The Filter No 4 February 2006
Oxidation in lubricant base oils
The ageing of the oil
Oxidation is a common problem in many industries. When the oil is being used in a machine, it oxidizes over
a period of time depending on the type of oil, the operational conditions and the environment. Oxidation can
have negative effects on lubrication and hydraulic system, all of which may have serious consequences for
the performance of the machinery. In this article you can read about the problems connected with oxidation.
By Laura Corvinos Ancho, B.Eng. Chemical Engineering, C.C.JENSEN A/S
Deposit formation on key komponent
Oxidation is a complex pri-
mary chemical degradation
process in the base oil. It
can be defined as the chem-
ical breakdown of the base
oil molecules with oxygen
as reagent where the princi-
ple source of oxygen is air.
The following parameters
act as a catalyst:
Temperature
Wear transition metals
....(wear particles)
Water (both free and dissolved)
Contaminants (in general
....and oxidation products)
This process involves a
series of chain reactions pro-
ducing acid compounds that
undergo further reactions
forming polymeric com-
pounds, which lead to
sludge, lacquer, varnish, i.e.
deposit formation.
The anti-oxidant additives,
used in most oils, protect the
oil from oxidation. They react
with the intermediate oxida-
tion compounds (i.e. partly
degraded oil) and counteract
the acid formation. As the oil
oxidizes, the anti-oxidant
additives are depleted over
time and then the oil is
exposed to oxidation. On the
other hand, the principle
source of oxygen (i.e. the
oxygen from the atmosphere)
may be inexhaustible.
6 7
Oxidation process in
lubricant base oils
The base oil consists of a
mixture of many different
hydrocarbons. The oxidation
process occurs when these
hydrocarbons react with
oxygen. It is a self-propagating
process that occurs via free
radicals.
Temperature is of great impor-
tance in oxidation. At lower
temperatures (up to about
150 C) the pattern of oxida-
tion reactions may differ
substantially from those at
high temperatures.
In a general case it is assumed
that oxidation of oil proceeds
in three stages: initiation
stage, propagation stage and
termination stage.
The following model shows
the oxidative degradation in
lubricant base oils.
Initiation stage
RH
Base oil
Mn+/O2
hydrocarbon
Propagation stage
R O2
Hydrocarbon + Oxygen
free radical
R ROOH
Hydrocarbon
free radical
References
Chemistry and Technology of Lubricants - R.M. Mortier and S.T. Orszulik - Blackie Academic & Professional
Longer life for Hydraulic Fluids - P.V. Madhavan, Fluid Power Engineering & Technology Guide - Machine design, December 6, 1990
Initiation stage:
The hydrocarbons react with
oxygen forming hydrocar-
bon free radicals. The reac-
tion is catalysed by traces of
transition metal ions like
copper, iron, cobalt, chromi-
um, etc.
Propagation stage:
The hydrocarbon free radi-
cals react with oxygen form-
ing peroxide radicals, that
are highly reactive, and react
further with hydrocarbons
from the oil. This leads to
hydroperoxides and hydro-
carbon free radicals, which
can react with oxygen.
Termination stage:
The hydroperoxides, formed
in the propagation stage,
cleave homolytically and
form oxygenated compounds
like aldehydes, ketones,
alcohols and water. These
compounds can react further
forming organic acids and
high molecular weight poly-
meric products. Further
polycondensation and poly-
merisation of these products
lead to insoluble products
called sludge, which may
Oil oxidation
R HOO
Hydrocarbon Hydroperoxide
free radical + radical
ROO
Peroxide
radical
RH
+ Base oil
hydrocarbon
+ Hydroperoxide
Diagram showing the oxidative degradation in lubricant base oils
precipitate as a thin film material that will trap hard troscopy. It can verify oxida- above, can monitor the
forming lacquers or varnish contaminants creating a tion in lubricants by identifi- additive depletion.
deposits on hot or cold metal sandpaper surface, which cation of functional groups
surfaces. can cause accelerated wear (e.g. ketones, carboxylic acids) RULER test
in the components. In addi- in molecules. (Remaining Useful Life
Consequences of the tion to this, varnish acts as Evaluation Routine)
oxidative degradation in an insulator, reducing the QSA It measures the remaining
lubricant base oils effect of the heat exchangers (Quantitative Spectrophoto- anti-oxidants by voltametric
which again means higher metric Analysis) analysis.
