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Rapid Oil Analysis

TEXACO STAR TREATMENT IS JUST A CALL AWAY


ATLANTA
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LOS ANGELES
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MIDWEST LUBE DIVISION
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A Technical Publication Devoted to the Selection and Use of Lubricants
Published by
Texaco Inc. 2000 Westchester Avenue, White Plains, N.Y. 10650
Officers of Texaco Inc,: John K. McKinley, Chairman and Chief Executive Officer
R G Bdnkman, Vice-President and Treasurer; C. B. Davidson, Secretary.
Officers of Texaco Canada Inc.: J. L, Dunlap, President and Chief Executive Officer;
K. D. Keegan, Vice-President and Treasurer; E. J, Little, Secretary.
Volume 70
Number 2 1984
To request a new subscription, obtain back issues, or to report a change of address (enclose mailing label), please write to:
In the United States:
R. W. Strecker, Texaco Inc., 2000 Westchester Avenue, White Plains, N.Y. 10650
In Canada:
D. E. Presley, Texaco Canada Inc., 90 Wynford Drive, Don Mills, Ontario M3C 1K5 Canada
COPYRIGHTS: The contents of LUBRICATION are copyrighted and cannot be reprinted legally by other publications
without written prior approval from Texaco and then only if the article is quoted exactly and accompanied by the credit
line "Courtesy of Texacos magazine LUBRICATION". Copyright 1984 by Texaco Inc. Copyright under International
Copyright Convention. All rights reserved under Pan American Copyright Convention.
EDITOR: FRANK H. PINCHBECK
PUBLISHER: R. W. STRECKER
RAPID OIL ANALYSIS
R. W. Erickson and W. V. Taylor, Jr.
R
apid analysis of used lubricating oils has
become a major part of maintenance pro-
. grams for many operators of automotive and
industrial equipment? The high cost of parts and
labor, coupled with the cost of downtime for equip-
ment which has been idled by mechanical or lubri-
cant-related failures, provides a strong incentive for
conducting used oil analysis on a regular schedule.
This type of regular analysis can contribute signifi-
cantly to the success of a preventive maintenance
program.
While periodic examination of the condition of
lubricating oils has been recommended by equip-
ment manufacturers for many years, it is only in the
past fifteen years that analysis services have been
widely available. Prior to that time, only the largest
corporations had the in-house facilities to conduct
lubricant analysis, and the services provided by lubri-
cant suppliers were directed primarily toward meet-
ing the needs of major lubricant customers and
responding to customer complaints. A significant
exception was the service provided to owners or
operators of large ships, particularly steam turbine
driven vessels.
2
Those vessels are characterized by
having an extremely large system oil charge, an
operating environment in which water contamination
is often severe, and propulsion systems that are very
expensive to repair or replace.
A major increase in awareness of the value of
lubricant analysis as part of a preventive mainte-
nance program occurred during the Vietnam conflict.
That military operation saw extensive use of helicop-
ters and jet-powered aircraft, both of which are sen-
sitive to mechanical or lubricant-related problems.
The military services determined that mobile labora-
tories were required on-site, and that spectrographic
analyzers to determine wear metals and contami-
nants were a vital part of such installations.
It was logical that the procedures developed for
minimizing the failures of military aircraft would be
recognized by industry as a means of controlling
maintenance costs and of increasing safety. The
commercial airlines were among the first to set up
elaborate laboratories for the analysis of their jet
engine oils. Publicity relating the success of these
efforts in reducing engine failures, and extending the
time interval between major overhauls, soon led to a
demand for commercial laboratories which could
provide analysis service for a variety of used lubri-
cants.
13
LUBRICATION
Today, rapid oil analysis services are available for
the engines of bus and truck fleets, hydraulic sys-
tems of industrial plants, paper machine lubricant
systems, diesel and steam turbine powered ships,
natural gas fueled engines driving pumps and com-
pressors, and nearly the entire spectrum of equip-
ment requiring oil lubrication. The cost of laboratory
analysis can easily be justified when it is part of a
comprehensive preventive maintenance plan
directed toward eliminating or minimizing cata-
strophic failures and extending the useful life of
expensive equipment.
