surface active additives attach themselves Condensation settling: Some additives in size.

itives in size. However, the additives that work engines that are overheating. However, not HOW DO OILS

52
DEGRADE?
to the wear debris lying in the bottom such as dispersants work by keeping by attaching themselves to contaminants all additives will appear to increase at the
of the sump. Surface adsorption is the contaminants like soot in suspension, such as soot and water can be removed same rate, as the more volatile additives will
same phenomenon applied to intact metal however, when the additives get used up, by filtration but these are essentially ‘dead’ evaporate as well.

ISSUE
surfaces. the soot will start to agglomerate and will additives that are being removed.
eventually settle out of the oil, forming Centrifugation: Components that are fitted
Rubbing contact: Certain gear and deposits on metal surfaces and collecting Aggregate adsorption: Often the laboratory with centrifugal filters, usually engines, may
extreme pressure (EP) additives work by at the bottom of the sump. Other additives will be presented with a bank bag full of sludge be prone to additive loss by filtration. Once
chemically reacting with the metal surfaces
of the gear teeth. Borate gear oils work by
that have interfacial properties, such as
defoamants and demulsifiers, can also be
that looks incredibly like grease and has a
very similar feel and texture. The customer
again, these will tend to be additives that have
interfacial properties and it is ‘dead’ additives
by John Evans [Link].
forming boron-based crystalline structures prone to condensation settling too. wants to know what is contaminating the that are being removed from the system.
on the gear surfaces, which results in lubrication system. Invariably the sludge is a Analysis of filter cake from these types of
greatly improved frictional properties. With Filtration: A commonly-asked question is: combination of very fine (less than 5 micron filters reveals very high levels of oil additives used up during the lifetime of the
time it is possible for these compounds can an oil filter remove the additives from in size) wear debris (usually iron), coarse along with wear metals and contaminants. oil. As the oil is used to lubricate
to break down during rubbing contact, the oil? This is most often asked when dirt, a trace of water and some oil residues. a piece of machinery, the additives
resulting in the loss of the effectiveness ultra-filtration or centrifugal filters are This mixture is held together by the oil itself, This explains the most common mechanisms become depleted and deactivated
of the oil additive. Other EP additives being used on engines. Can this super- much the same way that milk might hold that cause lubricant additive depletion and and eventually the oil will wear out
that contain sulphur and phosphorus fine filtration damage the oil additive flour together in a batter. The bottom of degradation. As can be seen, the process is and will need to be replaced.
react by forming metal sulphides and package? Essentially, no, the filter will not most sumps will have varying concentrations quite complex and there are many competing
phosphides on the gear surface under the remove additives. It is possible for a filter of this sludge and surface active additives mechanisms that are taking place at the Why oils degrade has been covered
high contact temperatures and pressures to remove the anti-foamant additive as will be attracted to these aggregates and same time. Lubrication technology is very in numerous Technical Bulletins
encountered. These compounds have the molecules are quite big and can form be removed or stripped from the oil. The oil intricate and each can of oil is a very delicate but this issue will deal with how
good frictional properties too, but can also micelles, however, the other additives will residues will also be part of the lubricant’s and sophisticated blend of many chemicals lubricants degrade, in other words,
be lost during rubbing and sliding contact. all be well less than one tenth of a micron additive package. *** that all have very specific jobs to do. The what are the mechanisms for
base stock is also an elaborate mix of additive depletion and degradation.
Evaporation: Some additives like ZDDP compounds. Additives can often compete
are quite volatile and it is possible for with each other for active sites in an attempt The mechanisms we will look at are:
evaporation to take place, particularly where to do the jobs that are required of them.
high temperatures are being experienced; Likewise, the degradation of the oil is also a  Neutralisation
this usually occurs in engine applications. In complex web with many competing processes  Shear down
the case of thermal degradation of oil, the taking place at the same time. Even the best  Hydrolysis
loss of light ends may result in the apparent oil, in the best equipment, operating in an  Oxidation
increase in additives. This is due to the loss ideal environment with perfect maintenance  Thermal degradation
of the more volatile components of the base practices will eventually degrade, wear out  Water washing
stock, resulting in the apparent concentration and need to be changed.  Particle scrubbing
John Evans
of additives. This is particularly noted in  Surface adsorption
Oils have a finite lifetime - they will  Rubbing contact
eventually degrade and/or become  Condensation settling
contaminated and will need to be  Filtration
changed. Lubricants consist of  Aggregate adsorption
Copies of previous Technical Bulletins can be accessed on WearCheck’s web site: [Link] a base stock that can either be  Evaporation
mineral or synthetic. In the case  Centrifugation
of synthetic base stocks, these

