoring this
problem.

Table 1. Oxidation Test Conditions

The Steps of Oxidation

The oxidation of a hydrocarbon fluid involves three basic steps: initiation, propagation
and termination.
With these steps in mind, oxidation can be managed through the control of one or more
of its steps or phases. This is achieved by limiting the source of oxygen (the initiation),
shortening the number of reaction cycles (the propagation) or adding alternate stopping
methods (increasing termination). To some extent, all of these methods are employed in
the lubricant formulation. The initiation starts the process, and preventing oxygen is the
first line of defense.
Understanding what is causing the propagation steps can also enable the decrease of
oxidation. The termination step stops the cycle. Antioxidants are used to break into this
propagation and form radicals that are stable, thus halting the cycle. One of the most
effective testing methods for understanding the health of the fluid is to be aware of the
health of these antioxidants.

Figure 1. Oxidation Analyses from Sequence Testing

Temperature
Heat is often employed to accelerate the oxidation process because temperature has
two effects on any reaction. The first effect involves activation energy. If the system does
not contain enough energy to push the reaction over the threshold, nothing will happen.
The second effect is related to the speed of the reaction. A reaction (oxidation) will
approximately double in rate for every 10°C (18°F) increase in temperature. Which
means that the oil life will be reduced by one-half for every 10°C (18°F) increase in
temperature.
Tests are often developed to study the fluid's oxidation that has resulted with an
increase in temperature or an addition of a catalyst. For convenience, these
modifications of "real life" are used to conduct a test in a shorter time frame.
The application of these methods is often useful; however, the resulting data should
always be carefully studied because it may not agree with the fluid's behavior in real-life
applications. Additional reaction pathways can become the major pathway and mislead
the researcher.

Analysis
Although most lubricants are formulated with antioxidants to control oxidation, the
inevitable breakdown cannot be prevented. For this reason, many tests have been
developed to evaluate the oxidation state of the lubricant. Some of these tests study the
potential lifetime of the lubricant while others look at the results of oxidation.

Oxidation Reserve
When an oil formulation is designed, a series of tests is required for this formulation to
meet. Regardless of the formulation's ultimate application, the test series always
includes several oxidation tests. The oxidation test requirement (time, temperature,
catalyst, atmosphere and interpretation methods) is designed around the lubricant's
application.
In most cases, the remaining oxidation reserve is measured by testing the lubricant's
behavior under an oxidation experiment. For example, rotary pressure vessel oxidation
test - RPVOT (D2272), universal oxidation test (D6514), turbine oil stability test - TOST
(D943), universal oxidation test (D5846) and pressure differential scanning calorimetry -
PDSC (D6186) are used to study the oxidation potential of a turbine oil.
The tests differ in the reaction temperature or concentration of oxygen. A lubricant is
often measured by several of these tests to assess the temperature effects of the
lubricant.1 Because a lubricant is operating in multiple temperature zones, testing at
different temperatures provides a better assessment of the lubricant's overall quality.

Figure 2. FTIR Spectra of an Engine Sequence Test

Test Methods
Except for the PDSC and RPVOT, the resulting oxidized lubricant from the above test is
also evaluated by another oxidation consumption or property test method. The oxidized
lubricants are analyzed by tests including base number, AN, FTIR oxidation or viscosity
change. This evaluation further indicates the lubricant's oxidation state.
In the automotive sector, crankcase lubricants are subjected to engine tests (D4485)
designed to cause severe oxidation, forcing the lubricant to easily oxidize in a short time.
The resultant used oil is measured for BN, AN, FTIR-oxidation and viscosity to
determine speed and amount of oxidation. These engine tests are analogous to the
actual use that the lubricant could be subjected to in the field, but at a shorted interval.
Figure 1 shows an example from one of these test studies. The effects of the acids
reacting to lower the base reserve, BN, are clear, while the oxidation cannot immediately
be observed in the FTIR or viscosity regions.

