ANTI-OXIDANTS AND

CONTAMINATION CONTROL

YOUR EQUIPMENT’S
HEALTH DEPENDS ON THEM

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 To appreciate the need for the monitoring of anti-oxidants and
contamination a brief look at the composition of a typical modern
lubricant is beneficial.
The next slide depicts the components of a lubricant and
describes their function in the lubrication process. Each
component of the lubricant wheel is hyperlinked to the
appropriate description of the additive or base oil allowing you to
progress as fast or a slow as you want through the information
provided. Use the CONTINUE button to proceed.
Once a better understanding of the lubricant is realised, the
need to monitor these properties becomes more evident for the
continued protection of the lubricant as well as the compartment.

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 ANTI- POUR POINT
BASE OIL DEPRESSANT
OXIDANT

BLENDED
ANTI-FOAM TOGETHER TO CORROSION
ADDITIVE PRODUCE INHIBITOR
LUBRICANTS TO
SPECIFICATION

ANTI-WEAR and DETERGENT & VISCOSITY

EP ADDITIVES DISPERSANT INDEX
ADDITIVES IMPROVER
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 MINERAL BASE OILS
Base oils transport additives to areas where protection is needed.
The lubricating oil fractions from the refinery after purifying and de-waxing are
referred to as mineral base oils. They are made up of:
Normal paraffinic (or saturated) molecules, most stable to oxidation
Branched chain paraffinic molecules (naphthenics), less stable to oxidation
Aromatic (or unsaturated) molecules, prone to oxidation
Base oils are classified by Group Numbers:
GROUP I Normal Paraffin content 50 % typical
Naphthenic content 45 % typical
Aromatic content 5% typical

GROUP II Normal Paraffin content 65 % typical

Naphthenic content 34 % typical
Aromatic content 1% typical

GROUP III Normal Paraffin content 85 % typical

Naphthenic content 15 % typical
Aromatic content 0% typical
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 SYNTHETIC BASE OILS
Although GROUP III oil based products can be marketed as synthetic or semi-
synthetic products, they are not truly synthesised in the true sense of the word.
The two main types of synthetic oils are:
POLYALPHAOLEFIN (PAO) and ESTER based synthetic oil are chemically
manufactured from appropriate raw materials.
GROUP IV PAO base oils are manufactured using unsaturated hydrocarbon
molecules called olefins. The simplest olefin is ethylene gas which
can be manufactured synthetically or obtained as a product from the
crude oil refining process and is usually the olefin of choice for
manufacture of PAO base oils. By combining individual molecules of
ethylene (known as an alpha olefin) in a process called
polymerisation saturated long chain paraffinic hydrocarbons are
produced. Oil produced in this way is very oxidation stable. Being a
synthetically produced hydrocarbon, these base oils are compatible
with mineral base oils.

GROUP V These oils are synthetically manufactured by reacting organic

chemicals together to form a very stable ester in the form of an oil.
They are typically characterised by being very light (ISO 22-ISO 32)
grade, very stable to oxidation and fluid at very low temperatures.
Polyol ester base oils have higher viscosities.

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Treatment of metal surfaces to prevent corrosion due to
entrapped air is catered for by the inclusion of a
CORROSION INHIBITOR similar to that supplied in cooling
systems. The inhibitor acts in two main ways:

• wetting the exposed surfaces with a layer of

additive
• react preferentially with air and water thus
preventing its attack on metals surfaces.

Typically the corrosion inhibitors are of the amine and

phosphate type compounds which absorb oxygen and
prevent rusting. They also react with acidic by-products of
wear to prevent attack on vulnerable metal surfaces.
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Frictional forces within a lubricated system tend to generate wear by
metal to metal contact. The heat generated by this contact is so severe
that the metals weld together and further motion of the surfaces tears
these welded sections apart creating a rough surface and wear debris.

An additive called ANTI-WEAR Additive utilises the heat generated to

chemically bond with the metal surfaces and prevent future welding and
in doing so retards the wear effect.