JOINING TOGETHER TO SUPPORT THE PLANET are a family of compounds that are
manufactured in a laboratory to
Neutralisation: Although the sulphur
levels of fossil fuels have been
If you would prefer to receive future issues of WearCheck Monitor and Technical Bulletin have precisely the properties that reduced dramatically over the last
via e-mail in pdf format instead of in printed form, please e-mail a request to: the chemists and engineers want. ten years, many fuels still contain
support@[Link]. This option also applies to printed reports.
Mineral base stocks are derived small amounts of sulphur and some
from crude oil that comes out of the parts of the world still use fuels with
H ead Of f i c e K w aZu lu - N at al Br an c h es
9 L e Mans Pl ace, Johannesburg +27 (0 ) 1 1 3 9 2 6 3 2 2
ground and is refined to produce a sulphur in excess of 0.5%. Residual
Westm ead, KZN, 3610 Cape Tow n +27 (0) 2 1 9 8 1 8 8 1 0 base stock that can do the desired fuels used in marine applications can
PO Box 15108, Por t El izabeth +27 (0) 4 1 3 6 0 1 5 3 5
Westm ead, KZN, 3608 East L ondon +27 (0 ) 8 2 2 9 0 6 6 8 4
job. Synthetic bases are superior have sulphur contents very much
t +27 (0) 31 700 5460 Rustenburg +27 (0 ) 1 4 5 9 7 5 7 0 6 to mineral ones but are much more higher than this.
f +27 (0) 31 700 5471 Middel burg +27 (0) 1 3 2 4 6 2 9 6 6
e suppor t@ w earcheck . co. za Zam bia +260 (0 ) 9 7 7 6 2 2 2 8 7 expensive.
w w w w. w earcheck . co. za U AE +971 ( 0 ) 5 5 2 2 1 6 6 7 1 During combustion the sulphur
India +91 (0 ) 4 4 4 5 5 7 5 0 3 9
The other component of a lubricant is oxidised to form sulphur oxides
is the additive package. This is a which in turn react with water
range of twenty or more chemicals vapour (also a combustion by-
that the refinery blends with the product) to form sulphur acids.
base stock so that it can do its These acids are neither good for
Sludge like this is often found at the bottom of many sumps Publications are welcome to reproduce articles or extracts from them providing they acknowledge WearCheck, a member of the Set Point Group.
job. Most additives are sacrificial in the machinery (engine) nor the
nature and this means that they get oil. Engine oils are blended with

Sharon Fay Public Relations 09/2011 WEARCHECK IS A REGISTERED ISO 9001 AND ISO 14001 COMPANY
5 6
 additives that neutralise these acids. They higher VI as temperature increases. deposit that is sometimes found in engines higher boiling points and higher viscosities.
are typically over-based sulphonates of that have been contaminated with water.
calcium or magnesium and this is where The VI of an oil can be increased in a number A question that is often asked is ‘What is Oil flow
these results come from on an oil analysis of ways. Typical mineral multigrade oils have Oxidation: Oxidation can cause a the maximum temperature that this oil
report. an additive, VII or viscosity index improver, fundamental change in the base stock of the can withstand?’ Unfortunately there is no
which is a long chain organic polymer that oil and is the reason that even very clean answer as the lifetime of the oil is not only
As has already been noted, these additives remains tightly curled up when it is cold. As and well-maintained oils eventually wear out dependent on operating temperature but
Filter
are sacrificial and once they have neutralised the temperature increases the polymers and need to be changed. Oxidation is the time as well. So, what we need to know is,
the acids they cannot be regenerated to uncoil and retard the thinning action of the reaction between the oil’s base stock (and how hot and for how long? An engine oil
do the job again. Once all the additive has increase in temperature. Very highly refined its additives) and the oxygen that is found in might happily deal with 150ºC for an hour
Air bubbles are
been used up, acid build up will proceed very mineral oils have a naturally high VI as the the atmosphere. The air that we breathe is or so but degrade severely at 100ºC over a compressed Temperature
quickly. refining process removes the components about 20% oxygen. It is this gaseous element longer period of time. *** according to rises and the
of the crude oil that have poor VI properties. that permits us to live on planet earth and is Boyle’s law tiny amounts of
Nitrogen fixation from the atmosphere can also responsible for the combustion of fuels oil surrounding
generate nitrogen-based acids through a Unfortunately these long organic polymers that takes place in the cars we drive and Pump the air bubble
similar mechanism and these also need to that uncoil when the oil heats up are not the buses, trucks and bulldozers that we are cooked
be neutralised in the same manner to avoid completely shear stable. This means that operate. The rate at which the oil reacts
damage to both the oil and the equipment. when the compounds are subjected to high with oxygen is critically dependent on the
This becomes more of an issue with high shearing forces, such as may be encountered temperature at which that reaction takes
combustion temperatures found in gas in an automatic transmission, they start to place; the higher the temperature, the
engines. *** break up, resulting in a permanent viscosity faster the oil will oxidise. Resins,
loss. Oils that achieve varnishes and
a high VI through For every 10˚C increase in oil operating 1 bar 40˚C lacquers are
the refining process temperature, the rate at which the oil oxidises
50 bar 700˚C formed and
or by virtue of their is doubled and, by logical extension, the life plate out on