Oxidation Profile
These results are common when trending the lubricant's oxidation profile. As oxidation
occurs to the lubricant, it depletes the antioxidants and produces carboxylic acids. The
base reserve will neutralize these oxidation-produced acids to carboxylate salts; thus,
resulting in a depletion of the base reserve. As previously discussed, many of the
esterification and condensation reactions that produce viscosity increases are acid
catalyzed.
The base reserve will help prevent this chain growth and viscosity problem. Therefore, in
addition to the corrosion problems of the acid components, it is important to prevent BN
from getting too low or AN too high. The oxidation reaction produces esters and
carboxylate salts (from the base reserve neutralization); however, carboxylate salts are
not being measured by the oxidation analyses2 even though it is an oxidation product.
Figure 2 shows how oxidation is progressing in this complex experiment. The lowest plot
(line) in the figure was generated on an oil sample early in the test. Successively higher
lines are generated from additional oil samples taken during the test.
In Figure 2, the acids can be observed at 1,715 cm-1, while nitrate oxidation is at 1,631
cm-1 and carboxylate salts at 1,555 cm-1. All the components in the 1,800 to 1,500 cm-1
range are oxidation-related components.
 Figure 3. LSV (D6971) of New and Used Turbine Oil

Protection
The majority of analytical tests that measure oxidation protection measure the amount of
oxidation that has occurred to the lubricant. The Linear Scanning Voltammetry (LSV)
(D6971) and FTIR are two tests capable of measuring the concentration of the
antioxidant additive(s) present in the oil to control oxidation.
The LSV is an application of linear sweep voltammetry (LSV), which utilizes a sweep
voltage to measure both amine and phenolic antioxidants (Figure 3). When calibrated
against the new oil, the remaining antioxidant concentration can be determined to
estimate the lubricant's remaining oxidative life.
Similar information can be obtained from FTIR. As shown in Figure 4, the phenolic and
amine antioxidants are visible in the FTIR spectrum. Like LSV, the peak area of the FTIR
spectrum can be used to quantitate the antioxidant's concentration.
The remaining lifetime of the lubricant obtained from both FTIR and LSV can be
expressed only as a percentage of the new oil life. It can be related to the number of
hours of oil life remaining only if the historic life of the oil is known in hours and the
application's conditions have remained stable. For systems like turbine oils that have
controlled operations, there can be established contaminations limits for the percentage
useful life.
 Figure 4. FTIR Spectrum Showing Antioxidants

Oxidation Progress
A common method for studying oxidation is to trend its progression. Oxidation results
can be followed by measuring the increase in the acid number of the fluid (or the loss in
base number in engine oils caused by the formation of acids), viscosity (caused by the
formation of condensation products), FTIR carbonyl oxidation (the ketones, aldehydes,
esters and acids formed form the oxidation reactions) and insoluble products.
Although certain tests like the Pentane/Toluene Insolubles D893 measure both hard and
soft insolubles, applying tests like Pentane Insolubles by Membrane Filtration D4055,
QSAsm3 or the filter paper Blotter Spot Test can also follow the amount of oxidation
products. In the case of oxidation, measuring the formation of condensation products
that are insoluble in the fluid is tracking or monitoring the oxidation.
Performing these different methods and following the results can provide an
understanding of the root cause and mechanism of oxidation. For example, if oxidation
occurs at low temperature, significant FTIR oxidation and a small amount of insoluble
products will be apparent.
On the other hand, high temperatures can cause condensation reactions and increase
insoluble products. Many thermal-cracking processes (like microdieseling or combustion)
will promote oxidation, but will also produce nitrates that can be observed through FTIR
nitration as a flag of the process.
Other less widely utilized tests have been used to measure oxidation. The most
promising of these methods employs the measurement of the electrical polarity or
permittivity of the fluid.5, 6 Both the real and imaginary parts of the impedance
measurement contains information about the fluid.
The real parts of the impedance, the conductivity, and the imaginary part, the permittivity
or dielectric coefficient, are both affected by the change in polarity of the fluid. Oxidation
is a major source of this change in lubricant polarity. Therefore, new sensor technologies
are emerging that utilize these resistance-related measurements to assess the oil
quality, in many cases as a real- time measurement.
Although oxidation has been studied for more than 140 years, it remains to be fully
understood. Fluid chemistry, reaction temperature and reaction conditions are varied in
testing experiments in an attempt to predict the in-service behavior of the lubricant.
Tests have been designed to measure oxidation reserve (the amount of protection
remaining) and oxidation progress (the amount of oxidation that has occurred). Both
testing methods have their advantages, and the effectiveness of these tests depends on
the operation of the in-service fluid. The better that a test can measure what is occurring,
the more information is available concerning the life of the fluid.
Understanding how the fluid is handling the oxidation problem can enhance the attempt
in correcting this root cause of fluid failures. The lubricant chemist should be aware of
the measuring tools available and what they may indicate. Therefore, one can address
and potentially reduce this source of fluid failure.