Rapid oil analysis is not specifically intended as a
means of determining oil drain intervals or of provid-
ing a basis for selecting a particular type of lubricant.
These are decisions which should be made by the
maintenance supervisor or shop foreman after
reviewing the equipment manufacturers recommen-
dations and consulting with the lubricant engineer.
Analytical data will be most effectively used by the
maintenance supervisor in scheduling preventive
inspections of the machinery and confirming suit-
ability of the lubricant for further service between oil
drain intervals. If a decision is made to extend the
periods between oil changes, regular periodic analy-
ses should be conducted and a record of operating
hours, oil consumption, and filter changes should be
maintained. A history of spectrometric metal levels
and chemical analysis results is particularly impor-
tant when lubricant service periods are increased.
SAMPLE COLLECTION AND
SUBMITTAL
The first step in a rapid oil analysis program is to
obtain a sample which is representative of the lubri-
cant in the system. The importance of this step can-
not be overemphasized because the interpretation of
results of the laboratory analyses can only be as valid
as the sample is representative. For example, water
and sediment observed in a sample obtained from a
low point in a system and where the oil is stagnant
are, in all likelihood, meaningless observations. Simi-
larly, an analysis on a truly representative sample of
oil drawn into a dirty container is equally mean-
ingless.
For rapid oil analysis results to be of value, sam-
ples must be drawn into clean containers from a
flowing system at operating temperature. Hand
pumps are available which can withdraw a sample
from the lubricant sump or crankcase directly into a
sample bottle. The oil does not get into the pump
body, so it is necessary to clean only the flexible
sample tube and replace the sample bottle between
successive samples. Alternatively, samples can be
taken during an oil drain soon after operation while
the equipment is still at service temperature.
To avoid mixups, a sample should be labeled
immediately. A description of the equipment and type
of service, identification of the lubricant used, date of
sampling, time since last oil change, and makeup
TABLE I
BASIC TEST SCHEDULE FOR USED ENGINE OILS
Enqine Type
ASTM Natural Automotive Marine
Property Method Gasoline Gas Diesel Diesel
Appearance -- X X X X
Odor -- X X X X
Water (Crackle) -- X X X X
(Distillation) D 95 (a) (a) (a) (a)
Viscosity, (~ 40C D 445 X X X X
Fuel Dilution
(Distillation)
D 322
(b) -- -- --
(Gas Chromatography)
D 3524 -- -- (b) (c)
Fuel Soot
-- -- -- (d) --
Pentane Insolubles D 893 -- -- --
X
Ash Content D 874 -- -- -- X
Emission Spectrometry -- X X X X
Glycol Content D 2982
(e) (e) (e)
--
Infrared Spectrometry ~ --
(f)
-- --
Neutralization No. D 664 -- -- (g) --
Total Base Number D 2896 -- -- -- X
(a) Determined only if crackle test is positive.
(b) Determined if viscosity is low or if fuel dilution is critical.
(c) Estimated from flash point.
(d) Determined if viscosity is high or if fuel soot is critical.
(e) Determined if boron and sodium are present in emission spectrometry.
(f) For determination of oxidation and/or nitration.
(g) Determined only for critical engines or if additive level is low.
14
LUBRICATION
rate, if applicable, should be recorded and submitted
with the sample. The sample should then be deliv-
ered to the laboratory as rapidly as possible. The
following discussion will describe procedures which
are used by the oil analysis laboratory, and the way
that the results of those procedures can be inter-
preted in evaluating the condition of the equipment
and the lubricant.
TEST DESCRIPTIONS AND
SIGNIFICANCE
The laboratory analyst will select tests to be run on
a used oil sample on the basis of the type and grade
of oil, the equipment it was taken from, and often a
sensory examination of the sample.
