This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles

for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

Designation: E2412 − 23a

Standard Practice for

Condition Monitoring of In-Service Lubricants by Trend
Analysis Using Fourier Transform Infrared (FT-IR)
Spectrometry1
This standard is issued under the fixed designation E2412; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.

1. Scope* 1.3 Spectra and distribution profiles presented herein are for
illustrative purposes only and are not to be construed as
1.1 This practice covers the use of FT-IR in monitoring
representing or establishing lubricant or machinery guidelines.
additive depletion, contaminant buildup and base stock degra-
dation in machinery lubricants, hydraulic fluids and other fluids 1.4 This practice is designed as a fast, simple spectroscopic
used in normal machinery operation. Contaminants monitored check for condition monitoring of in-service lubricants and can
include water, soot, ethylene glycol, fuels and incorrect oil. be used to assist in the determination of general machinery
Oxidation, nitration and sulfonation of base stocks are moni- health through measurement of properties observable in the
tored as evidence of degradation. The objective of this moni- mid-infrared spectrum such as water, oil oxidation, and others
toring activity is to diagnose the operational condition of the as noted in 1.1. The infrared data generated by this practice is
machine based on fault conditions observed in the oil. Mea- typically used in conjunction with other testing methods. For
surement and data interpretation parameters are presented to example, infrared spectroscopy cannot determine wear metal
allow operators of different FT-IR spectrometers to compare levels or any other type of elemental analysis. The practice as
results by employing the same techniques. presented is not intended for the prediction of lubricant
1.2 This practice is based on trending and distribution physical properties (for example, viscosity, total base number,
response analysis from mid-infrared absorption measurements. total acid number, etc.). This practice is designed for monitor-
While calibration to generate physical concentration units may ing in-service lubricants and can aid in the determination of
be possible, it is unnecessary or impractical in many cases. general machinery health and is not designed for the analysis of
Warning or alarm limits (the point where maintenance action lubricant composition, lubricant performance or additive pack-
on a machine being monitored is recommended or required) age formulations.
can be determined through statistical analysis, history of the
1.5 The values stated in SI units are to be regarded as
same or similar equipment, round robin tests or other methods
standard. No other units of measurement are included in this
in conjunction with correlation to equipment performance.
standard.
These warning or alarm limits can be a fixed maximum or
minimum value for comparison to a single measurement or can 1.6 This standard does not purport to address all of the
also be based on a rate of change of the response measured safety concerns, if any, associated with its use. It is the
(1).2 This practice describes distributions but does not preclude responsibility of the user of this standard to establish appro-
using rate-of-change warnings and alarms. priate safety, health, and environmental practices and deter-
NOTE 1—It is not the intent of this practice to establish or recommend mine the applicability of regulatory limitations prior to use.
normal, cautionary, warning or alert limits for any machinery. Such limits
should be established in conjunction with advice and guidance from the
1.7 This international standard was developed in accor-
machinery manufacturer and maintenance group. dance with internationally recognized principles on standard-
ization established in the Decision on Principles for the
Development of International Standards, Guides and Recom-
1
mendations issued by the World Trade Organization Technical
This practice is under the jurisdiction of ASTM Committee D02 on Petroleum
Products, Liquid Fuels, and Lubricants and is the direct responsibility of Subcom- Barriers to Trade (TBT) Committee.
mittee D02.96.03 on FTIR Testing Practices and Techniques Related to In-Service
Lubricants.
Current edition approved Nov. 1, 2023. Published November 2023. Originally
approved in 2004. Last previous edition approved in 2023 as E2412 – 23.
DOI:10.1520/E2412-23A.
2
The boldface numbers in parentheses refer to the list of references at the end of
this standard.

*A Summary of Changes section appears at the end of this standard

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 E2412 − 23a
2. Referenced Documents 3.2.2 in-service oil, n—as applied in this practice, a lubri-
2.1 ASTM Standards: 3 cating oil that is present in a machine which has been at
D445 Test Method for Kinematic Viscosity of Transparent operating temperature for at least one hour.
and Opaque Liquids (and Calculation of Dynamic Viscos- [Link] Discussion—Sampling a in-service oil after at least
ity) one hour of operation will allow for the measurement of a base
D2896 Test Method for Base Number of Petroleum Products point for later trend analysis.
by Potentiometric Perchloric Acid Titration [Link] Discussion—Any subsequent addition of lubricant
D4057 Practice for Manual Sampling of Petroleum and (for example, topping off) may change the trending baseline,
Petroleum Products which may lead to erroneous conclusions.
D4175 Terminology Relating to Petroleum Products, Liquid 3.2.3 machinery health, n—a qualitative expression of the
Fuels, and Lubricants operational status of a machine sub-component, component or
D5185 Test Method for Multielement Determination of entire machine, used to communicate maintenance and opera-
Used and Unused Lubricating Oils and Base Oils by tional recommendations or requirements in order to continue
Inductively Coupled Plasma Atomic Emission Spectrom- operation, schedule maintenance or take immediate mainte-
etry (ICP-AES) nance action.
D6304 Test Method for Determination of Water in Petro- 3.2.4 new oil, n—an oil taken from the original manufactur-
leum Products, Lubricating Oils, and Additives by Cou- er’s packaging, prior to being added to machinery.
lometric Karl Fischer Titration 3.2.5 reference oil, n—see new oil.
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D8321 Practice for Development and Validation of Multi-