Advice for Extending Lubricant Life

Noria Corporation

"I've heard that a lubricant's

life is cut in half for every 10 degrees C (18 degrees F) increase in operating
temperature. Is there any truth to this?"
Yes, this is generally true. The concept is based on the Arrhenius equation, named for
19th-century Swedish chemist Svante Arrhenius. In 1903, Arrhenius won a Nobel Prize
when he figured out the relationship between temperature and most chemical reaction
rates. Often called the Arrhenius Rate Rule, it relates to the fact that lubricants, once
they've exceeded their base activation temperature, will degrade (oxidize) twice as fast
for every 10 degrees C (18 degrees F) increase in temperature. In fact, there are a
range of problems associated with too much heat, such as:

 Additive and base oil decomposition is accelerated.

 Some additives will volatilize and escape into the atmosphere.
  Viscosity-index improvers shear down more rapidly.
 Microbial contaminants prefer warmer temperatures (but not scalding).
 Heat collapses oil films, causing accelerated abrasion and scuffing conditions.
 Hot oil shortens the life of filters and seals and accelerates corrosion.
 Both oil and grease are more prone to leakage.
 Grease separates faster (oil from thickener) at elevated temperatures.
 High surface temperatures can form carbonaceous gum and resins.

Heat increases both the collision rate of molecules and the activation energy of the
reaction. The higher activation energy helps overcome the barrier (or natural resistance)
molecules have to chemical reactions.
With oils, the chemical reaction that typically causes base oil degradation and additive
depletion is oxidation. The activation energy required to induce oxidation in oil is high
compared to other chemical reactions. The presence of contaminants such as water and
certain metal particles in the oil can considerably speed up the process, thus increasing
the activation rate. For most in-service mineral oils with typical contaminants, the
activation energy for oxidation corresponds to a doubling for every 10 degrees C
temperature increment.
Why does a refrigerator keep food from spoiling? Spoiling is a chemical reaction like oil
oxidation but proceeds at a much higher rate constant. Compared to a refrigerator (4
degrees F), food will spoil at a rate 142 times faster at room temperature (77 degrees F).
In other words, the speed of reaction in a freezer is much slower than at room
temperature.
So what happens if you let the oil degrade? The eventual breakdown of the molecules is
inevitable. It can be prolonged by keeping the oil clean, cool and dry, but it will eventually
happen. When it does, the byproducts of the reaction are harmful for machine health.
First to form are carboxylic acids. These acids are relatively weak, but they can start to
corrode machine surfaces if left in a system for a great deal of time. Left unchecked, the
now heavily oxidized oil will start to form sludge and varnish. This sludge and varnish
can cause filter plugging, blockage of critical oil clearances, valve stiction and many
other precursors to machinery failure.