synthetic base stock time of the oil is halved. This situation is not Oil tank
100 bar 850˚C metal surfaces
are not subject to this quite as dire as it sounds as oils naturally
phenomenon. have quite a long life time. Temperature
really only becomes a significant issue over 200 bar 1100˚C
Hydrolysis: Hydrolysis 65˚C and oils that are subjected to high
quite literally means temperatures for extended periods of time
‘water cutting’ and is are blended with additives that retard the
the reaction of water reaction of the oil with oxygen. Microdieseling
with certain additives
that cause them to So what happens to the oil when it reacts very high temperatures on a microscopic Particle scrubbing: This is also
break down. This is a with oxygen and why does it do so much scale. These high temperatures can sometimes known as additive stripping.
chemical reaction of damage? When crude oil is taken from the An engine oil sample with a very high viscosity due to overheating actually burn the tiny amounts of oil that Some additives such as EP additives,
water that alters the ground it contains many, many different surround the air bubbles and this leads metal deactivators, rust inhibitors,
chemical make-up of chemical compounds yet a lot of these to the formation of resins, varnishes and tackiness agents and friction modifiers
the additive or base chemicals are closely related. The crude oil Thermal degradation: The main effect of lacquers. *** work by attaching themselves to the
stock. As an example, is taken to a refinery where these chemicals both oxidation and the loss of the thermal metal surfaces that they are protecting.
esters are formed are separated according to various chemical stability (sometimes called the loss of light Water washing: Whereas hydrolysis However, these additives are not selective
by the chemical and physical properties. ends) is an increase in viscosity. Increased involves the chemical breakdown of the oil as to what metal surfaces they bind to.
reaction of an acid viscosity can result in oil pump cavitation, by the action of water, water washing is If there is a lot of very finely powdered
A technician testing oil samples for neutralisation additives with an alcohol and What follows is a very brief chemistry poor fluidity on start-up, increased energy the physical removal of additives from the wear metal sitting in the bottom of the
the subsequent loss lesson. When an oil is subjected to elevated consumption and the reduction of the oil’s oil. Almost all additives are formulated to sump then this is where the additives will
of a water molecule. temperatures in the presence of oxygen, the ability to shed water and release air. Poor be soluble in the oil’s base stock so will go. Also note that the more finely divided
Shear down: it is vitally important that the This reaction is reversible and water can base stock reacts and forms compounds fluidity, due to increased viscosity and cold have limited solubility in aqueous (water) a mass is, the greater its surface area.
temperature at which viscosity is measured be added to an ester to break it back down that are known as peroxides which, in turn, starts, is when the majority of engine wear solutions. However, some additives are Wear debris has the effect of stripping
be noted, as viscosity changes with into its constituent alcohol/acid parts. The form another class of compounds called free takes place. selectively soluble in water; this means the additives out of the oil where they do
temperature. As temperature increases, the process would be known as hydrolysis. radicals. Both peroxides and free radicals that some of the additives can become not do any good.
viscosity decreases. To further complicate are highly reactive species and cause the Another phenomenon that is related to dissolved in the water which will cause
matters, different oils thin out at different Water can be responsible for the breakdown formation of acids and sludge and make the overheating and can result in oil degradation them to be removed from the oil. As Surface adsorption: This is quite similar
rates as the temperature increases. This of ester-based synthetic base stocks but can viscosity of the oil increase. This increase in is micro-dieseling. Air can exist in oil in four water is not generally soluble in oil in high to particle scrubbing in that surface active
introduces the concept of a viscosity index or also react with additives such as zinc dithio viscosity of the oil is due to another chemical forms, dissolved, entrained, foam and free. concentrations, this process results in additives bind to metal surfaces. This can
VI. The VI of an oil is a unitless number that diphosphate, which make up the anti-wear process known as polymerisation which It is the microscopic bubbles of entrained air the water washing of additives from the happen selectively so that additives are
gives a measure of how quickly the viscosity and anti-oxidant chemicals found in almost all simply means the sticking together of the that cause the problem. These bubbles can oil. Hydrolysis is the chemical degradation taken out of circulation or certain additives
will change with temperature. Oils with a low engine oils. This is why engine oils are prone smaller fractions of the base stock to form be compressed, according to Boyle’s law, to of additives; water washing is the physical are selectively adsorbed at the expense
VI will thin out more rapidly than oils with a to emulsification – that mayonnaise-like fractions of larger chemicals which have very high pressures which, in turn, can create depletion. of others. Particle scrubbing occurs when