3,~,S,s
A list of
common analytical methods applied to used engine
lubricating oils is given in Table I. Analytical methods
frequently applied to used industrial lubricating oils
are shown in Table II. While a detailed description of
the test methods is beyond the scope of this article, a
brief discussion of each method is included to assist
in defining the significance of the test. A more
detailed description of the methods is contained in
the 1984 Annual Book of ASTM Standards, Volumes
5.01, 5.02, 5.03, and 14.02.
7
Sensory Inspections
Although appearance and odor are subjective
inspections, an experienced observer can recognize
whether the sample is typical of the product and type
of service. Evidence of contamination or deteriora-
tion can often be detected by sensory examination.
Diesel engine oils, for example, quickly develop a
black color due to dispersed fuel soot. Engine oils in
short service or those exhibiting little or no degrada-
tion have a bland or an additive odor, similar to that of
the unused oil. Those with longer service under
favorable operating conditions have a normal "used"
odor. The presence of significant amounts of fuel in
an engine crankcase sample can be detected by
odor and possibly by a thinning of consistency, while
an oil which has undergone extended service or
severe operating conditions may have a burnt odor
and be noticeably thickened.
Appearance and odor are particularly significant in
the examination of compressor, turbine, and hydrau-
lic oils. In normal service these oils are bright and
clear, and have a bland odor. While all petroleum oils
may contain some dissolved water, the presence of
even a small amount of suspended "free" water will
cause the oil to be hazy, and a larger amount of water
will result in a cloudy appearance. These conditions
are shown in Figure 1. The oil to the left is dry and
clear and the reference line behind the bottle is
sharply defined. The middle bottle, which contains
200 parts per million (ppm) water, is hazy while the
bottle on the right with 400 ppm water is so cloudy
that the line can barely be seen. Greater quantities of
water will coalesce and free water droplets will be
seen at the bottom of the container. Water separation
properties of an oil gradually deteriorate in service
and when contaminants are present.
A significant darkening from the normal color is an
indication of contamination or oxidation, and these
conditions can often be confirmed by characteristic
odors. A sharp or burnt odor is indicative of severe
oxidation, and certain chemical contaminants can be
indicated by odors described by terms such as fuel,
chlorinated solvent, or sour gas, i.e., a gas containing
sulfur compounds.* The analyst will normally call for
additional tests to confirm these indications.
*Care should be taken in checking the odor of used oil
samples as they may contain irritating material. For exam-
ple, compressor oil used in a commercial refrigeration sys-
tem may contain ammonia which can have a severe effect
on the respiratory tract.
TABLE II
BASIC TEST SCHEDULE FOR USED INDUSTRIAL OILS
ASTM Compressor Gear Turbine Hydraulic
Property Method Oil Oil Oil Oil
Appearance -- X X X X
Odor -- (a) X X X
Water (Crackle) -- -- X -- --
(Karl Fischer) D 1744 (b) X (b) (b)
Viscosity, (~ 40 D 445 X -- X X
(/~100 D 445 -- X -- --
Toluene Insolubles D 893 -- X -- --
Emission Spectrometry
-- X X X X
Infrared Spectrometry
-- X -- X X
Neutralization No. D 664
(c) (c) (c) (c)
Particle Count F 661
(d) -- (d) (d)
(a) Use caution when examining oils from ammonia or other noxious gas systems.
(b)
Determined if sample is hazy or if water content is critical.
(c) Determined when sensory or infrared methods indicate need.
(d)
Determined if cleanliness is a major criterion or to meet equipment manufacturers recommendations.
15
LUBRICATION
Figure 1--Various degrees of water contamination in a clear petroleum product.
Examination of the interior of the sample container
may reveal the presence of dirt granules, paint chips
or flakes of metal. Microscopic examination and/or
X-ray diffraction analyses often lead to the identifica-
tion of such particles.