Corrosion and wear temperatures and accelerated The oxidation by-products are
Acid formation will cause reaction rates. isolated from the oil sample RBOT test
corrosion and wear in the and a quantitative spektro- (Rotating Bomb Oxidation
internal surfaces of the Measuring oxidation in photometric analysis of the iso- Test)
machine. Water, which is also lubricant base oils lated contaminants is carried It measures the oils resistence
formed under the oxidation Oxidation by-products (aka out in order to determine the to oxidation under prescribed
process, increases the corro- soft particles) are compounds degree of oxidation. conditions.
sive effect of the acids. of molecular sizes less than
1 micron, which cannot be Ultracentrifuge test Removal of oxidation products
Increase in oil viscosity measured by conventional This test uses the gravitatory using filtration systems
The oil viscosity increases due particle counting methods. forces to extract and settle The key to prevent oil degra-
to the formation of oxidation the contaminants of the oil. dation is to remove the oxi-
products e.g. polymeric com- TAN analysis (total acid num- The sediment is compared dation by-products before
pounds and sludge. It will ber) and viscosity testing can with a sedimentation rating they can react further and
result in friction, wear and be used as indicators of oxi- system to determine oxidation. form insoluble slugde and
loss of energy. dation but they cannot varnish deposits. These com- Oxidation is a common problem in
determine whether or not Gravimetric analysis pounds are very difficult to many industries
Sludge and varnish the oil is oxidized. Dark This analysis examines oxi- remove by the conventional
Sludge and varnish can color, and sour, putrid odor dation by measuring the mechanical filters because we
result in valves blocking and usually indicate oxidation. weight of residual compo- are dealing with submicron
orifices clogging. Once var- nents. The oil sample is particles with a high level of
nish deposits are formed on There are several methods treated with the solvents solubility in hydrocarbons.
metal surfaces, it is very dif- to monitor oxidation in the pentane (hexane), toluene Adsorption of oxidation by-products
ficult to dissolve them even oil. Generally, these methods and pyridine to determine Electrostatic filters and cellu- in the CJC Fine Filter: Resin in the
at high temperatures. These are used to either determine the oxidation products. lose filters can remove oxi- oil attracts to the polar fibres in the
deposits are like a sticky oil degradation products from dation products, because filter mass and are retained
the oil or the consumption Colorimetric Analysis: oxidation compounds are
Termination stage of anti-oxidants in the oil. This analysis examines the polar - i.e. have electrically
The latter is used to predict color of contaminants col- positive and negative poles.
RCHO Aldehyde [O] when the onset of oxidation lected on membrane filters
RCOOH Acid
RCOCH3 Ketone will occur. by a colorimetric device. The electrostatic filters remove
the oil contaminants using
ROOH
Hydro- The following are examples The following are examples the principles of electrostatic
peroxide of methods to monitor the of methods to monitor the and electromagnetism. The
oxidative degradation: consumption of anti-oxidant cellulose filters, on the other
High molecular
RCH2OH [O] additives: hand, utilize the characteris-
weight polymeric
Alcohol
compounds FTIR analysis tic that the cellulose material
(Fourier Transformation FTIR analysis is also polar. The oil degrada-
Sludge and Varnish Infrared Spectroscopy) (Fourier Transformation tion products are attracted
This analysis is based on the Infrared Spectroscopy) and retained by the poles of
principles of molecular spec- This analysis, mentioned the cellulose fibers.