2 3 4
 additives that neutralise these acids. They higher VI as temperature increases. deposit that is sometimes found in engines higher boiling points and higher viscosities.
are typically over-based sulphonates of that have been contaminated with water.
calcium or magnesium and this is where The VI of an oil can be increased in a number A question that is often asked is ‘What is Oil flow
these results come from on an oil analysis of ways. Typical mineral multigrade oils have Oxidation: Oxidation can cause a the maximum temperature that this oil
report. an additive, VII or viscosity index improver, fundamental change in the base stock of the can withstand?’ Unfortunately there is no
which is a long chain organic polymer that oil and is the reason that even very clean answer as the lifetime of the oil is not only
As has already been noted, these additives remains tightly curled up when it is cold. As and well-maintained oils eventually wear out dependent on operating temperature but
Filter
are sacrificial and once they have neutralised the temperature increases the polymers and need to be changed. Oxidation is the time as well. So, what we need to know is,
the acids they cannot be regenerated to uncoil and retard the thinning action of the reaction between the oil’s base stock (and how hot and for how long? An engine oil
do the job again. Once all the additive has increase in temperature. Very highly refined its additives) and the oxygen that is found in might happily deal with 150ºC for an hour
Air bubbles are
been used up, acid build up will proceed very mineral oils have a naturally high VI as the the atmosphere. The air that we breathe is or so but degrade severely at 100ºC over a compressed Temperature
quickly. refining process removes the components about 20% oxygen. It is this gaseous element longer period of time. *** according to rises and the
of the crude oil that have poor VI properties. that permits us to live on planet earth and is Boyle’s law tiny amounts of
Nitrogen fixation from the atmosphere can also responsible for the combustion of fuels oil surrounding
generate nitrogen-based acids through a Unfortunately these long organic polymers that takes place in the cars we drive and Pump the air bubble
similar mechanism and these also need to that uncoil when the oil heats up are not the buses, trucks and bulldozers that we are cooked
be neutralised in the same manner to avoid completely shear stable. This means that operate. The rate at which the oil reacts
damage to both the oil and the equipment. when the compounds are subjected to high with oxygen is critically dependent on the
This becomes more of an issue with high shearing forces, such as may be encountered temperature at which that reaction takes
combustion temperatures found in gas in an automatic transmission, they start to place; the higher the temperature, the
engines. *** break up, resulting in a permanent viscosity faster the oil will oxidise. Resins,
loss. Oils that achieve varnishes and
a high VI through For every 10˚C increase in oil operating 1 bar 40˚C lacquers are
the refining process temperature, the rate at which the oil oxidises
50 bar 700˚C formed and
or by virtue of their is doubled and, by logical extension, the life plate out on
synthetic base stock time of the oil is halved. This situation is not Oil tank
100 bar 850˚C metal surfaces
are not subject to this quite as dire as it sounds as oils naturally
phenomenon. have quite a long life time. Temperature
really only becomes a significant issue over 200 bar 1100˚C
Hydrolysis: Hydrolysis 65˚C and oils that are subjected to high
quite literally means temperatures for extended periods of time
‘water cutting’ and is are blended with additives that retard the
the reaction of water reaction of the oil with oxygen. Microdieseling
with certain additives
that cause them to So what happens to the oil when it reacts very high temperatures on a microscopic Particle scrubbing: This is also
break down. This is a with oxygen and why does it do so much scale. These high temperatures can sometimes known as additive stripping.
chemical reaction of damage? When crude oil is taken from the An engine oil sample with a very high viscosity due to overheating actually burn the tiny amounts of oil that Some additives such as EP additives,
water that alters the ground it contains many, many different surround the air bubbles and this leads metal deactivators, rust inhibitors,
chemical make-up of chemical compounds yet a lot of these to the formation of resins, varnishes and tackiness agents and friction modifiers
the additive or base chemicals are closely related. The crude oil Thermal degradation: The main effect of lacquers. *** work by attaching themselves to the
stock. As an example, is taken to a refinery where these chemicals both oxidation and the loss of the thermal metal surfaces that they are protecting.
esters are formed are separated according to various chemical stability (sometimes called the loss of light Water washing: Whereas hydrolysis However, these additives are not selective
by the chemical and physical properties. ends) is an increase in viscosity. Increased involves the chemical breakdown of the oil as to what metal surfaces they bind to.
reaction of an acid viscosity can result in oil pump cavitation, by the action of water, water washing is If there is a lot of very finely powdered
A technician testing oil samples for neutralisation additives with an alcohol and What follows is a very brief chemistry poor fluidity on start-up, increased energy the physical removal of additives from the wear metal sitting in the bottom of the
the subsequent loss lesson. When an oil is subjected to elevated consumption and the reduction of the oil’s oil. Almost all additives are formulated to sump then this is where the additives will
of a water molecule. temperatures in the presence of oxygen, the ability to shed water and release air. Poor be soluble in the oil’s base stock so will go. Also note that the more finely divided
Shear down: it is vitally important that the This reaction is reversible and water can base stock reacts and forms compounds fluidity, due to increased viscosity and cold have limited solubility in aqueous (water) a mass is, the greater its surface area.
temperature at which viscosity is measured be added to an ester to break it back down that are known as peroxides which, in turn, starts, is when the majority of engine wear solutions. However, some additives are Wear debris has the effect of stripping
be noted, as viscosity changes with into its constituent alcohol/acid parts. The form another class of compounds called free takes place. selectively soluble in water; this means the additives out of the oil where they do
temperature. As temperature increases, the process would be known as hydrolysis. radicals. Both peroxides and free radicals that some of the additives can become not do any good.
viscosity decreases. To further complicate are highly reactive species and cause the Another phenomenon that is related to dissolved in the water which will cause
matters, different oils thin out at different Water can be responsible for the breakdown formation of acids and sludge and make the overheating and can result in oil degradation them to be removed from the oil. As Surface adsorption: This is quite similar
rates as the temperature increases. This of ester-based synthetic base stocks but can viscosity of the oil increase. This increase in is micro-dieseling. Air can exist in oil in four water is not generally soluble in oil in high to particle scrubbing in that surface active
introduces the concept of a viscosity index or also react with additives such as zinc dithio viscosity of the oil is due to another chemical forms, dissolved, entrained, foam and free. concentrations, this process results in additives bind to metal surfaces. This can
VI. The VI of an oil is a unitless number that diphosphate, which make up the anti-wear process known as polymerisation which It is the microscopic bubbles of entrained air the water washing of additives from the happen selectively so that additives are
gives a measure of how quickly the viscosity and anti-oxidant chemicals found in almost all simply means the sticking together of the that cause the problem. These bubbles can oil. Hydrolysis is the chemical degradation taken out of circulation or certain additives
will change with temperature. Oils with a low engine oils. This is why engine oils are prone smaller fractions of the base stock to form be compressed, according to Boyle’s law, to of additives; water washing is the physical are selectively adsorbed at the expense
VI will thin out more rapidly than oils with a to emulsification – that mayonnaise-like fractions of larger chemicals which have very high pressures which, in turn, can create depletion. of others. Particle scrubbing occurs when