A typical engine anti-wear additive is Zinc Dialkyl DithioPhosphate

(ZDDP) sometimes referred to merely as zinc anti-wear additives. ZDDP
also acts as an Anti-oxidant.
Extreme pressure (EP) additives are typically composed of
Phosphorus/Sulphur compounds which bond to the moving surfaces under
heat of welding and shearing of the metal to metal contact. This bonding
imparts a “slippery” surface on the moving components exposed to wear
and provides a better surface to counteract wear.

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Multigrade oils have been introduced into the modern lubricated
equipment to give them the capability to lubricate at cold starting to
minimise start-up wear while being able to provide the specified
lubrication at operating temperature.
Base oils by themselves have a characteristic “thinning out” when the
temperature increases from cold start to operating temperature.
The relationship between increasing temperature and corresponding
decrease in viscosity (thickness) of the oil is known as the Viscosity
Index (VI). To increase the natural VI of the oil and thus increase the
lubrication ability of the oil at elevated temperatures, an additive called a
VISCOSITY INDEX IMPROVER is added to the blended oil. VI
Improvers are typically long chain hydrocarbon compounds.
The VI improver retards the thinning out of the oil when heated but does
not interfere with the lubricant when cold.

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 Air is a lousy lubricant. Air entrapment in
lubricated components permits metal to
metal contact and results in excessive wear.
An additive must be included to permit the
air to quickly dissipate from the oil.

This is called ANTI-FOAM additive and is

generally in the form of a silicone type oil in
the order of up to 10 parts per million.

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ANTI-OXIDANTS are chemicals added to a lubricant to protect the base oil of
the lubricant and thereby protecting the equipment being lubricated.
The anti-oxidant additives are designed to be sacrificially consumed during
the life of the lubricant and are the first of the additives in an oil to deplete.
If the Anti-oxidant level depletes to below 30% of the original concentration, it
can no longer completely protect the lubricant nor the equipment.
Anti-oxidants operate in several ways.
• reacting with entrapped air to prevent varnish formation in the base
oil.
• preventing formation of degradation by-products in the oil in high
friction areas.
• neutralise the effects of metallic wear particles that could lead to
degradation of the oil.
• neutralise the effects of moisture that could lead to degradation of
the oil.

Conventional Anti-oxidant additives are amines and phenols. In some cases

anti-wear additives such as Zinc Di Alkyl Di ThioPhosphate (ZDDP) have an
anti-oxidant effect and can also be monitored.
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Detergents in oil clean surfaces within the lubricated
compartments (usually engines).
These additives also keep the material removed in
suspension until it can be removed by the system filters
or by change-out.
These additives chemically protect oil from attack and
neutralise acids that are formed by fuel combustion.
Dispersants are chemicals which when added to oils
assist the detergent additive keep the contamination
which it has cleaned from surfaces as well as other
introduced contaminants such as water (and soot in
engines) in suspension until the contamination can be
removed.
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 In cold climates, the oil may freeze and starve the
lubricated components of oil causing wear. An
additive that inhibits the freezing characteristics of
the oil (in much the same way as glycol in the
cooling system inhibits freezing of the water) is
blended into the oil.

This additive is the POUR POINT DEPRESSANT

The name POUR POINT relates to the temperature

at which the lubricant can just flow., ie a couple of
degrees cooler, the oil will, in fact, NOT FLOW.
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 How Do we Know that the Lubricant
is Performing as Required?
• Check the Chemical Properties
eg Anti-Oxidant Level (RULER) TBN and/or TAN and
Nitration and Oxidation Values
• Check Contamination Level
eg Water Content, Dirt Ingress , Particle Count, Glycol
Content and Fuel Dilution
• Check the Physical Properties
eg Viscosity and Viscosity Index
• Check Extent of Wear Metal Production
eg Iron, Copper, Lead, PQ Index etc..
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 Lubrication of a Compartment
requires an Oil with Additives to:
• Prevent wear • Clean & Disperse
(For engines)
• Counter Oxidation • inhibit corrosion
• Reduce Foaming • Keep the Oil Fluid