variate Analyses for Use in Predicting Properties of 3.2.6 trend analysis, n—as applied in this practice, moni-
Petroleum Products, Liquid Fuels, and Lubricants based toring of the level and rate of change over operating time of
on Spectroscopic Measurements measured parameters (1).
E131 Terminology Relating to Molecular Spectroscopy
E168 Practices for General Techniques of Infrared Quanti- 4. Summary of Practice
tative Analysis 4.1 Periodic samples are acquired from the engine or
E1421 Practice for Describing and Measuring Performance machine being monitored. An infrared absorbance spectrum of
of Fourier Transform Mid-Infrared (FT-MIR) Spectrom- the sample is acquired, typically covering the range of
eters: Level Zero and Level One Tests 4000 cm–1 to 550 cm–1, with sufficient signal-to-noise (S/N)
2.2 ISO Standard:4 ratio to measure absorbance areas of interest. Exact data
ISO 13372 Condition monitoring and diagnostics of acquisition parameters will vary depending on instrument
machines—Vocabulary manufacturer but most systems should be able to collect an
absorbance spectrum adequate for most measurements in less
3. Terminology than one minute. Features in the infrared spectrum indicative of
3.1 Definitions: the molecular level components of interest (1, 2) (that is, water,
3.1.1 For definitions of terms used in this practice, refer to fuel, antifreeze, additive, degradation, and so forth) are mea-
Terminology D4175. sured and reported. Condition alerts and alarms can then be
3.1.2 For definitions of terms relating to infrared spectros- triggered according to both the level and the trends from the
copy used in this practice, refer to Terminology E131. monitored system.
3.1.3 Fourier transform infrared (FT-IR) spectrometry, n—a
form of infrared spectrometry in which an interferogram is 5. Significance and Use
obtained; this interferogram is then subjected to a Fourier 5.1 Periodic sampling and analysis of lubricants have long
transform to obtain an amplitude-wavenumber (or wavelength) been used as a means to determine overall machinery health.
spectrum. E131 Atomic emission (AE) and atomic absorption (AA) spectros-
3.2 Definitions of Terms Specific to This Standard: copy are often employed for wear metal analysis (for example,
3.2.1 condition monitoring, n—a field of technical activity Test Method D5185). A number of physical property tests
in which selected physical parameters associated with an complement wear metal analysis and are used to provide
operating machine are periodically or continuously sensed, information on lubricant condition (for example, Test Methods
measured and recorded for the interim purpose of reducing, D445, D2896, and D6304). Molecular analysis of lubricants
analyzing, comparing and displaying the data and information and hydraulic fluids by FT-IR spectroscopy produces direct
so obtained and for the ultimate purpose of using interim result information on molecular species of interest, including
to support decisions related to the operation and maintenance additives, fluid breakdown products and external contaminants,
of the machine (ISO 13372). and thus complements wear metal and other analyses used in a
condition monitoring program (1, 2-6).
3
For referenced ASTM standards, visit the ASTM website, [Link], or
contact ASTM Customer Service at service@[Link]. For Annual Book of ASTM 6. Apparatus
Standards volume information, refer to the standard’s Document Summary page on
6.1 Required Components:
the ASTM website.
4
Available from American National Standards Institute (ANSI), 25 W. 43rd St., 6.1.1 Fourier Transform Infrared Spectrometer (FT-IR)—
4th Floor, New York, NY 10036, [Link] Instrument is configured with a source, beamsplitter and

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 E2412 − 23a
detector to adequately cover the mid-infrared range of 6.2.1 Sample Pumping System—A pumping system capable
4000 cm–1 to 550 cm–1. Most work has been done on systems of transporting the sample to the transmission cell, emptying
using a room temperature deuterated triglycine sulfate (DTGS) the cell and flushing the cell between samples may be used.
detector, air-cooled source and Germanium coating on Potas- Many commercial vendors offer various configurations of
sium Bromide (Ge/KBr) beamsplitter. Alternate source, beam- pump types, tubing and transmission cells for this type of
splitter and detector combinations covering this range are application. It should be noted that non-homogeneity might
commercially available but have not been investigated for use occur if the oils are left standing for too long.
in this practice. Other detectors may be suitable but should be 6.2.2 Filter—The use of a particulate filter (for example,
used with caution. In particular, liquid nitrogen cooled Mer- 0.090 mm) to trap large particles is strongly recommended to
cury Cadmium Telluride (MCT) detectors are known to exhibit prevent cell clogging when a pumping system is used. If a
significant nonlinearities. particulate filter is not used, the cell should be back-flushed
6.1.2 Infrared Liquid Transmission Sampling Cell— regularly to prevent clogging.
Sampling cells can be constructed of zinc selenide (ZnSe), 6.2.3 Sealed Sample Compartment—The system configura-
barium fluoride (BaF2), potassium bromide (KBr), or other tion should be consistent with preventing harmful, flammable
suitable window material, with a pathlength of 0.1 mm or explosive vapors from reaching the IR source.
6.2.4 Hydrocarbon Leak Alarm—When a sample pumping
(100 µm), parallel (<0.5° variance) cell spacer. Acceptable
system is used, an independent flammable vapor sensor and
pathlength ranges are from 0.080 mm to 0.120 mm. Outside
alarm system should be used to alert the operator when a leak
this range, poor sensitivity or data nonlinearity can occur. For
occurs in the tubing, connectors or transmission cell. This
the data provided in this document, the cells used were ZnSe,
alarm system is strongly recommended when a pumping
NaCl, or KBr as the measurements ranged from 4000 cm–1 to
system is used to pump samples and wash solvents into an
700 cm–1. Some cell material information is given below.
enclosed area.
Transmission 6.2.5 Check Fluid—A check fluid or quality control fluid
Material Comments
Range, cm–1
ZnSe see [Link] 4000 – 550 can be analyzed as needed for individual laboratory quality
KBr susceptible to water damage 4000 – 400 control and procedure issues and for comparison to other
NaCl susceptible to water damage 4000 – 650
BaF2 ammonium salts can damage 4000 – 850
laboratories. One IR manufacturer has used heptane. A check
CaF2 ammonium salts can damage 4000 – 1100 sample should be a material that provides consistent results
using the methods presented in the annexes to this practice. The
Results should be corrected to 0.100 mm pathlength to
purpose of this quality control fluid is to verify proper
account for cell path variation and improve data comparison to
operation of the FT-IR spectrometer/transmission cell
other instruments using this practice.
combinations, as well as any associated sample introduction
[Link] Due to the large refractive index change when the and cleaning hardware.
infrared beam passes from air into the ZnSe windows, fringe
reduction is necessary to provide consistent results. Fringe 7. Sampling and Sample Handling
reduction can be achieved electronically, optically or mechani-
7.1 Sample Acquisition—The objective of sampling is to
cally for ZnSe cells. For further explanation, see Appendix X1.
obtain a test specimen that is representative of the entire
Care should be taken in selecting window materials to ensure
quantity. Thus, laboratory samples should be taken in accor-
that the desired parameters can be measured within the
dance with the instructions in Practice D4057.
transmission region of that material and compatibility with the
specific application; for example, salt windows (KBr, NaCl, 7.2 Sample Preparation—No sample preparation is re-
quired. Laboratory samples should be shaken or agitated to
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KCl) can be used and may not require fringe correction but are
susceptible to damage from water contamination in the oil. ensure a representative sample is taken from the bottle.
Coates and Setti (3) have noted that oil nitration products can
react with salt windows, depositing compounds that are ob- 8. Instrumentation Preparation
served in later samples. 8.1 Spectral Acquisition Parameters:
6.1.3 Cell Flushing/Cleaning Solvent—The ideal solvent to 8.1.1 Spectral Resolution—8 cm–1 or better (lower numeric
flush the cell between samples to minimize carryover should value).
have no significant absorption in the condition monitoring 8.1.2 Data Point Spacing Resolution—4 cm–1 or better
areas of interest and should dry quickly when air is pumped (lower numeric value).
through the system. Typical wash solvents used for common 8.1.3 Typical Range—4000 cm–1 to 550 cm–1 (see 6.1.2).
petroleum and some synthetic lubricants are technical grade, 8.1.4 Spectral Format—Absorbance as a function of wav-
light aliphatic hydrocarbons such as heptane or cyclohexane. enumber.
Other solvents may be required for more specialized synthetic 8.1.5 Other Optical, Electronic Filtering and Interferogram
lubricants. Health and safety issues on using, storing, and Computational Parameters—These parameters should be as
disposing of these solvents will not be covered here. Local recommended by the manufacturer or as determined necessary
for adequate measurement quality. Individual parameters and
regulations and Material Safety Data Sheets (MSDS) should be
settings will vary depending on instrument manufacturer but
consulted.
most FT-IR spectrometers should be able to collect an adequate
6.2 Optional Components: spectrum in less than one minute.