2 3 4
 additives that neutralise these acids. They higher VI as temperature increases. deposit that is sometimes found in engines higher boiling points and higher viscosities.
are typically over-based sulphonates of that have been contaminated with water.
calcium or magnesium and this is where The VI of an oil can be increased in a number A question that is often asked is ‘What is Oil flow
these results come from on an oil analysis of ways. Typical mineral multigrade oils have Oxidation: Oxidation can cause a the maximum temperature that this oil
report. an additive, VII or viscosity index improver, fundamental change in the base stock of the can withstand?’ Unfortunately there is no
which is a long chain organic polymer that oil and is the reason that even very clean answer as the lifetime of the oil is not only
As has already been noted, these additives remains tightly curled up when it is cold. As and well-maintained oils eventually wear out dependent on operating temperature but
Filter
are sacrificial and once they have neutralised the temperature increases the polymers and need to be changed. Oxidation is the time as well. So, what we need to know is,
the acids they cannot be regenerated to uncoil and retard the thinning action of the reaction between the oil’s base stock (and how hot and for how long? An engine oil
do the job again. Once all the additive has increase in temperature. Very highly refined its additives) and the oxygen that is found in might happily deal with 150ºC for an hour
Air bubbles are
been used up, acid build up will proceed very mineral oils have a naturally high VI as the the atmosphere. The air that we breathe is or so but degrade severely at 100ºC over a compressed Temperature
quickly. refining process removes the components about 20% oxygen. It is this gaseous element longer period of time. *** according to rises and the
of the crude oil that have poor VI properties. that permits us to live on planet earth and is Boyle’s law tiny amounts of
Nitrogen fixation from the atmosphere can also responsible for the combustion of fuels oil surrounding
generate nitrogen-based acids through a Unfortunately these long organic polymers that takes place in the cars we drive and Pump the air bubble
similar mechanism and these also need to that uncoil when the oil heats up are not the buses, trucks and bulldozers that we are cooked
be neutralised in the same manner to avoid completely shear stable. This means that operate. The rate at which the oil reacts
damage to both the oil and the equipment. when the compounds are subjected to high with oxygen is critically dependent on the
This becomes more of an issue with high shearing forces, such as may be encountered temperature at which that reaction takes
combustion temperatures found in gas in an automatic transmission, they start to place; the higher the temperature, the
engines. *** break up, resulting in a permanent viscosity faster the oil will oxidise. Resins,
loss. Oils that achieve varnishes and
a high VI through For every 10˚C increase in oil operating 1 bar 40˚C lacquers are
the refining process temperature, the rate at which the oil oxidises
50 bar 700˚C formed and
or by virtue of their is doubled and, by logical extension, the life plate out on
synthetic base stock time of the oil is halved. This situation is not Oil tank
100 bar 850˚C metal surfaces
are not subject to this quite as dire as it sounds as oils naturally
phenomenon. have quite a long life time. Temperature
really only becomes a significant issue over 200 bar 1100˚C
Hydrolysis: Hydrolysis 65˚C and oils that are subjected to high
quite literally means temperatures for extended periods of time
‘water cutting’ and is are blended with additives that retard the
the reaction of water reaction of the oil with oxygen. Microdieseling
with certain additives
that cause them to So what happens to the oil when it reacts very high temperatures on a microscopic Particle scrubbing: This is also
break down. This is a with oxygen and why does it do so much scale. These high temperatures can sometimes known as additive stripping.
chemical reaction of damage? When crude oil is taken from the An engine oil sample with a very high viscosity due to overheating actually burn the tiny amounts of oil that Some additives such as EP additives,
water that alters the ground it contains many, many different surround the air bubbles and this leads metal deactivators, rust inhibitors,
chemical make-up of chemical compounds yet a lot of these to the formation of resins, varnishes and tackiness agents and friction modifiers
the additive or base chemicals are closely related. The crude oil Thermal degradation: The main effect of lacquers. *** work by attaching themselves to the
stock. As an example, is taken to a refinery where these chemicals both oxidation and the loss of the thermal metal surfaces that they are protecting.
esters are formed are separated according to various chemical stability (sometimes called the loss of light Water washing: Whereas hydrolysis However, these additives are not selective
by the chemical and physical properties. ends) is an increase in viscosity. Increased involves the chemical breakdown of the oil as to what metal surfaces they bind to.
reaction of an acid viscosity can result in oil pump cavitation, by the action of water, water washing is If there is a lot of very finely powdered
A technician testing oil samples for neutralisation additives with an alcohol and What follows is a very brief chemistry poor fluidity on start-up, increased energy the physical removal of additives from the wear metal sitting in the bottom of the
the subsequent loss lesson. When an oil is subjected to elevated consumption and the reduction of the oil’s oil. Almost all additives are formulated to sump then this is where the additives will
of a water molecule. temperatures in the presence of oxygen, the ability to shed water and release air. Poor be soluble in the oil’s base stock so will go. Also note that the more finely divided
Shear down: it is vitally important that the This reaction is reversible and water can base stock reacts and forms compounds fluidity, due to increased viscosity and cold have limited solubility in aqueous (water) a mass is, the greater its surface area.
temperature at which viscosity is measured be added to an ester to break it back down that are known as peroxides which, in turn, starts, is when the majority of engine wear solutions. However, some additives are Wear debris has the effect of stripping
be noted, as viscosity changes with into its constituent alcohol/acid parts. The form another class of compounds called free takes place. selectively soluble in water; this means the additives out of the oil where they do
temperature. As temperature increases, the process would be known as hydrolysis. radicals. Both peroxides and free radicals that some of the additives can become not do any good.
viscosity decreases. To further complicate are highly reactive species and cause the Another phenomenon that is related to dissolved in the water which will cause
matters, different oils thin out at different Water can be responsible for the breakdown formation of acids and sludge and make the overheating and can result in oil degradation them to be removed from the oil. As Surface adsorption: This is quite similar
rates as the temperature increases. This of ester-based synthetic base stocks but can viscosity of the oil increase. This increase in is micro-dieseling. Air can exist in oil in four water is not generally soluble in oil in high to particle scrubbing in that surface active
introduces the concept of a viscosity index or also react with additives such as zinc dithio viscosity of the oil is due to another chemical forms, dissolved, entrained, foam and free. concentrations, this process results in additives bind to metal surfaces. This can
VI. The VI of an oil is a unitless number that diphosphate, which make up the anti-wear process known as polymerisation which It is the microscopic bubbles of entrained air the water washing of additives from the happen selectively so that additives are
gives a measure of how quickly the viscosity and anti-oxidant chemicals found in almost all simply means the sticking together of the that cause the problem. These bubbles can oil. Hydrolysis is the chemical degradation taken out of circulation or certain additives
will change with temperature. Oils with a low engine oils. This is why engine oils are prone smaller fractions of the base stock to form be compressed, according to Boyle’s law, to of additives; water washing is the physical are selectively adsorbed at the expense
VI will thin out more rapidly than oils with a to emulsification – that mayonnaise-like fractions of larger chemicals which have very high pressures which, in turn, can create depletion. of others. Particle scrubbing occurs when