The Effects of Heat Exchangers on Oil

Noria Corporation
 Heat exchangers are often used on
equipment to cool the system, but what effect does this have on the oil and on
equipment life?
Many heat exchangers are installed at the factory depending on the size or criticality of
the machine. For these types of equipment, the maintenance staff must keep the heat
exchanger operating within a certain parameter. If these parameters are exceeded, the
equipment will eventually go down, usually because of a safety feature that trips the
equipment due to a high temperature.
If you have had the opportunity to attend one of Noria’s Fundamentals of Machinery
Lubrication classes, you are aware of the importance of keeping lubricants clean, cool
and dry, and equipment balanced, aligned and well-oiled. These are some of the
proactive practices that help ensure your equipment has the best opportunity to stay as
healthy as possible. Heat exchangers can be utilized as part of one of these proactive
practices — keeping the lubricant cool.
Heat is one of the four pro-oxidants. The others are air, water and metal catalysts. These
pro-oxidants lead to the formation of acids, varnish, sludge and high viscosity, which
normally result from oxidation. Oxidation is the permanent degradation of a lubricant by
chemical reactions involving oxygen. As oxidation progresses, long-chain molecules are
produced, which promotes the formation of sludge, tar, varnish and acids.
Individuals who review oil analysis reports typically look at an increase in viscosity and
acid number to determine the health of the lubricant. While this is important, it is critical
to change the lubricant before the critical limit is exceeded. Don’t forget that the health of
your lubricant is your insurance for maintaining healthy equipment. Whenever you
neglect your lubricants, you are also neglecting your equipment and allowing sludge, tar
and varnish to become contaminants that can damage bearings, servo valves, etc., and
cause equipment failure. As oxidation increases, so do acids, which results in corrosion
of internal components.
Heat exchangers can play an important role in reducing heat within a system.
Regardless of the type of heat exchanger used, it should be operated within its limits to
ensure that the lubricant is kept cool. Refer to the manufacturer of the heat exchanger to
make sure you are within the appropriate limits.
You should also keep in mind that for every 10 degrees C (18 degrees F) over the
operating temperature, oil life is cut in half (Arrhenius rate rule). This means that if you
have high temperatures and a heat exchanger that is not set up properly, it will produce
more rapid oxidation.
In the reliability world, it is understood that oil will need to be changed more frequently in
a machine that is running hot than in a cooler machine, but you can also apply the
Arrhenius rate rule to your car. For instance, the hotter the oil in your vehicle, the more
frequently you will need to change the oil.
However, do not think that only heat leads to oxidation. You still must deal with air,
water, metal catalysts and all of the other contaminants that can enter into the lubricant.
So look a little more carefully at the machines in your plant that are currently running hot.
They may be good candidates for a heat exchanger. In addition, if you can cool the
lubricant by 10 degrees C (18 degrees F) of its operating temperature, you can double
the oil’s life. Remember, a cool lubricant will increase the health of the lubricant along
with the reliability of the equipment.

The Importance of Timely Oil Drains

Noria Corporation

Oils do not wear out. That is to say, the base oil does not generally deteriorate.
However, oil gradually loses its ability to carry out its functions of lubricating, reducing
friction and dissipating heat.
This gradual loss of lubrication quality is caused by self-generated contamination of
components within the oil, oxidation due to overheating, viscosity changes caused by
fuel dilution or oxidation, water entry into the system (either directly or through
condensation) and the gradual depletion of the additive package, as the additives
counteract acids and disperse and suspend foreign materials.
There are other conditions that also contribute to oil degradation to a lesser degree,
such as poor-quality fuel, operation of equipment in over-cooled conditions, lean air/fuel
ratios and emission control systems that are malfunctioning or have been removed or
disconnected.
The conditions that contribute to oil degradation and necessitate regular oil drains are
described in detail below:

Self-Generation of Contamination in the Oil

Every engine, hydraulic pump, gearset or other component gradually wears as it
operates. Tiny, sub-micronic particles of elements such as iron and copper become
catalysts that slowly attack the oil, causing acids to form.
These tiny metal contaminants, combined with carbon soot particles resulting from the
combustion process in engines, also circulate in the system and through their abrasive
action create more wear. These solid particles become just like a fine-grinding
compound and will slowly scratch and score bearing surfaces, turbocharger bearings,
crankshaft journals, cylinder liners and hydraulic pump and valve surfaces.
Normal full-flow filters are rated at about 10 microns in hydraulic systems and 40
microns in engines and will not remove these sub-micronic particles. Furthermore, if the
filters become plugged or if the bypass valves within them remain open for long periods
of time, such as at cold startup, contaminated oil will be pumped throughout the system.
It is important to remember that if the levels of self-generated contamination are allowed
to increase until some damage by abrasion is caused, it will be too late to prevent more
on-going damage, even if the dirty oil is drained.