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 E2412 − 23a
NOTE 2—Identical scanning acquisition parameters should be used for the cell being used. The manufacturer’s suggestions and
all samples to be trended. recommendations should be considered.
8.2 Background Collection: 9.2.1 Petroleum based lubricants have their maximum ab-
8.2.1 The single-beam background collection (empty sys- sorbance in the 3000 cm–1 to 2800 cm–1 range (or transmit-
tem reference scanned and stored on an FT-IR spectrometer) tance value close to 0 %T).
should be performed frequently enough such that ambient 9.2.2 Ester based lubricants have their maximum absor-
changes in atmospheric water vapor levels and other changing bance in the 1390 cm–1 to 1090 cm–1 range (or transmittance
ambient conditions do not significantly affect the sample value close to 0 %T).
results (see Practice E1421). The frequency of background 9.3 Sample System Cleaning and Checks—To ensure the
checks should be determined by the individual laboratory minimum amount of sample cross-contamination or sample
conditions and sampling technique; for example, at the carry-over, either a minimum volume of the next sample can be
completion of each run when an autosampler is used. flushed, or a volatile solvent can be flushed through the cell and
8.2.2 Note that changing water vapor levels will have the the cell dried. If the cell is dried, the amount of absorbance
strongest effect, as water vapor is a strong infrared absorber. A from either the previous sample or residual wash solvent in the
water vapor check may be included in the software to monitor sample cell can be checked. This check is performed by the
the intensity of the water vapor in the single-beam background same spectral analysis operation as described above. The
spectrum. For example, the water vapor bands superimposed maximum absorbance intensity should be below a preset
on the single-beam spectrum at 1540 cm–1, 1559 cm–1, and threshold in the monitoring region (that is, CH stretch in
1652 cm–1 may be measured relative to the average of baseline petroleum based fluids). For most petroleum and synthetic
points at 1609 cm–1 to 1582 cm–1. Acceptable limits for opera- lubricants and wash solvents, this intensity will be less than 0.2
tion can be set; for example, measured peaks due to water absorbance units. The optimal threshold will depend upon the
vapor superimposed on the single-beam background should not specific system configuration, in that some systems are de-
be more than 10 % of the single-beam intensity. signed to “push-out” the residual oil sample and wash solvent
8.2.3 Most of the research and development work used in with the next sample. The manufacturer’s suggestions and
the development of this practice used a background collection recommendations should be considered.
at least every 2 h. Individual parameters and settings will vary
depending on instrument manufacturer but most FT-IR spec- 9.4 Data Processing—All spectra will be processed in units
trometers should be able to collect an adequate spectrum in less of absorbance as a function of wavenumber. Calculated data
than one minute. must be corrected to the reference pathlength of 0.100 mm
prior to reporting to account for cell pathlength variation that
8.3 Cell Pathlength Check—A cell pathlength check is will be seen in commercially available cells. Any other spectral
needed to verify the pathlength consistency of the cell. Results data treatment should occur prior to calculating results from the
are referenced to 0.100 mm as mentioned in 6.1.2. This check spectrum.
is particularly important for water-soluble salt cell windows
9.4.1 Spectral data processing results can be trended di-
(for example, KBr). For systems using a fixed flow cell, the
rectly from the in-service oil spectrum (direct trending). The
check can be performed at the same time as the background
only spectral data treatment is the correction of the spectrum or
collection. Different instrument manufacturers may use differ-
results to the 0.100 mm reference pathlength and the applica-
ent techniques for cell pathlength checks that may require the
tion of fringe reduction algorithms to the spectrum, if required.
use of a reference or calibration fluid(s). A fringe-based method
9.4.2 Spectral data processing results can also be obtained
for determining cell pathlength is discussed in the appendix.
by spectral subtraction processing, which requires a reference
Manufacturers’ instructions and recommendations should be
spectrum (spectral subtraction). Where spectral subtraction is
considered.
used, processing of results is done from the difference spec-
9. Procedures, Calculation, and Reporting trum that is generated by subtracting the appropriate new oil
reference spectrum from the spectrum of the in-service oil
9.1 Sample Introduction—A representative sample is intro- sample. The in-service oil spectrum and new oil reference
duced into the infrared transmission cell, either manually or by spectrum must both be corrected to the reference pathlength of
an automatic pumping system. Autosamplers that hold a 0.100 mm prior to subtraction and a 1:1 subtraction factor used.
variety of oil sample container sizes are available from several The subtracted spectral results can be trended over time and
manufacturers. treated in a manner similar to those collected using the direct
9.2 Sample Integrity Check—To ensure accurate and con- infrared trending method.
sistent results, the infrared spectrum of the sample should be [Link] The most commonly used reference is a sample of
checked to verify that the cell is completely filled and that air new oil. If possible, the new oil should be from the same lot
bubbles passing through the cell during data collection are not and drum as the in-service oil. An alternate approach that might
affecting the results. Multiple, automatic, computerized inter- yield a more representative reference would be to take a sample
pretation methods exist for this procedure. A sample integrity of oil one hour after the oil has reached operating temperatures.
check based on measurement of the absorbance intensity over 9.4.3 Post-analysis data treatment can use simple multipli-
the wavenumber range from 3000 cm–1 to 1090 cm–1 is suit- ers and other scaling techniques; for example, “value × 100” at
able for multiple lubricant types. The exact absorbance inten- the request of maintenance personnel for ease in evaluation and
sity will depend on the spectral resolution and the pathlength of presentation (see Annex A1).
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9.5 Spectral Analysis of Sample Data—Selected spectral
regions containing information relevant to condition monitor-
ing are measured and reported. The regions analyzed are
specific to different lubricating fluid types. New oil sample
parameters can be used as the point from which to trend when
initially implementing an analysis process for a lubricant type.
Statistical analysis shown in the annexes also provides ex-
amples. Details of the spectral analysis process can be found in
the annexes to this Practice.
10. Effects of Oil Formulation
10.1 Differences in oil formulations can affect the results
reported for the various measurements described in Annex A1.
For example, Fig. 1 shows spectra of four 10W-30 oils in the
carbonyl region where oxidation is measured for petroleum
lubricants. In this example, absorbances for carbonyl-
containing additives in these unused oil formulations contrib-
ute nearly a factor of 2 difference in the oxidation result
measured by direct trending.
10.2 Results should be:
10.2.1 Interpreted relative to values measured for unused oil
of the same formulation, or FIG. 1 Example of Carbonyl Containing Components in New Oil
10.2.2 Trended directly from the component sample history. Formulations
10.3 Distribution profiles for results for different oil formu-
lations should typically not be combined unless justified by
field experience in condition monitoring programs.
fuel; glycol; infrared; IR; lubricating oils; nitration; oxidation;
11. Keywords petroleum based extreme pressure lubricants; petroleum lubri-
11.1 additive packages; base stock degradation; condition cants; polyol ester synthetic lubricants; soot; sulfates; trend
monitoring; contamination; Fourier transform infrared; FT-IR; analysis; water