AND filtration to

KEEP THE OIL CLEAN

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 Although the lubricant is still considered the
cheapest replaceable item in large plant and
equipment, the oil has a finite cost, both to
purchase as well as dispose of, and to obtain full
value, the oil should be changed out only when it
can no longer effectively protect the oil and the
moving surfaces. The additive in the oil
formulation that provides this protection is the
ANTI-OXIDANT which can be measured using
RULER.
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 RULER Oil Condition Monitoring

• R emaining
• U seful
• L ife
• E valuation
• R outine

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 RULER Oil Condition Monitoring

Definition:
Remaining Useful Life of lubricants
= Length of equipment operating
time from the time a lubricant is
sampled based on anti-oxidant level
readings of a standard for the lubricant

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A small amount of the lubricant is tested in a special
vial by applying a low voltage through the
instrument probe . The result is compared to a
sample of unused oil (100%RUL- Remaining Useful Life )
and the % RUL value of the used oil is determined.

Trending the %RUL over time enables predictions of

Anti-Oxidant additive depletion to a point where it
cannot effectively protect the lubricant and the
equipment (usually 30% RUL). At this point
decisions can be made about changing out the
lubricant or re-dosing the lubricant with anti-oxidant
additive.

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 RULER Oil Condition Monitoring
Remaining Useful Life dependent on:
ANTI-OXIDANT OPERATING
TYPE CYCLE

%RUL
PRESENCE OF BASE OIL
METALS &/OR OXIDATION
WATER STABILITY

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 RULER Oil Condition Monitoring
RULER & Oil Degradation:
R.U.L.
Anti-Oxidant Viscosity
Depletion
100%
Critical
Point
50%
TAN

0%
Operating Time (hours; months; km …)
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 Critical
Point
In the service life of a lubricant the anti-oxidant (AO) additive
incorporated into the formula preferentially depletes until a stage
is reached where there is insufficient AO left to FULLY protect the
base oil(s) and the equipment. This point is referred to as the
CRITICAL POINT and is typically set at 30% RUL. Continued use
of the lubricant after the critical point has been reached will result
in escalating values for Total Acid Number (TAN) and viscosity
due to oil oxidation. Oil oxidation is evidenced by formation of
lacquers/varnishes and gums which renders the oil unsuitable for
redosing with additives.
Redosing with AO or changing out of the lubricant prior to
achieving the critical point will enhance the longevity of oil, if
redosing, and the equipment making RULER a true maintenance

PRO-ACTIVE CONDITION MONITORING TOOL

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 What are RULER APPLICATIONS ?
 Petrol engine oil
 Diesel engine oil
 Aircraft engine oils
 Steam turbine oils
 Gas turbine oils
 Hydraulic oils
 Compressor lubricants
 Transmission fluids
 Greases
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 RULER Oil Condition Monitoring
What is RULER METHOD ?
LUB OIL/FLUID SOLVENT

EXTRACTION OF ADDITIVES
OIL PHASE ADDITIVES
Substrate +oil in solution
settles down to electrolytic cell
bottom of vial
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 RULER Oil Condition Monitoring

auxiliary working electrode

electrode
Cyclic Voltage reference
0 - 1,5 V electrode
11 / 17 sec.

RULER Probe

Solvent + Additives
mixture+
RULER Sand +
Oil & Insolubles CE320 INSTRUMENT

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 Detection & Measurement
of Oxidation Inhibitors
Linear Ramp (Voltage)
Compound “B”
Phenyl - -naphthylamine
Current milli-amps

NH

Compound “A”
Compound “C”
ZDDP
BHT
OH
(CH3)3 C C(CH3)3

Solution Blank CH3

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 RULER Oil Condition Monitoring
C QUALITATIVE +
QUANTITATIVE – PEAK HEIGHT &
U
QUANTITATIVE – PEAK AREA
ADDITIVE B
R
ADDITIVE A
R
E
N
T V O L T A G E
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 RULER Oil Condition Monitoring

S
T
A
N
D
A
R
D
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 RULER Oil Condition Monitoring

T
E
S
T

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 RULER Oil Condition Monitoring