2 3 4
 surface active additives attach themselves Condensation settling: Some additives in size. However, the additives that work engines that are overheating. However, not HOW DO OILS

52
DEGRADE?
to the wear debris lying in the bottom such as dispersants work by keeping by attaching themselves to contaminants all additives will appear to increase at the
of the sump. Surface adsorption is the contaminants like soot in suspension, such as soot and water can be removed same rate, as the more volatile additives will
same phenomenon applied to intact metal however, when the additives get used up, by filtration but these are essentially ‘dead’ evaporate as well.

ISSUE
surfaces. the soot will start to agglomerate and will additives that are being removed.
eventually settle out of the oil, forming Centrifugation: Components that are fitted
Rubbing contact: Certain gear and deposits on metal surfaces and collecting Aggregate adsorption: Often the laboratory with centrifugal filters, usually engines, may
extreme pressure (EP) additives work by at the bottom of the sump. Other additives will be presented with a bank bag full of sludge be prone to additive loss by filtration. Once
chemically reacting with the metal surfaces
of the gear teeth. Borate gear oils work by
that have interfacial properties, such as
defoamants and demulsifiers, can also be
that looks incredibly like grease and has a
very similar feel and texture. The customer
again, these will tend to be additives that have
interfacial properties and it is ‘dead’ additives
by John Evans [Link].
forming boron-based crystalline structures prone to condensation settling too. wants to know what is contaminating the that are being removed from the system.
on the gear surfaces, which results in lubrication system. Invariably the sludge is a Analysis of filter cake from these types of
greatly improved frictional properties. With Filtration: A commonly-asked question is: combination of very fine (less than 5 micron filters reveals very high levels of oil additives used up during the lifetime of the
time it is possible for these compounds can an oil filter remove the additives from in size) wear debris (usually iron), coarse along with wear metals and contaminants. oil. As the oil is used to lubricate
to break down during rubbing contact, the oil? This is most often asked when dirt, a trace of water and some oil residues. a piece of machinery, the additives
resulting in the loss of the effectiveness ultra-filtration or centrifugal filters are This mixture is held together by the oil itself, This explains the most common mechanisms become depleted and deactivated
of the oil additive. Other EP additives being used on engines. Can this super- much the same way that milk might hold that cause lubricant additive depletion and and eventually the oil will wear out
that contain sulphur and phosphorus fine filtration damage the oil additive flour together in a batter. The bottom of degradation. As can be seen, the process is and will need to be replaced.
react by forming metal sulphides and package? Essentially, no, the filter will not most sumps will have varying concentrations quite complex and there are many competing
phosphides on the gear surface under the remove additives. It is possible for a filter of this sludge and surface active additives mechanisms that are taking place at the Why oils degrade has been covered
high contact temperatures and pressures to remove the anti-foamant additive as will be attracted to these aggregates and same time. Lubrication technology is very in numerous Technical Bulletins
encountered. These compounds have the molecules are quite big and can form be removed or stripped from the oil. The oil intricate and each can of oil is a very delicate but this issue will deal with how
good frictional properties too, but can also micelles, however, the other additives will residues will also be part of the lubricant’s and sophisticated blend of many chemicals lubricants degrade, in other words,
be lost during rubbing and sliding contact. all be well less than one tenth of a micron additive package. *** that all have very specific jobs to do. The what are the mechanisms for
base stock is also an elaborate mix of additive depletion and degradation.
Evaporation: Some additives like ZDDP compounds. Additives can often compete
are quite volatile and it is possible for with each other for active sites in an attempt The mechanisms we will look at are:
evaporation to take place, particularly where to do the jobs that are required of them.
high temperatures are being experienced; Likewise, the degradation of the oil is also a  Neutralisation
this usually occurs in engine applications. In complex web with many competing processes  Shear down
the case of thermal degradation of oil, the taking place at the same time. Even the best  Hydrolysis
loss of light ends may result in the apparent oil, in the best equipment, operating in an  Oxidation
increase in additives. This is due to the loss ideal environment with perfect maintenance  Thermal degradation
of the more volatile components of the base practices will eventually degrade, wear out  Water washing
stock, resulting in the apparent concentration and need to be changed.  Particle scrubbing
John Evans
of additives. This is particularly noted in  Surface adsorption
Oils have a finite lifetime - they will  Rubbing contact
eventually degrade and/or become  Condensation settling
contaminated and will need to be  Filtration
changed. Lubricants consist of  Aggregate adsorption
Copies of previous Technical Bulletins can be accessed on WearCheck’s web site: [Link] a base stock that can either be  Evaporation
mineral or synthetic. In the case  Centrifugation
of synthetic base stocks, these