ANNEXES

(Mandatory Information)

A1. MEASUREMENT OF MOLECULAR PARAMETERS IN VARIOUS SYSTEMS—DIRECT TRENDING

A1.1 This annex does not purport to discuss all lubricant gasoline is also possible but not as widely applied, as com-
types. Measurement parameters for petroleum lubricants (for paratively few gasoline engines are enrolled in condition

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example, crankcase), extreme pressure petroleum lubricants monitoring programs. In addition, monitoring of the zinc
and polyol esters are presented. As data becomes available, dialkyldithiophosphate (ZDDP) based antiwear component of
other lubricant types can be added to the annex. the additive package is also possible. The most common FT-IR
NOTE A1.1—It is not the intent of this practice to establish or condition monitoring parameters for crankcase engines are
recommend normal, cautionary, warning or alert limits for any machinery presented in Table A1.1, with some spectral measurement
or fluids. Such limits should be established in conjunction with advice and examples presented as a guide in using band areas. Throughout
guidance from the machinery manufacturer and maintenance group. these examples, the use of integrated band area is preferred as
noted in Practice E168 because it has been “found to be more
A1.2 Petroleum Lubricants (Typically Diesel Engines)—
accurate than peak-height measurements because one is, in
Monitoring of diesel crankcase oil is one of the most common
effect, averaging multipoint data.”
applications of lubricant condition monitoring. Condition
monitoring in these systems is divided into contaminant A1.2.1 Water:
monitoring (typically water, soot, fuel, glycol) and oil degra- A1.2.1.1 Water contamination is monitored in diesel crank-
dation monitoring (typically oxidation and nitration). Sulfation case lubricants by measuring the hydrogen-bonded OH stretch
degradation products may arise from lubricant component region given in Table A1.1. An example of varying levels of
breakdown but commonly arise from the by-products of water contamination is shown in Fig. A1.1. In the following
sulfur–containing diesel fuels. Measuring contamination from examples (except soot) the infrared spectrum is shaded down to