Chemical and Physical Tests
Water Content
The crackle test is the most useful screening test
for the presence of water in an oil. The test can be
conducted by placing a few drops of oil in a small cup
made from aluminum foil and heating rapidly over a
small flame or on a hot plate, as shown in Figure 2. An
alternative method involves the use of a hot electric
soldering iron which is immersed in the oil, as shown
Figure 2~rackle test for water using a small aluminum foil cup on a
hot plate.
in Figure 3. In these methods an audible crackling
sound may be indicative of as little as 0.1 per cent free
water.
When a positive crackle test is observed, a quan-
titative test for water by distillation (ASTM D 95)
Karl Fischer (ASTM D 1744) should be made. The
apparatus used for determining water by ASTM D 95
Figure 3~Crackle test for water using a hot soldering iron.
16
LUBRICATION
is shown in Figure 4. In this test, a measured quantity
of oil is dissolved in a water-immiscible hydrocarbon
solvent such as xylene and heated in a distillation
flask. The boiling solvent drives the water vapor along
with its own vapor upward into a condenser where the
vapors condense and fall into a calibrated trap. The
heavier water settles to the bottom of the trap where
its volume can be measured, while the solvent over-
flows back to the distillation flask.
dissolved water concentrations in the parts per mil-
lion range, but it is normally used only for relatively
clean industrial oils or unused engine oils, since
combustion residues in used engine oils may cause
fouling of the sensitive electrodes in the apparatus.
The presence of water in a lubricant system is
indicative of contamination through leaking seals,
blowby of combustion gases, coolant seepage, or
improper storage or application of the oil. Free water
is a prime cause of rusting, sludging, and impaired
lubrication, so the source of water should be located
and eliminated as soon as possible.
Figure 4---The apparatus for determining water in petroleum prod-
ucts, ASTM D 95.
In the Karl Fischer method, the water present in a
small weighed sample of oil is titrated with a complex
solution of iodine and sulfur dioxide in pyridine, and
the water concentration is calculated from the volume
of iodine solution consumed and a factor for the
milligrams of water equivalent to a millilitre of the
iodine solution*. Many laboratories are now
equipped with an automated apparatus in which the
iodine solution is generated coulometrically and the
water concentration is calculated and displayed by
an electronic readout device. One such instrument is
shown in Figure 5. The Karl Fischer method has the
advantage of being able to determine both free and
*The solution is called a titrant and chemical procedures of
this type are commonly referred to as titrations.
Figure 5--An automated apparatus for determining water in
petroleum products using the Karl Fischer method.
Viscosity
Viscosity is the most important single physical
property of a lubricating oil. It is a measure of
resistance to flow resulting from internal friction of the
molecules moving past each other under stress. It is
the sole property of a lubricant that influences the oil
film thickness between moving parts and hence influ-
ences wear. An oil of inadequate viscosity will not
form films sufficiently thick to prevent or minimize
wear, whereas an oil of unduly high viscosity will
generate unnecessary heat and waste energy. The
ease of starting an automotive engine on a frigid
winter morning depends largely on the viscosity of
the crankcase oil. Viscosity is also an essential con-
sideration in the proper functioning of hydraulic sys-
tems, automatic transmissions, and shock absorb-
ers.
8
Temperature is the factor which has the greatest
effect on viscosity, and laboratory determinations
must be made under precisely controlled tem-
perature conditions. While several methods for deter-
mination of viscosity are available, the kinematic
method (ASTM D 445) is the one most commonly
used for lubricating oils? In the kinematic method, a
measured volume of oil is passed through a capillary
tube and the time of passage is precisely deter-
mined. The viscosity, designated in centistokes (cSt),
is calculated from the time and a calibration factor for
17
LUBRICATION
Figure 6~A constant-temperature bath containing several glass
capillary kinematic viscometers, ASTM D 445.
the capillary used. Figure 6 illustrates an apparatus
for the determination of viscosity.
The analyst compares the viscosity determined for
the used oil sample against the standard value for an
unused oil of that grade. A deviation of less than
10 per cent from the mid-point of the ISO viscosity
range of the unused oil is usually considered normal.