RULER TRENDING:
Successive samples measurement
antioxidant additive depletion rate

PROACTIVE FLUID & MACHINE

CONDITION MONITORING
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 RULER Oil Condition Monitoring

T
E 500 hours 2000 hours 3000 hours 3500 hours

S
T
S

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 RULER Oil Condition Monitoring

T
R
E
N
D
I
N
G
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 RULER Oil Condition Monitoring

CE320 RULER IS A VALUABLE TOOL FOR

:

 Used oil condition monitoring

 Incoming lubricant batch control
 Additive replenishment/top-up detection
 Detecting abnormally operating equipment
 Detecting abnormally operating equipment
 Predicting & extending oil change intervals

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 RULER augments standard analysis methods
Diagnostic oil analysis programs are a “jigsaw” puzzle of
many pieces in which all pieces are required to give a full
picture of oil and equipment condition. RULER supplies the vital
piece which can can tell how long the lubricant can last and
how much protection it can supply to the lubricated component.

 RULER technology has been investigated

and is now included in ASTM list of methods
as ASTM D6810-02 and ASTM D6971-04

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 RULER Oil Condition Monitoring

FRESH Oil replenishment

RUL (%) CHANGE in operating conditions

NORMAL Trending

Operating Time

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 ANTI-OXIDANT DEPLETION can:
be a reflection of normal wear
– rate would generally be linear with the slope of the rate line indicating the severity of
the wear.

% SOME
WEAR
R
U
MORE
L
WEAR
SEVERE
WEAR

TIME

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 ANTI-OXIDANT DEPLETION can:
be a reflection of changing wear
– rate would increase indicating change in wear. Change may be due to:
INGRESS OF EXTERNAL SOLID CONTAMINATION e.g dirt
INGRESS OF EXTERNAL LIQUID CONTAMINATION e.g. moisture
CHANGE IN LOAD
CHANGE IN OPERATOR
USE OF A LIGHTER VISCOSITY OR DIFFERENT OIL FOR TOP-UP OR CHANGE
PRODUCTION OF WEAR PRODUCING PARTICLES IN SYSTEM
RATE
% CHANGE
POINT
R
U
L

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 FILTRATION
One of the major factors affecting the useable life of a lubricant is its
cleanliness. Accordingly it is appropriate to provide a few details of
filtration and the various classes of cleanliness commonly encountered

Filtration is the physical or

mechanical process of
retention or “capture” of
particles in a fluid by the
passage of the fluid through
a porous filter medium.
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 ROLLER 3-5 MICRON
.

OIL FILM
FRICTIONAL AREA
INNER
RACE
The lubricant is separating loaded surfaces by
means of a fluid film of between 3 and 5 micron in
thickness.
The next slide gives a comparison of micron sizes

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COMPARATIVE SIZES IN MICRONS

GRAIN OF SALT 120

HUMAN HAIR 80
FLOOR DUST 40
WHITE BLOOD CELLS 20
TALCUM POWDER 10
BACTERIA 3
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Solids of any size are detrimental to the operational efficiency
of lubricated components leading to wear of moving surfaces
and degradation of the lubricant by depletion of anti-oxidants
and then oxidation of the base oil.
Having looked at the monitoring of the properties of the
lubricant and assessing the lubricant’s condition, particularly
the RULER determinations of active anti-oxidant content, it is
just as wise to inspect the cleanliness of the lubricant to
determine the effectiveness of the filtration in the system.
The PODS instrument depicted in the following slide is typical
of the affordable particle counting technology for industry that
makes testing on-site a reality in the same way as RULER.
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May 2005 ABN 78 087 393 020
PODS - PORTABLE OIL DIAGNOSTIC SYSTEM
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 CLASSIFICATION OF
FILTRATION

•MACRO FILTRATION - >2 MICRON IN SIZE

•MICRO FILTRATION - 2 MICRON TO 0.2

MICRON IN SIZE

•ULTRA FILTRATION - < 0.2 MICRON IN SIZE

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 FILTRATION PROCESS

• Gravitational separation from fluid- achieved

by rotational forces applied to the fluid
eg Glacier or Spinner
• Depth retention - direct interception and /
or adsorption
• Surface retention - direct interception and /
or adsorption