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 E2412 − 23a
the described baseline, giving a visual example of how the vary. Work is currently active on other IR measurement areas
integrated absorbance area is measured. Measurement of these and techniques. The measurement listed can be used as a
band areas by computer assisted techniques is common in most guideline but is not intended to be the only infrared based fuel
infrared manufacturers’ software packages. For the water contamination measurement. An independent test, such as
measurement in crankcase oils, the area under the curve viscosity change, flash point, or gas chromatography can be
between 3500 cm–1 and 3150 cm–1 is shaded, showing an used to confirm an indication of fuel presence in the FT-IR
example of the measurement described above. spectrum of the oil.
A1.2.1.2 Water Interferences—High soot levels (~10 % w/w A1.2.5 Glycol Antifreeze Contamination:
solids) may interfere with water measurements in diesel
engines, but interference has not been seen until the soot limit A1.2.5.1 Glycol contamination is monitored in diesel crank-
has been exceeded (that is, > 3 % to 5 % w/w solids). As a case lubricants by measuring the carbon-oxygen stretch region
condition limit (soot) has already triggered, action should be as noted in Table A1.1. Spectral characteristics of glycol
taken irrespective of water. Exact quantitative measurement of contamination are shown in Fig. A1.6.
soot is difficult (that is, % w ⁄w) due to multiple infrared A1.2.5.2 Ethylene glycol will interfere with the ability to
contributing factors as well as the many different soot mea- accurately quantify water level when present since it also
surement methods available. contains hydroxyl groups. However, the converse is not true
since glycol has other spectral features that are used for
A1.2.2 Soot: detection and quantification. Therefore, when glycol is present,
A1.2.2.1 Soot loading is measured from the baseline offset water can be detected but not reliably quantified using FT-IR
at 2000 cm–1 as described in Table A1.1. Fig. A1.2 shows some spectroscopy. This is not considered a problem because of the
examples of spectra showing low, intermediate, high and very greater significance the presence of glycol has to engine
high soot loading levels (increasing levels from 1 through 5). operation. As with fuel, the presence of glycol can be con-
A1.2.2.2 Soot Interference—High water levels have been firmed by gas chromatography or a colorimetric test, or more
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observed to interfere with the measurement of soot in internal commonly, corroborated using elemental analysis results for
combustion engine crankcases. However, this interference does sodium and boron.
not become significant until the water level is on the order of
>5 % (50 000 ppm), levels which will immediately condemn A1.3 Extreme Pressure (EP) Fluids (Typically Petroleum
the lubricant and require immediate maintenance action irre- Gear or Hydraulic Fluids):
spective of any other indicators. A1.3.1 In addition to the above crankcase oil analysis,
A1.2.3 Oxidation, Nitration and Sulfation: condition monitoring of gear and hydraulic oil is also widely
A1.2.3.1 Unlike the previous examples, oxidation, nitration applied. In these systems, the most common parameters
and sulfation breakdown products in crankcase oils cannot be measured are water contamination and oxidative breakdown of
easily quantified by comparison to pure prepared standards. the oil, which are presented in Table A1.2.
Here, there are a large number of different oxidation and A1.3.2 Water:
nitration compounds that can be produced and gradually build
A1.3.2.1 As water is the most common contaminant in
up in the oil. Fig. A1.3 shows the measurement areas for
crankcase oils, it is also the most common contaminant in
oxidation and nitration product buildup monitoring, with the
gearboxes and hydraulic systems. In these systems, unlike the
sulfation region highlighted in Fig. A1.4.
crankcase oils, however, interactions between water and the EP
A1.2.3.2 Oxidation, Nitration and Sulfation additives alter the infrared response, and thus water is mea-
Interferences—As in the soot measurement, very high water sured differently than in the crankcase lubricants. Fig. A1.7
levels can generate false positives for oxidation and nitration. demonstrates this different response of water. Water contami-
However, water levels of this magnitude will immediately nation is manifested as a general, horizontal baseline offset of
condemn the lubricant. Very high (>5 %) glycol levels in a the entire infrared spectrum. Here, the integrated area for the
crankcase oil may start interfering with sulfation measurement, spectrum representing 3000 ppm (0.3 %) water is shaded.
but again contaminant levels of this magnitude would dictate While this measurement becomes the principal water measure-
immediate maintenance action. Various additive packages, ment in EP fluid systems, very high water levels (greater than
such as detergents, dispersants, antioxidants, overbase 2 %) will begin to show a similar hydrogen-bonded OH stretch
additives, etc. may also generate significant absorbance in the band as seen in the crankcase oils.
condition monitoring regions of interest. Blends of petroleum
A1.3.2.2 Water Interferences—As the principal water mea-
lubricants with significant amounts of ester, whether part of the
surement is based on the integrated absorbance with no local
base-stock package or as an additive, will absorb strongly in
baseline correction, soot, dirt and high concentrations of
the oxidation area. These lubricants are not presented at this
infrared scattering particulates will generate higher than ex-
time.
pected readings for water. However, typical gearboxes and
A1.2.4 Fuel Contamination: hydraulic systems will not contain particulate levels high
A1.2.4.1 The possibility of fuel contamination may be enough to cause a significant baseline offset and tilt. Wear
indicated in diesel crankcase lubricants by measuring the peak metal analysis, particle counting or other applicable tests
at 810 cm-1. Spectral characteristics of diesel (Figs. A1.5 and should condemn gear and hydraulic systems that manifest such
A1.6) and other fuels noted in Table A1.1 have been found to extreme particulate levels.