Greater deviations from the standard value may indi-
cate use of the wrong grade or a mixture of oils,
thickening due to oxidation or fuel soot contamina-
tion, or thinning due to fuel dilution. In the case of fuel
dilution, the quantity of No. 2 diesel fuel in a crank-
case oil sample can be estimated from the reduction
in viscosity as shown in Figure 7. This value can be
confirmed by a gas chromatographic determina-
tion.
1
Fuel dilution in gasoline engine oils is determined
by steam distillation (ASTM Method D 322). In this
test measured volumes of used crankcase oil and
water are placed in a flask and distilled. The distillate
(gasoline and water) is collected in a graduated
receiver as illustrated in Figure 8. The gasoline floats
on the water in the receiver, its volume is measured,
and the percentage gasoline in the oil is calculated.
The presence of 5 per cent fuel diluent can result in
a viscosity reduction equal to approximately one
SAE grade. This is normally taken as an indication of
significant fuel system problems and the need for an
oil drain. When an oil is diluted excessively, an ade-
quate hydrodynamic lubricating film is not main-
tained between the moving parts and metal-to-metal
contact follows, resulting in increased wear and pos-
sible bearing failure. The presence of fuel soot or
oxidative degradation of the oil can result in an
increase in viscosity, which in turn can mask the
presence of fuel diluent. When fuel soot is greater
than 4 per cent with no increase in viscosity, fuel
dilution should be determined.
Deviations in the viscosity of in-service industrial
lubricants are often the result of using the wrong
viscosity grade of oil as makeup to the system. Other
causes of viscosity changes are leakage from an
adjacent compartment or dilution by a process fluid
such as is sometimes encountered in compressor
service when oil soluble gases are being com-
pressed.
I I I I
I
4
6 8 I0 12
DIESEL FUEL DILUTION,
Figure 7--Viscosity-dilution curves for four grades of crankcase lubricants.
18
LUBRICATION
the soot content. Reference spots made by oil with
known soot content assist in estimating the soot con-
tent of the used oil sample.
For dark or cloudy high viscosity oils, such as gear
oils, a determination of particulate contaminants, as
well as water content, can be made by centrifugation
in a cone-shaped tube (ASTM D 893). A measured
portion (25 or 50 millilitres) of the oil is placed in the
tube, and an appropriate solvent (pentane or
toluene) is added up to the 100 ml mark. After thor-
oughly mixing the oil and solvent, the tube is placed
in a centrifuge. Regardless of the solvent used, water
and sediment become concentrated in the bottom of
the centrifuge tube and can be measured by refer-
ence to the graduated marks on the tube.
In this method, if pentane is used as the solvent,
wear metal particles and foreign contaminants such
as dirt and water are collected in the tip of the tube
after centrifuging. Oil oxidation products tend to con-
centrate at the interface between the water and oil
phases. If toluene is used as the solvent, the cen-
trifuge method will show the wear metals and foreign
contaminants along with the water, while the oil
oxidation products will normally be dissolved. If par-
ticulate sediment is present it can be recovered from
the tube for further characterization.
Figure 8---The apparatus for determining gasoline dilution in crank-
case oils, ASTM D 322.
Insolubles or Sediment
There are several methods for measuring insolu-
bles in an oil. These include filtration, centrifugation,
blotter spot tests, and optical methods. The most
common insoluble contaminant in diesel engine oils
is fuel soot, since diesel fuel combustion is by nature
more sooty than gasoline or natural gas combustion.
The formation of soot is more severe under certain
abnormal operating conditions, such as overfueling
or a restricted air intake.
A simple method for the estimation of fuel soot
content in a diesel engine oil is the optical procedure
in which a very small, measured amount of used oil is
placed in a clear tall-form glass inspection bottle filled
with toluene, shaken, and visually compared with
standards prepared using oils with known fuel soot
content. This method compares favorably with the
blotter spot method. In the latter method, several
drops of oil are placed on a piece of blotter paper and
allowed to sit for several hours until the oil diffusion is
complete. As the oil spot diffuses from the point of
application, the insoluble fuel soot remains at the
center as a dark spot with an intensity proportional to
Emission Spectrographic Analysis
The identification of inorganic contaminants, as
well as the metallo-organic oil additive elements, is
accomplished by use of the emission spectrometer.