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 FILTER RATINGS

ABSOLUTE RATING
Diameter of largest hard spherical
particle permitted to pass

NOMINAL RATING
Based on % of largest particles permitted
to pass

BETA RATING
Ratio of upstream particles of nominated
size with downstream particles

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 BETA RATING
Ratio of upstream particles of nominated size
with downstream particles

BETA RATIO EFFICIENCY

1 0%
2 50 %
20 95 %
50 98 %
100 99 %
Usual
200 99.5 %
specification
1000 99.9 %
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 FILTRATION
All filters will reduce the solid matter contamination to
the appropriate micron size without detriment to the
properties of the lubricant, that is, they cannot remove
the additives from the oil formulations. Even polymers
employed as viscosity index improvers and tackifiers
will pass through the filters as they are dissolved in the
oil base.

A good rule of thumb to use when considering filtration

of oil is

"If It Can Be Removed By Filtration It Shouldn't Be

There".
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SAE AS 4059(c) – Aerospace standard recording
particles counted per 100 ml for
all size ranges from 4 micron to
to greater than70 micron
ISO 4406 (c) International Standard recording
particles counted per ml for
size ranges from >4 micron to
to >14 micron
Condition Monitoring Programmes should include Particle Size Distribution
analysis for Hydraulic and Transmission and Drive systems that incorporate
forced lubrication and filtration to gauge the effectiveness of the filtration.

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 INTERNATIONAL STANDARD 4406(c)
MEASUREMENT RANGE: >4um / >6um / >14um

MORE THAN LESS THAN ISO CODE

5 000 000 particles/ml 10 000 000 particles/ml 30
2 500 000 5 000 000 29
1 300 000 2 500 000 28
640 000 1 300 000 27
320 000 640 000 26
160 000 320 000 25
80 000 160 000 24
40 000 80 000 23
20 000 40 000 22
10 000 20 000 21
5 000 10 000 20
2 500 5 000 19
1 300 2 500 18
640 1 300 17
320 640 16
160 320 15
80 160 14
40 80 13
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 ISO REPORTING
> 4 MICRON / >6 MICRON/ >14 MICRON
INCLUDES INCLUDES INCLUDES
SILT FINE WEAR COARSE WEAR
&/OR DIRT &/OR DIRT &/OR DIRT
+ +
FINE WEAR COARSE WEAR
&/OR DIRT &/OR DIRT
+
COARSE WEAR
&/OR DIRT
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 SAE AS 4059(c) MAXIMUM CONTAMINATION LIMITS (particles/100ml)
Size – ISO 11171
>4um(c) > 6um(c) > 14um(c) >21um(c) >38um(c) >70um(c)
Calibration (Projected
Area Equivalent Diameter)

000 195 76 14 3 1 0
00 390 152 27 5 1 0
0 780 304 54 10 2 0
1 1560 609 109 20 4 1
CLASSES

2 3120 1220 217 39 7 1

3 6250 2430 432 76 13 2
4 12 500 4860 864 152 26 4
5 25 000 9730 1 730 306 53 8
6 50 000 19 500 3 460 612 106 16
7 100 000 38 900 6 920 1 220 212 32
8 200 000 77 900 13 900 2 450 424 64
9 400 000 156 000 27 700 4 900 848 128
10 800 000 311 000 55 400 9 800 1 700 256
11 1 600 000 623 000 111 000 19 600 3 390 512
12 3 200 000 1 250 000 222 000 39 200 6 780 1 020

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May 2005 ABN 78 087 393 020
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MONITORING THE ACTIVE ANTI-OXIDANT
LEVEL AND PARTICULATE
CONTAMINATION LEVEL LETS YOU KNOW
HOW GOOD THE LUBRICANT STILL IS
AS OPPOSED TO
MONITORING WEAR AND OTHER
ABNORMAL VALUES WHICH LETS YOU
KNOW HOW BAD IT HAS BECOME.
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