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A1.3.3 Oxidation: Fig. A1.10. As this area is closely associated with the water
A1.3.3.1 The oxidative breakdown measurement shown in measurement area, a localized, single–point baseline at
Fig. A1.8 in petroleum EP fluids is the same as in the 3595 cm–1 provides a correction for low levels of water
petroleum-based crankcase fluids discussed in A1.2.3.2. Note buildup (Fig. A1.10).
that while Fig. A1.8 also shows an increase in sulfation A1.4.3.3 Ester Base-Stock Breakdown II—In addition to the
by-products, not all EP systems will show this effect. breakdown area I, a second area associated with the traditional
OH stretch (as measured for water in crankcase oils) also
A1.4 Synthetic Polyol Ester Lubricants (Typically Aero- increases as the lubricant breaks down. This ester base-stock
Derivative Gas Turbines): breakdown II area is also monitored as a measurement of
A1.4.1 Condition monitoring of high-performance aircraft degradation of the polyol ester lubricants. The breakdown II
turbine engines is widely applied in both the military and region is also highlighted in Fig. A1.10.
commercial aviation maintenance industries. In addition, many A1.4.3.4 Ester Base-Stock Breakdown Interferences—As
aero-derivative gas turbines are used in power generation, noted above in A1.4.2.2 where excessive base-stock break-
marine transport and other non-aeronautical applications. In down interferes with the water measurement, a similar effect
these systems, the primary lubricant is a synthetic polyol ester has also been noted with the lubricant breakdown measure-
and is available under a variety of different military specifica- ment. Excessive water levels may cause the lubricant break-
tions and commercial item descriptions and brand names. down reading to be higher than the actual level. Once again
Table A1.3 lists the condition monitoring properties of interest however, water levels of this magnitude will condemn the
measured by FT-IR along with the band measurement area and lubricant irrespective of the actual breakdown level.
the baseline point(s).
A1.4.4 Antiwear Components:
A1.4.2 Water: A1.4.4.1 While the antiwear compounds used in crankcase
A1.4.2.1 Just as the infrared measurement for water was oils and polyol ester lubricants are typically different species,
adjusted to account for the different interactions in the formu- the most common compounds used for both oils have a
lations in crankcase and EP oils, a different water measurement phosphate functional group. For this reason, the measurement
area is also required for the polyol esters. Fig. A1.9 shows the area developed for monitoring levels and trends of ZDDP has
area under the curve that is integrated for the determination of been found to be equally useful for monitoring tricresyl
water contamination in these systems, with the measurement phosphate (TCP). Fig. A1.11 shows varying levels of TCP
highlighted for a sample containing 1000 ppm of added water. blended into a polyol ester lubricant. As previously noted,
Note that the water in these systems shows up as a broad band, building calibration curves for measurement parameters (when
similar to what is observed for water in the crankcase oils, but pure or prepared standards are available) is possible. However,
the strongest response occurs at higher frequencies than in the this is not necessary, as lubricant condition monitoring requires
case of the crankcase oils (~3700 cm–1 to 3600 cm–1 for polyol only reliable, repeatable measurements. Correlation of FT-IR
esters versus 3500 cm–1 to 3150 cm–1 for crankcase oils). measurements to physical values is not necessary.
A1.4.2.2 Water Interferences—The most significant interfer-
ence found in the determination of water is interference from A1.4.5 Fuel Contamination:
the polyol ester lubricant breakdown I (see A1.4.3). Under A1.4.5.1 Fuel contamination is monitored in polyol ester
severe conditions of lubricant degradation, this band will begin lubricants by measuring the peak at 810 cm–1 as given in
to overlap and contribute to the integrated water measurement section A1.2.4.
area. As seen below in Fig. A1.10 however, this effect is only A1.4.6 Other Fluid Contamination:
seen when the lubricant is already severely degraded, which A1.4.6.1 In addition to fuel contamination, foreign oils and
dictates maintenance action from the degradation irrespective hydraulic fluids may contaminate lubricating oils (for example,
of the actual water level. polyol ester contaminated by a petroleum based fluid). In most
A1.4.3 Ester Base-Stock Breakdown: cases, identifying the presence of a foreign fluid is all that is
A1.4.3.1 As the polyol esters are a different chemical required to generate an appropriate maintenance response. The
system than petroleum based lubricants, degradation of the wide variety of potential contaminants suggests an equally
polyol ester lubricant produces different breakdown products. wide variety of measurement methods may be desirable. In
The most common degradation pathway in ester based lubri- addition, multiple frequency distributions may also be required
cants is the conversion of the ester into organic acids and and are not given here. The measurement areas given in Table
alcohols. A1.3 demonstrate the measurement used to indicate the pres-
A1.4.3.2 Ester Base-Stock Breakdown I—The resulting ence of petroleum oils, phosphate ester oils, or polyalphaolefin
polyol ester degradation products are first seen between (PAO)/diester blend oils contaminating polyol ester oils. Fig.
3595 cm–1 and 3500 cm–1, and the measurement is noted as A1.12 shows an example of polyol ester oil contaminated by a
ester base-stock breakdown I in Table A1.3 and highlighted in polyalphaolefin (PAO)/diester blend oil.

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TABLE A1.1 Petroleum Lubricant (for example, Crankcase) Condition Monitoring Parameters—Direct Trending
Component Measurement Area, cm-1 Baseline Point(s), cm-1 ReportingA
Water Area 3500 to 3150 Minima 4000 to 3680 and 2200 to 1900 Report Value as Measured
Soot Loading Absorbance intensity at 2000 None Value × 100
Oxidation Area 1800 to 1670 Minima 2200 to 1900 and 650 to 550 Report Value as Measured
Nitration Area from 1650 to 1600 Minima 2200 to 1900 and 650 to 550 Report Value as Measured
Antiwear Components Area 1025 to 960 Minima 2200 to 1900 and 650 to 550 Report Value as Measured
(Phosphate based, typically ZDDP)
Gasoline Area 755 to 745 Minima 780 to 760 and 750 to 730 Report Value as Measured
Diesel (JP-5, JP-8)B Area 815 to 805 Minima 835 to 825 and 805 to 795 (Value + 2) × 100
Sulfate by-products Area 1180 to 1120 Minima 2200 to 1900 and 650 to 550 Report value as measured
Ethylene Glycol Coolant Area 1100 to 1030 Minima 1130 to 1100 and 1030 to 1010 Report value as measured
A
Reporting values in absorbance/0.1 mm (see 6.1.2).
B
Spectral characteristics of diesel and other noted fuels have been found to vary. Work is currently active on other IR measurement areas and techniques. The
measurement listed can be used as a guideline but is not intended to be the only infrared based fuel contamination measurement. Checking suspect fuel sources is
suggested to verify presence of indicator absorbance bands.
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FIG. A1.1 Example of Integrated Band Measurement Area for Water in Crankcase Oil

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FIG. A1.2 Soot Measurement in Diesel Crankcase Oils

FIG. A1.3 Oxidation and Nitration Measurement in Crankcase Oils

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FIG. A1.4 Sulfation Measurement in Crankcase Oils

FIG. A1.5 Fuel Measurement in Crankcase Oils

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FIG. A1.6 Glycol Contamination Measurement in Diesel Engine Oils

TABLE A1.2 Petroleum Based EP Fluid Condition Monitoring Parameters—Direct Trending

Component Measurement Area, cm-1 Baseline Point(s), cm-1 ReportingA
Water Area 3400 to 3250 No Baseline Value × 20
Oxidation Area 1800 to 1670 Minima 2200 to 1800 and 650 to 550 Report Value as Measured
A
Reporting values in absorbance/0.1 mm (see 6.1.2).

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FIG. A1.7 Water Contamination Measurement in EP Fluids

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FIG. A1.8 Oxidation Measurement in EP Fluids

TABLE A1.3 Polyol Ester Fluid Condition Monitoring Parameters—Direct Trending

Measurement Area,
Component Baseline Point(s), cm-1 ReportingA
cm-1
Water Area 3700 to 3595 Minima 3950 to 3770 Value x 10
and 2200 to 1900
Ester Base-Stock Breakdown I Area 3595 to 3500 Single point at 3595 Value x 10
Ester Base-Stock Breakdown II Area 3330 to 3150 Minima 3950 to 3770 Value x 10
and 2200 to 1900
Antiwear Components (typically TCP) Area 1025 to 960 Minima 2200 to 1900 Report value as measured
and 650 to 550
Fuel (JP-4, JP-5, JP-8)B Area 815 to 805 Minima 835 to 825 (Value + 2) x 100
and 805 to 795
Other Contaminants in Polyol Ester Synthetics Area 1425 to 1390 None Report value as measured
(for example, Petroleum Lubricants and Hydraulic Fluids) and 1090 to 1030C
A
Reporting values in absorbance/0.1 mm (see 6.1.2).
B
Spectral characteristics of noted fuels have been found to vary. Work is currently active on other IR measurement areas and techniques. The measurement listed can
be used as a guideline but is not intended to be the only infrared based fuel contamination measurement. Checking suspect fuel sources is suggested to verify presence
of indicator absorbance bands.
C
Alternate multivariate techniques such as PCR, PLS and factor analysis such as given in Guide D8321 can also be used.