The sample excitation stand of an emission spec-
trometer for oil analysis is shown in Figure 9. In this
instrument a film of oil is carried on a rotating graphite
wheel to a sharpened graphite rod electrode where it
is subjected to a high voltage arc. The metallic ele-
ments in the sample are excited by the energy of the
arc and each emits a characteristic spectrum of light
which is collected and measured by a series of pho-
tomultiplier tubes. The light intensities are converted
to element concentrations by a computer and printed
for examination by the analyst.
Emission spectrographic analysis is a powerful
tool for detecting wear metal levels. The significance
of wear metal values varies with the make and model
of the equipment and with the type of service, includ-
ing working environment, drain interval, filter change
interval, etc. Metal concentrations are normally low
and increase slowly with longer operating periods. A
sudden upward change in the concentration of any
metallic element, such as copper, lead, or iron, which
is present in the lubricant-wetted parts of the equip-
ment suggests an increased wear rate, and possibly
abnormal operating conditions.
The presence of silicon combined with a higher
level of wear metals signifies the entry of dirt into the
system. Combinations of certain trace elements
offen provide clues to the components undergoing
wear. By reference to literature supplied by the equip-
19
LUBRICATION
Figure 9---An emission spectrometer. The oil sample excitation stared is shown in the inset.
ment manufacturers and his own experience, the
analyst can often detect evidence of incipient failure
and alert the customer before a severe mechanical
problem occurs. Trends in concentrations of metals
observed for several successive samples from the
same equipment are particularly useful in diagnosing
possible adverse conditions or operating problems.
While several modern crankcase lubricant formu-
lations use boron-containing additives, the presence
of boron, usually along with sodium, in the spec-
trographic analysis may also suggest the presence
of antifreeze, indicative of a glycol coolant leak. A
chemical test for ethylene glycol will usually be run to
confirm the presence of the antifreeze. Glycol can
cause thickening and sludge formation, and may
attack certain alloy bearings when present in a crank-
case oil at levels over 0.1 per cent. When glycol is
present at that level, the oil should be drained and the
source of coolant entry should be found and cor-
rected.
Infrared Analysis
Infrared (IR) spectrometry is another powerful
technique for oil analysis which can detect organic
contaminants, water, and oil degradation products at
low levels. IR provides a simple, rapid method for
establishing (1) general lubricant type (paraffinic
naphthenic) (2) the presence and often the quantity
of certain contaminants, such as alcohols, polar sol-
vents, and free water (but not normally dissolved
moisture), (3) the depletion or degradation of additive
components, such as antioxidants, and (4) the pres-
ence of lubricant degradation products resulting from
oxidation or nitration.
In normal practice a double-beam IR spectrometer
is employed in the differential mode. The used oil is
placed in a cell in the sample side of the instrument
and an unused reference oil is placed in the reference
cell. The instrument traces a curve which represents
the difference between the sample and the refer-
ence, and clearly defines those spectral regions
characteristic of the organic contaminant or the oil
degradation products. A newer procedure for differ-
ential infrared (DIR) spectrometry utilizes a Fourier
Transform infrared (FT/IR) analyzer in which the
sample is placed in a single-beam cell and the spec-
trcm is compared to that of a reference oil spectrum,
which has been stored in a computer. A photograph
of the F-F/IR screen display (in absorbance mode)
during DIR analysis of a used gas engine oil is shown
in Figure 10. Use of the computer assisted FT/IR
offers convenience as well as greater sensitivity
20
LUBRICATION
Figure IO--A differential infrared spectrometer screen display showing absorbance versus wavenumber for a used gas engine oil. The
spectrometer is shown immediately above.
A particularly important application of DIR analysis
is in the testing of oils from natural gas fueled
engines." In these engines the combustion process
frequently promotes the fixation of nitrogen by com-
bining nitrogen and oxygen from the combustion air.