Using Oil Analysis to Control Varnish and Sludge http://www.noria.com/learning_center/category_article.asp?articleid=59
New Varnish Test Improves Predictive Maintenance Program http://www.practicingoilanalysis.com/article_detail.asp?articleid=761&relatedbookgroup=OilAnalysis
The Filter No 4 February 2006
Oxidation in lubricant base oils
The ageing of the oil
Oxidation is a common problem in many industries. When the oil is being used in a machine, it oxidizes over
a period of time depending on the type of oil, the operational conditions and the environment. Oxidation can
have negative effects on lubrication and hydraulic system, all of which may have serious consequences for
the performance of the machinery. In this article you can read about the problems connected with oxidation.
By Laura Corvinos Ancho, B.Eng. Chemical Engineering, C.C.JENSEN A/S
Deposit formation on key komponent
Oxidation is a complex pri-
mary chemical degradation
process in the base oil. It
can be defined as the chem-
ical breakdown of the base
oil molecules with oxygen
as reagent where the princi-
ple source of oxygen is air.
The following parameters
act as a catalyst:
Temperature
Wear transition metals
....(wear particles)
Water (both free and dissolved)
Contaminants (in general
....and oxidation products)
This process involves a
series of chain reactions pro-
ducing acid compounds that
undergo further reactions
forming polymeric com-
pounds, which lead to
sludge, lacquer, varnish, i.e.
deposit formation.
The anti-oxidant additives,
used in most oils, protect the
oil from oxidation. They react
with the intermediate oxida-
tion compounds (i.e. partly
degraded oil) and counteract
the acid formation. As the oil
oxidizes, the anti-oxidant
additives are depleted over
time and then the oil is
exposed to oxidation. On the
other hand, the principle
source of oxygen (i.e. the
oxygen from the atmosphere)
may be inexhaustible.
6 7
Oxidation process in
lubricant base oils
The base oil consists of a
mixture of many different
hydrocarbons. The oxidation
process occurs when these
hydrocarbons react with
oxygen. It is a self-propagating
process that occurs via free
radicals.
Temperature is of great impor-
tance in oxidation. At lower
temperatures (up to about
150 C) the pattern of oxida-
tion reactions may differ
substantially from those at
high temperatures.
In a general case it is assumed
that oxidation of oil proceeds
in three stages: initiation
stage, propagation stage and
termination stage.
The following model shows
the oxidative degradation in
lubricant base oils.
Initiation stage
RH
Base oil
Mn+/O2
hydrocarbon
Propagation stage
R O2
Hydrocarbon + Oxygen
free radical
R ROOH
Hydrocarbon
free radical
References
Chemistry and Technology of Lubricants - R.M. Mortier and S.T. Orszulik - Blackie Academic & Professional
Longer life for Hydraulic Fluids - P.V. Madhavan, Fluid Power Engineering & Technology Guide - Machine design, December 6, 1990
Initiation stage:
The hydrocarbons react with
oxygen forming hydrocar-
bon free radicals. The reac-
tion is catalysed by traces of
transition metal ions like
copper, iron, cobalt, chromi-
um, etc.
Propagation stage:
The hydrocarbon free radi-
cals react with oxygen form-
ing peroxide radicals, that
are highly reactive, and react
further with hydrocarbons
from the oil. This leads to
hydroperoxides and hydro-
carbon free radicals, which
can react with oxygen.
Termination stage:
The hydroperoxides, formed
in the propagation stage,
cleave homolytically and
form oxygenated compounds
like aldehydes, ketones,
alcohols and water. These
compounds can react further
forming organic acids and
high molecular weight poly-
meric products. Further
polycondensation and poly-
merisation of these products
lead to insoluble products
called sludge, which may
Oil oxidation
R HOO
Hydrocarbon Hydroperoxide
free radical + radical
ROO
Peroxide
radical
RH
+ Base oil
hydrocarbon
+ Hydroperoxide
Diagram showing the oxidative degradation in lubricant base oils
precipitate as a thin film material that will trap hard troscopy. It can verify oxida- above, can monitor the
forming lacquers or varnish contaminants creating a tion in lubricants by identifi- additive depletion.
deposits on hot or cold metal sandpaper surface, which cation of functional groups
surfaces. can cause accelerated wear (e.g. ketones, carboxylic acids) RULER test
in the components. In addi- in molecules. (Remaining Useful Life
Consequences of the tion to this, varnish acts as Evaluation Routine)
oxidative degradation in an insulator, reducing the QSA It measures the remaining
lubricant base oils effect of the heat exchangers (Quantitative Spectrophoto- anti-oxidants by voltametric
which again means higher metric Analysis) analysis.