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FIG. A1.9 Water Contamination Measurement in Polyol Ester Lubricants

FIG. A1.10 Ester Base-Stock Breakdown Measurements in Polyol Ester Lubricants

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FIG. A1.11 Measurement of Antiwear (TCP) in Polyol Ester Lubricants

FIG. A1.12 Polyol Ester Lubricant Contaminated with PAO/Diester Oil

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A2. MEASUREMENT OF MOLECULAR PARAMETERS IN VARIOUS SYSTEMS—SPECTRAL SUBTRACTION

A2.1 This annex does not purport to discuss all lubricant A2.2.1.3 Interferences—Ethylene glycol will interfere with
types. Measurement parameters for petroleum lubricants are the ability to accurately quantify water level when present
presented. As data becomes available, other lubricant types can since it also contains hydroxyl groups. However, the converse
be added to the annex. is not true since glycol has other spectral features that are used
NOTE A2.1—It is not the intent of this practice to establish or for detection and quantification. Therefore, when glycol is
recommend normal, cautionary, warning or alert limits for any machinery present, water can be detected but not reliably quantified using
or fluids. Such limits should be established in conjunction with advice and FT-IR. This is not considered a problem because of the greater
guidance from the machinery manufacturer and maintenance group.
significance the presence of glycol has to engine operation.
A2.1.1 Searching a spectral library to find the best selection
A2.2.2 Soot Particles:
for reference subtraction should not be used. This approach
will generate incorrect results, particularly for antifreeze, fuel A2.2.2.1 Suspended soot is the result of the incomplete
and water. It is better to make a choice of lubricant type and use combustion of fuel. It is usually only a consideration in diesel
it consistently if the oil type is not known. If an appropriate engines but could be indicative of carburetor or injector
reference oil cannot be obtained, spectral subtraction should problems with other fuel systems. While soot has no specific
frequency of absorption in the infrared spectrum, it causes a
not be performed.
shift in the baseline of the spectrum due to absorption and
A2.2 Petroleum-Based Crankcase Lubricants—As stated in scattering of light. Since there are no other spectral features in
Annex A1, condition monitoring of crankcase oils is divided the region at 1950 cm–1, this area is used to assess the level of
into contaminant monitoring and degradation monitoring. The soot in a sample as is shown in Fig. A2.2.
analysis parameters for spectral subtraction are similar to those A2.2.2.2 In the case of soot, the baseline absorbance is
for the direct trending approach. Different laboratories have measured prior to reference oil subtraction. Because the soot
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developed slight variations on these analyses. These different absorbance obtained is a measure of the amount of tilt in the
approaches are equally valid for trending but will produce spectral baseline, a correction should be applied to the data to
results that differ numerically. Consistent analyses should be account for the contribution of the transmission cell to the
applied for each application. Table A2.1 give examples of baseline tilt if the background is taken without the cell in the
specific analysis parameters used to obtain data from difference beam path. This value can be significant in the case of a ZnSe
spectra of in-service minus new oil. The information in the cell, on the order of 0.2 absorbance units with clean oil in the
remainder of this section provides more detail about the cell as can be seen in the figure. The baseline shift caused by
individual parameters. The footnotes to Table A2.1 should be soot is affected by the amount of soot present and the effective
reviewed carefully. particle size. The effective particle size is determined by the
nature of the combustion system and the dispersants in the oil.
A2.2.1 Water Contamination:
This fact makes it difficult to directly assess or calibrate the
A2.2.1.1 Water has two characteristic absorptions in the quantity of soot, so factors that relate the amount of soot to the
infrared (3400 cm–1 and 1640 cm–1) which make detection infrared absorbance value must be established with the engines
possible at around the 0.05 % to 0.1 % by weight level. While and lubricants of interest.
this is not as sensitive as some other techniques, it is at a level
where problems from the presence of water in the crankcase A2.2.3 Oxidation (Carbonyl Oxidation Products):
could begin. Water is detected using a broad feature, centered A2.2.3.1 The broad feature centered at 1730 cm–1 is due to
around 3400 cm–1, that is caused by stretching of the the presence of carbonyl-containing degradation products of
hydrogen-bonded hydroxyl (-OH) group. Water is measured as oil. These have been identified as lactones, esters, aldehydes,
depicted in Fig. A2.1 using a single-point baseline at ketones, carboxylic acids, and carboxylate salts. This feature is
3700 cm–1 and a peak height at 3428 cm–1. Alternatively, the shown in Fig. A2.3. The baseline for carbonyl oxidation
water maximum can be measured relative to a two-point measurement, referred to as oxidation, is taken at 1950 cm–1
baseline drawn from 3740 cm–1 to 3120 cm–1. The concentra- and the maximum peak height between 1800 cm–1 and
tion values shown in the figure are for weight percent (wt%) 1650 cm–1 is determined. Alternatively, some labs measure the
water. absorbance of the peak closest to 1709 cm–1 relative to a
A2.2.1.2 Calibration—Calibration is typically done over the single-point baseline at 1900 cm–1.
range from 0.05 % to 0.5 % by weight, but may go as high as A2.2.3.2 For ester based synthetic oils; the measurement
1.0 % by weight water. Beyond this point the behavior of water region can be shifted to range from 1710 cm–1 to 1660 cm–1 to
in petroleum lubricants becomes very nonlinear when mea- avoid the large carbonyl feature of the ester base oil. The
sured in lubricating oil by an optical measurement technique broadness of the peak is a result of the wide variety of materials
such as infrared. Standards are prepared locally by adding present. The point of maximum intensity will vary as the oil
water to dry oil. Water standards should be freshly prepared and conditions of its use are changed. The increase in peak
and analyzed. Adequate mixing is necessary to obtain valid height that occurs as the number of hours the oil has been run
results. Mixing, sonicating or mechanical shaking for at least in the engine increases has significance in the measurement of
15 min is considered adequate. Do not use plastic containers. degradation related to TAN and viscosity.