JOINING TOGETHER TO SUPPORT THE PLANET are a family of compounds that are
manufactured in a laboratory to
Neutralisation: Although the sulphur
levels of fossil fuels have been
If you would prefer to receive future issues of WearCheck Monitor and Technical Bulletin have precisely the properties that reduced dramatically over the last
via e-mail in pdf format instead of in printed form, please e-mail a request to: the chemists and engineers want. ten years, many fuels still contain
support@[Link]. This option also applies to printed reports.
Mineral base stocks are derived small amounts of sulphur and some
from crude oil that comes out of the parts of the world still use fuels with
H ead Of f i c e K w aZu lu - N at al Br an c h es
9 L e Mans Pl ace, Johannesburg +27 (0 ) 1 1 3 9 2 6 3 2 2
ground and is refined to produce a sulphur in excess of 0.5%. Residual
Westm ead, KZN, 3610 Cape Tow n +27 (0) 2 1 9 8 1 8 8 1 0 base stock that can do the desired fuels used in marine applications can
PO Box 15108, Por t El izabeth +27 (0) 4 1 3 6 0 1 5 3 5
Westm ead, KZN, 3608 East L ondon +27 (0 ) 8 2 2 9 0 6 6 8 4
job. Synthetic bases are superior have sulphur contents very much
t +27 (0) 31 700 5460 Rustenburg +27 (0 ) 1 4 5 9 7 5 7 0 6 to mineral ones but are much more higher than this.
f +27 (0) 31 700 5471 Middel burg +27 (0) 1 3 2 4 6 2 9 6 6
e suppor t@ w earcheck . co. za Zam bia +260 (0 ) 9 7 7 6 2 2 2 8 7 expensive.
w w w w. w earcheck . co. za U AE +971 ( 0 ) 5 5 2 2 1 6 6 7 1 During combustion the sulphur
India +91 (0 ) 4 4 4 5 5 7 5 0 3 9
The other component of a lubricant is oxidised to form sulphur oxides
is the additive package. This is a which in turn react with water
range of twenty or more chemicals vapour (also a combustion by-
that the refinery blends with the product) to form sulphur acids.
base stock so that it can do its These acids are neither good for
Sludge like this is often found at the bottom of many sumps Publications are welcome to reproduce articles or extracts from them providing they acknowledge WearCheck, a member of the Set Point Group.
job. Most additives are sacrificial in the machinery (engine) nor the
nature and this means that they get oil. Engine oils are blended with

Sharon Fay Public Relations 09/2011 WEARCHECK IS A REGISTERED ISO 9001 AND ISO 14001 COMPANY
5 6
 surface active additives attach themselves Condensation settling: Some additives in size. However, the additives that work engines that are overheating. However, not HOW DO OILS

52
DEGRADE?
to the wear debris lying in the bottom such as dispersants work by keeping by attaching themselves to contaminants all additives will appear to increase at the
of the sump. Surface adsorption is the contaminants like soot in suspension, such as soot and water can be removed same rate, as the more volatile additives will
same phenomenon applied to intact metal however, when the additives get used up, by filtration but these are essentially ‘dead’ evaporate as well.