Oxidation Degradation of the Oil

Oxidation is defined as a chemical deterioration of an oil that is the result of continued
contact with oxygen and catalysts such as copper. Oxidation causes the oil to thicken or
increase in viscosity. This leads to reduced oil flow and reduced heat dissipation, which
in turn accelerates the oxidation process.
Any practice that increases the operating temperatures of an engine, gear drive or
hydraulic oils must be avoided. Oil sump temperatures in engines operating at high
speed and under heavy loads can reach or exceed 150 degrees C (302 degrees F), with
piston ring temperatures exceeding 310 degrees C (590 degrees F). Turbochargers may
operate at up to 100,000 rpm with oil temperatures exceeding 315 degrees C (600
degrees F).
If engines or turbines are shut down immediately after operating at these temperatures,
oxidation degradation of the oil can take place very quickly. Furthermore, if extremely hot
oil is allowed to remain in the turbocharger or turbine bearing housings on hot
shutdowns, oxidation can occur so rapidly that the oil may actually "coke" into a tar-like
or carbon substance, which will plug turbocharger and turbine bearing oil passages.
Inoperative emission controls, retarded spark timing and thermostats with too high
opening temperatures will increase the thermal load on gasoline engines, in turn
increasing the rate of oxidation. In addition, improperly adjusted air/fuel ratios contribute
to oxidative oil thickening because they produce blow-by gases containing high
concentrations of nitrogen-dioxide compounds that rapidly promote oil thickening.
Hydraulic systems, on the other hand, operate best when the bulk oil in the reservoir
does not exceed 60 degrees C (140 degrees F). Oxidation rates within hydraulic oils will
approximately double for every 10 degrees C (18 degrees F) increase in temperature.
Continued oxidation of oil will cause sludge and varnish deposits to form and acid
buildup to cause corrosion.

Water Contamination
Any water entry into hydraulic or turbine systems can cause severe damage, particularly
in systems with very close tolerances, such as hydrostatic transmission systems that use
piston pumps.
Water contamination caused by condensation is a common problem in North American
climates due to dramatic changes in temperatures.
Hydraulic or turbine oil with a "milky" appearance is an indication of water in excess of
2,000 ppm, prompting action to be taken to replace the oil or remove the water through
special filtration systems that are available for this purpose.
In gasoline engines, the combustion of 1 gallon of gasoline produces about 1 gallon of
water. Any moisture entering the crankcase through "blow-by" can cause rusting,
corrosion, sludge deposits and the separation of additives from the base oil.
Water entering the oil in a diesel engine can also be extremely harmful, particularly if
poor-quality fuel is used. Low-quality fuel is generally high in sulfur content, and when
water combines with sulfur dioxide, acids are formed, which will immediately attack
bearing surfaces.

Additive Depletion
When base oils are formulated and blended with additives, these elements are slowly
"used up" in performing their functions. Anti-wear and extreme-pressure agents are
depleted as they are deposited on metal surfaces.
Detergents and dispersants are used up as they continue to counteract various
contaminant particles in the oil. Additives that protect against acid attacks are depleted
as they counteract acid formations within the oil. The additive package will eventually
become depleted or ineffective if the oil is allowed to remain in service for extended
periods.

Incorrect or Poor-Quality Fuels

As noted previously, the use of low-quality diesel fuel can cause severe corrosion
problems due to the formation of acids resulting from high sulfur content. If, however, it
is necessary to use fuels with more than 0.5-percent sulfur content, a lubricating oil with
a minimum API service rating of CG-4 should be used. These oils generally are better
able to counteract acids than oils of lesser quality.
Today, the more serious problem is premature wear of fuel system components due to
the poor lubricity of diesel fuel as a result of the removal of the natural lubricant sulfur.
Ensure that water jacket temperatures are generally maintained above 79.5 degrees C
(175 degrees F) to minimize sulfur attack.
This means never operating an engine without a thermostat or with the wrong
thermostat. It also requires that excessive idling of diesel engines must be avoided.
Unleaded gasoline is recommended for all gasoline engines not only to reduce
emissions but also to reduce the formation of lead compounds that form deposits and
can contribute to self-generating contaminant wear within the engine.
The conditions described above can be prevented by:

 The continued use of top-quality lubricating and hydraulic oils in all equipment.
 Regular oil and filter changes based on a regularly scheduled oil analysis
program.
 The correct selection of fuels for both gasoline and diesel use.