Nitrogen fixation is most severe in naturally aspirated
four-cycle gas engines and with air/fuel ratios char-
acterized by 0.5 to 5.5 per cent excess oxygen as
measured in the exhaust air. The reaction of these
fixed nitrogen compounds with lubricating oil forms
acidic materials which ultimately become oil insolu-
ble, accelerating the formation of varnish and sludge,
and promoting further oxidation and thickening of the
oil.
DIR analysis is used to quantify the nitration prod-
ucts, provide a basis for recommending correction of
adverse engine operating conditions, and suggest
an oil change before deposit formation becomes a
problem. Knowing the characteristic DIR patterns of
used oils from various engines and by maintaining a
record of changes in absorbance ratios, it is often
possible to detect one or more of the following seven
conditions:
1. Hot spots on pistons or cylinder walls.
2.
High crankcase oil temperatures (possible faulty
cooling).
3.
Improper air/fuel ratio.
4. Improper spark timing.
5.
High rates of combustion blow-by.
6.
Faulty operation of crankcase ventilating sys-
tem.
7. Engine overload.
21
LUBRICATION
I00
9o
oc 80
70
4400
WATER AND/OR GLYCOL
ACID CARBONYL (OXIDATION)
NITRO COMPOUNDS
(NITRATION)
NITRATE ESTER
(NITRATION)
I I I I
3200 2000 1400 800
WAVENUMBERS, CM-I
Figure 11--A typical differential infrared curve in the transmittance mode.
A typical DIR curve, in the more familiar transmit-
tance mode, showing evidence of nitration, oxida-
tion, and water and/or glycol contamination is shown
in Figure 11.
Neutralization Number
With the exception of heavy duty engine oils, which
characteristically display a fairly high degree of
alkalinity imparted by their additive components,
most lubricating oils are essentially neutral. That is to
say, they do not contain acidic or alkaline compounds
and are analogous to an aqueous solution having a
pH of 7. Strictly speaking, a lubricating oil can not
have apH since the term is defined by reference to
the hydrogen ion concentration of a water solution.
However, pH is used for convenience to indicate the
acidity or alkalinity of an oil in a non-aqueous solvent
when being tested for neutralization number. Values
of pH higher than 7 signify alkalinity, while values
below 7 reflect acidity. Acidity can result from
oxidative degradation of an oil due to overextended
service intervals or abnormal operation. ApH less
than 4 denotes the presence of strong, and probably
corrosive, acids.
Neutralization number is defined as the milligrams
of potassium hydroxide required to neutralize the
acidity in one gram of oil. The alkalinity of an oil is
defined as the quantity of hydrochloric acid,
expressed in terms of the equivalent number of mili-
grams of potassium hydroxide, to neutralize one
gram of oil. Titration (reaction of the dissolved oil
sample with a standardized solution of either acid or
base) is used to determine the neutralization number
of an oil. Results can be expressed in terms of total
base number (TBN), total acid number (TAN),
strong acid number (SAN). Methods in common use
for determining the neutralization numbers of oils
include: ASTM D 664, an electrometric titration using
a recording potentiometer for determination of TBN,
TAN, SAN, and initial pH; ASTM D 974, a colorimetric
titration for determining TAN; and ASTM D 2896, an
electrometric titration for TBN using perchloric acid in
glacial acetic acid as titrant.
22
LUBRICATION
Figure 12--Particle count determinations are made in this automated apparatus.
TBN is a measure of the alkaline or basic compo-
nents of an engine oil. Alkalinity is imparted to the oil
by the additive components, and the level of alkalinity
of an unused oil is characteristic of the type of service
for which the oil is designed. Engine oils for moderate
service such as automotive or light truck operation
have relatively low levels of alkalinity. The alkalinity
levels of oils for engines in heavy construction equip-
ment are in an intermediate range. Oils designed for
extended operation under severe conditions, such as
large slow-speed diesel engines operating with a
high sulfur content fuel oil, have a high alkalinity. In
order to avoid corrosion of oil-wetted parts of the
system, engine oils must be replaced when their TBN
falls below a prescribed level.