Corrosion and wear temperatures and accelerated The oxidation by-products are
Acid formation will cause reaction rates. isolated from the oil sample RBOT test
corrosion and wear in the and a quantitative spektro- (Rotating Bomb Oxidation
internal surfaces of the Measuring oxidation in photometric analysis of the iso- Test)
machine. Water, which is also lubricant base oils lated contaminants is carried It measures the oils resistence
formed under the oxidation Oxidation by-products (aka out in order to determine the to oxidation under prescribed
process, increases the corro- soft particles) are compounds degree of oxidation. conditions.
sive effect of the acids. of molecular sizes less than
1 micron, which cannot be Ultracentrifuge test Removal of oxidation products
Increase in oil viscosity measured by conventional This test uses the gravitatory using filtration systems
The oil viscosity increases due particle counting methods. forces to extract and settle The key to prevent oil degra-
to the formation of oxidation the contaminants of the oil. dation is to remove the oxi-
products e.g. polymeric com- TAN analysis (total acid num- The sediment is compared dation by-products before
pounds and sludge. It will ber) and viscosity testing can with a sedimentation rating they can react further and
result in friction, wear and be used as indicators of oxi- system to determine oxidation. form insoluble slugde and
loss of energy. dation but they cannot varnish deposits. These com- Oxidation is a common problem in
determine whether or not Gravimetric analysis pounds are very difficult to many industries
Sludge and varnish the oil is oxidized. Dark This analysis examines oxi- remove by the conventional
Sludge and varnish can color, and sour, putrid odor dation by measuring the mechanical filters because we
result in valves blocking and usually indicate oxidation. weight of residual compo- are dealing with submicron
orifices clogging. Once var- nents. The oil sample is particles with a high level of
nish deposits are formed on There are several methods treated with the solvents solubility in hydrocarbons.
metal surfaces, it is very dif- to monitor oxidation in the pentane (hexane), toluene Adsorption of oxidation by-products
ficult to dissolve them even oil. Generally, these methods and pyridine to determine Electrostatic filters and cellu- in the CJC Fine Filter: Resin in the
at high temperatures. These are used to either determine the oxidation products. lose filters can remove oxi- oil attracts to the polar fibres in the
deposits are like a sticky oil degradation products from dation products, because filter mass and are retained
the oil or the consumption Colorimetric Analysis: oxidation compounds are
Termination stage of anti-oxidants in the oil. This analysis examines the polar - i.e. have electrically
The latter is used to predict color of contaminants col- positive and negative poles.
RCHO Aldehyde [O] when the onset of oxidation lected on membrane filters
RCOOH Acid
RCOCH3 Ketone will occur. by a colorimetric device. The electrostatic filters remove
the oil contaminants using
ROOH
Hydro- The following are examples The following are examples the principles of electrostatic
peroxide of methods to monitor the of methods to monitor the and electromagnetism. The
oxidative degradation: consumption of anti-oxidant cellulose filters, on the other
High molecular
RCH2OH [O] additives: hand, utilize the characteris-
weight polymeric
Alcohol
compounds FTIR analysis tic that the cellulose material
(Fourier Transformation FTIR analysis is also polar. The oil degrada-
Sludge and Varnish Infrared Spectroscopy) (Fourier Transformation tion products are attracted
This analysis is based on the Infrared Spectroscopy) and retained by the poles of
principles of molecular spec- This analysis, mentioned the cellulose fibers.
Using Oil Analysis to Control Varnish and Sludge http://www.noria.com/learning_center/category_article.asp?articleid=59
New Varnish Test Improves Predictive Maintenance Program http://www.practicingoilanalysis.com/article_detail.asp?articleid=761&relatedbookgroup=OilAnalysis