ISSUE
surfaces. the soot will start to agglomerate and will additives that are being removed.
eventually settle out of the oil, forming Centrifugation: Components that are fitted
Rubbing contact: Certain gear and deposits on metal surfaces and collecting Aggregate adsorption: Often the laboratory with centrifugal filters, usually engines, may
extreme pressure (EP) additives work by at the bottom of the sump. Other additives will be presented with a bank bag full of sludge be prone to additive loss by filtration. Once
chemically reacting with the metal surfaces
of the gear teeth. Borate gear oils work by
that have interfacial properties, such as
defoamants and demulsifiers, can also be
that looks incredibly like grease and has a
very similar feel and texture. The customer
again, these will tend to be additives that have
interfacial properties and it is ‘dead’ additives
by John Evans [Link].
forming boron-based crystalline structures prone to condensation settling too. wants to know what is contaminating the that are being removed from the system.
on the gear surfaces, which results in lubrication system. Invariably the sludge is a Analysis of filter cake from these types of
greatly improved frictional properties. With Filtration: A commonly-asked question is: combination of very fine (less than 5 micron filters reveals very high levels of oil additives used up during the lifetime of the
time it is possible for these compounds can an oil filter remove the additives from in size) wear debris (usually iron), coarse along with wear metals and contaminants. oil. As the oil is used to lubricate
to break down during rubbing contact, the oil? This is most often asked when dirt, a trace of water and some oil residues. a piece of machinery, the additives
resulting in the loss of the effectiveness ultra-filtration or centrifugal filters are This mixture is held together by the oil itself, This explains the most common mechanisms become depleted and deactivated
of the oil additive. Other EP additives being used on engines. Can this super- much the same way that milk might hold that cause lubricant additive depletion and and eventually the oil will wear out
that contain sulphur and phosphorus fine filtration damage the oil additive flour together in a batter. The bottom of degradation. As can be seen, the process is and will need to be replaced.
react by forming metal sulphides and package? Essentially, no, the filter will not most sumps will have varying concentrations quite complex and there are many competing
phosphides on the gear surface under the remove additives. It is possible for a filter of this sludge and surface active additives mechanisms that are taking place at the Why oils degrade has been covered
high contact temperatures and pressures to remove the anti-foamant additive as will be attracted to these aggregates and same time. Lubrication technology is very in numerous Technical Bulletins
encountered. These compounds have the molecules are quite big and can form be removed or stripped from the oil. The oil intricate and each can of oil is a very delicate but this issue will deal with how
good frictional properties too, but can also micelles, however, the other additives will residues will also be part of the lubricant’s and sophisticated blend of many chemicals lubricants degrade, in other words,
be lost during rubbing and sliding contact. all be well less than one tenth of a micron additive package. *** that all have very specific jobs to do. The what are the mechanisms for
base stock is also an elaborate mix of additive depletion and degradation.
Evaporation: Some additives like ZDDP compounds. Additives can often compete
are quite volatile and it is possible for with each other for active sites in an attempt The mechanisms we will look at are:
evaporation to take place, particularly where to do the jobs that are required of them.
high temperatures are being experienced; Likewise, the degradation of the oil is also a  Neutralisation
this usually occurs in engine applications. In complex web with many competing processes  Shear down
the case of thermal degradation of oil, the taking place at the same time. Even the best  Hydrolysis
loss of light ends may result in the apparent oil, in the best equipment, operating in an  Oxidation
increase in additives. This is due to the loss ideal environment with perfect maintenance  Thermal degradation
of the more volatile components of the base practices will eventually degrade, wear out  Water washing
stock, resulting in the apparent concentration and need to be changed.  Particle scrubbing
John Evans
of additives. This is particularly noted in  Surface adsorption
Oils have a finite lifetime - they will  Rubbing contact
eventually degrade and/or become  Condensation settling
contaminated and will need to be  Filtration
changed. Lubricants consist of  Aggregate adsorption
Copies of previous Technical Bulletins can be accessed on WearCheck’s web site: [Link] a base stock that can either be  Evaporation
mineral or synthetic. In the case  Centrifugation
of synthetic base stocks, these

JOINING TOGETHER TO SUPPORT THE PLANET are a family of compounds that are
manufactured in a laboratory to
Neutralisation: Although the sulphur
levels of fossil fuels have been
If you would prefer to receive future issues of WearCheck Monitor and Technical Bulletin have precisely the properties that reduced dramatically over the last
via e-mail in pdf format instead of in printed form, please e-mail a request to: the chemists and engineers want. ten years, many fuels still contain
support@[Link]. This option also applies to printed reports.
Mineral base stocks are derived small amounts of sulphur and some
from crude oil that comes out of the parts of the world still use fuels with
H ead Of f i c e K w aZu lu - N at al Br an c h es
9 L e Mans Pl ace, Johannesburg +27 (0 ) 1 1 3 9 2 6 3 2 2
ground and is refined to produce a sulphur in excess of 0.5%. Residual
Westm ead, KZN, 3610 Cape Tow n +27 (0) 2 1 9 8 1 8 8 1 0 base stock that can do the desired fuels used in marine applications can
PO Box 15108, Por t El izabeth +27 (0) 4 1 3 6 0 1 5 3 5
Westm ead, KZN, 3608 East L ondon +27 (0 ) 8 2 2 9 0 6 6 8 4
job. Synthetic bases are superior have sulphur contents very much
t +27 (0) 31 700 5460 Rustenburg +27 (0 ) 1 4 5 9 7 5 7 0 6 to mineral ones but are much more higher than this.
f +27 (0) 31 700 5471 Middel burg +27 (0) 1 3 2 4 6 2 9 6 6
e suppor t@ w earcheck . co. za Zam bia +260 (0 ) 9 7 7 6 2 2 2 8 7 expensive.
w w w w. w earcheck . co. za U AE +971 ( 0 ) 5 5 2 2 1 6 6 7 1 During combustion the sulphur
India +91 (0 ) 4 4 4 5 5 7 5 0 3 9
The other component of a lubricant is oxidised to form sulphur oxides
is the additive package. This is a which in turn react with water
range of twenty or more chemicals vapour (also a combustion by-
that the refinery blends with the product) to form sulphur acids.
base stock so that it can do its These acids are neither good for
Sludge like this is often found at the bottom of many sumps Publications are welcome to reproduce articles or extracts from them providing they acknowledge WearCheck, a member of the Set Point Group.
job. Most additives are sacrificial in the machinery (engine) nor the
nature and this means that they get oil. Engine oils are blended with

Sharon Fay Public Relations 09/2011 WEARCHECK IS A REGISTERED ISO 9001 AND ISO 14001 COMPANY
5 6