Particle Count
Modern high capacity turbine systems, the sophis-
ticated hydraulic systems of automated machine
tools, and newer paper machine circulating systems
have placed a new demand on the oil analysis labo-
ratory. The detection and quantitative measurement
of particulate matter in the lubricant is of great con-
cern, since several major equipment manufacturers
recommend fine filtration of the oil. Regular periodic
determination of particle count is recommended by
these manufacturers as part of a used oil analysis
program.
There are several instruments available for making
particle counts on lubricating oils. The measurement
principle is either a photometric or an electrical
resistivity measurement while the oil is passed
through a small orifice. In one widely used instru-
ment, shown in Figure 12, a fixed volume of the oil
sample is pumped by air pressure through the mea-
suring orifice at a fixed flow rate while a collimated
beam of light is passed across the orifice at right
angles. The beam of light is attenuated by the parti-
cles before reaching the photodiode detector and the
reduction in light intensity is proportional to the area
23
LUBRICATION
of the particle divided by the area of the detector
window. The results are read from a series of six
electronic counters which have accumulated the
results during the counting period. These results are
then normalized and expressed as the number of
particles in each of five size ranges per 100 millilitres
of sample.
The significance of a particle count determination
is established when the values for a used oil are
compared with criteria defined by the equipment
manufacturer. Particle size ranges in microns
(micrometres) that are often used in defining lubricat-
ing oil cleanliness are: 5 to 10, 10 to 25, 25 to 50, 50 to
100, and over 100.
SUMMARY
Rapid analysis of used lubricating oil can be a
significant factor in establishing a preventive mainte-
nance program for automotive and industrial equip-
ment. Samples are taken from the operating equip-
ment according to an established schedule based on
hours of operation or miles of service, or by calendar
period for continuously operating units. The samples
should be forwarded to the laboratory promptly, and
testing should be completed in a timely manner. Lab-
oratory specialists select appropriate tests from
those outlined above on the basis of the type and
model of the equipment and the service conditions.
The shop foreman or maintenance supervisor should
be alerted promptly in the event that analysis reveals
a condition which could lead to equipment failure or
require prompt corrective action. While it can not
reveal every bearing, gear or system component
problem, rapid used oil analysis, with intelligent,
experienced interpretation of the test results, can
make a significant contribution to a well-planned pre-
ventive maintenance program.
REFERENCES
1.
Steenbergen, J.E., "Comprehensive Lube Oil Analysis
Programs: A Cost-Effective Preventive Maintenance
Tool," LUBRICATION ENGINEERING, 34, pp 625-628,
1978.
2. Cashin, R.E, "Marine Turbine and Diesel Engine Oil
Analysis," LUBRICATION, Vol. 56, No. 3, 1970.
3. Snook, W.A., "Used Engine Oil Analysis," LUBRICA-
TION, Vol. 54, No. 9, 1968.
4. Tarbell, L.E., "Analysis of Used Refrigeration Com-
pressor Lubricants," LUBRICATION, VoI. 57, No. 1,
1971.
5. Vail, O.D., "Used Compressor Oil Analysis," LUBRICA-
TION, Vol. 63, No. 3, 1977.
6. Young, C.H., "Used Hydraulic Oil Anlaysis," LUBRICA-
TION, Vol. 63, No. 4, 1977.
7. American Society for Testing and Materials, Phila-
delphia, PA, 1984.
8. Rein, S.W., "Viscosity-I," LUBRICATION, Vol. 64, No. 1,
1978.
9.
Rein, S.W., "Viscosity--II," LUBRICATION, Vol. 64, No.
2, 1978.
10. Bauccio, M.L., "Efficient Analysis of Used Lubricating
Oil Using Gas Chromatography," LUBRICATION
ENGINEERING, 38, pp 549-556, 1982.
11. "Gas Engines," LUBRICATION, VoI. 53, No .1, 1967.
24
TEXCHEK
RAPID OIL ANALYSIS