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A2.2.4 Nitrogen Oxidation Products: A2.2.7.3 The accuracy of measurement is strongly affected
A2.2.4.1 The sharp feature at 1630 cm–1 is the result of by the standard material used to calibrate the instrument and
nitrogen oxide fixation into the oil as is shown in Fig. A2.3. the level to which the fuel is evaporated within the engine
The materials leading to this feature are nitrate esters. The crankcase. This is why weathered fuel should be used to
measurement of the nitrogen oxide feature is done by choosing calibrate the system and calibration of fuel should be done
the maximum peak intensity over the range of 1650 cm–1 to based on fuels obtained regionally. In addition, there is a
1610 cm–1 with a single-point baseline at 1950 cm–1 or critical need to match the new-oil reference properly, as
1900 cm–1. discussed earlier. It is the change in base oil aromatic content
A2.2.4.2 Because of the interference that can be seen over that is the major factor leading to errors from reference
the same region from metal soap products, some people prefer mismatch.
to measure the sharp feature as a shoulder on the broad A2.2.7.4 Calibration for diesel fuel is typically done over a
underlying feature as a more correct measure of nitration. The range from 2 % to 10 % by weight and gasoline from 1 % to
formation of nitrogen fixation products is most significant in 10 % by weight. Weathered fuel is used as the standard
gasoline and natural gas engines as well as some diesel systems material. Procedures for preparing representative weathered
that use exhaust gas re-circulation. fuel may vary, but the following should serve as a guideline:
A2.2.5 Sulfur Oxidation Products: Diesel fuel is brought to approximately 107 °C then held at this
A2.2.5.1 Another broad spectral feature, centered around temperature for 30 min. This represents a loss of around 5 % of
1150 cm–1 as shown in Fig. A2.3, is the result of sulfate the original volume. Gasoline is heated at low temperature
compounds as well as overlap with oxidation products (car- until around 40 % of the original volume is evaporated.
boxylate). A baseline point at 1950 cm–1 is used. (Warning—Great care should be taken when preparing these
A2.2.5.2 Sulfate material results from the introduction of materials to avoid fire hazard or exposure to the vapors.)
sulfur from the combustion of diesel fuels or from the A2.2.7.5 Gasoline contamination detection is less problem-
oxidation of sulfur from the base oil and additives in gasoline atic than detection of diesel fuel contamination because of the
or natural gas engines. This band is a fairly specific measure of higher relative aromatic content of gasoline. Quantification of
over basing additive consumption and directly relates to the gasoline is calibrated using a peak area over the range of
TBN assay for engine oils. 734 cm–1 to 721 cm–1.
A2.2.6 Phosphate Antiwear Additive Depletion: A2.2.7.6 An independent test, such as viscosity change,
A2.2.6.1 Monitoring the disappearance of phosphate anti- flash point, or gas chromatography, can be used to confirm an
wear additive (typically zinc dialkyldithiophosphate) can indi- indication of fuel presence in the FT-IR spectrum of the oil.
cate unusual wear or severe operating conditions. The deple- A2.2.8 Glycol Contamination:
tion of these additives will occur prior to the point where the A2.2.8.1 This contaminant has characteristic absorptions in
oxidation of the lubricant begins to accelerate, making its the infrared that make its detection possible at around the 0.1 %
trending a useful indicator of the lubricant’s remaining useful level. While this is not as sensitive as some other techniques, it
life. This component is monitored as a negative peak in the is at a level where problems from the presence of these
difference spectrum since the new oil will contain a greater contaminants in the crankcase could begin. Glycol has the
concentration of the additive than the in-service oil. In this case same broad hydroxyl (-OH) group feature, centered on
the maximum negative peak in the range from 1020 cm–1 to 3400 cm–1, as seen for water. However, glycol has other
930 cm–1 with baseline points over the same range is used as characteristic peaks that differentiate it from water around
shown in Fig. A2.3. 880 cm–1, 1040 cm–1, and 1080 cm–1 as can be seen in Fig.
A2.2.7 Fuel Residue: A2.5.
A2.2.7.1 As mentioned previously, the measurement of fuel A2.2.8.2 The peak height at 883 cm–1 with a single-point
residues or raw fuel is very difficult by any method. The main baseline at 917 cm–1 is used to quantify glycol since it is not
difference between the fuel and base oil is in molecular weight subject to interferences to the same extent as the bands at
or boiling range and the relative percentage of aromatic 1040 cm–1 and 1080 cm–1. This effect can be seen by looking
materials. Fuel has a lower boiling range and a higher at Fig. A2.5, which shows a large sulfate band with glycol
percentage of aromatic material. Conventional methods such as peaks on the right shoulder. Even though the peaks at
gas chromatography or flash point make use of the lower 1040 cm–1 and 1080 cm–1 are larger than the one at 880 cm–1,
boiling range, while the infrared approach examines the it is very difficult to accurately measure them in the presence of
aromatic content to indicate if fuel is present. other oil breakdown product. Instead the peaks at 1040 cm–1
A2.2.7.2 The spectral feature caused by aromatic bands and 1080 cm–1 are used to confirm the presence of glycol.
over the range from 817 cm–1 to 804 cm–1 is used for this A2.2.8.3 In practice, a second derivative spectrum can be
purpose. A peak area over this range is used as is depicted in used to find the correct peak location for these peaks and
Fig. A2.4. The figure shows the peak area increase as the wt% absorbance intensity limits can be used to trigger whether
of weathered diesel fuel increases. In some cases, notably glycol appears to be present. Fig. A2.5 shows the intensity
winter diesel fuel, the peak used for fuel residue is broader than increase in the glycol bands at the concentration increases over
that shown in Fig. A2.4. A wider range for the baseline points the range from 0.05 % to 0.8 % by weight.
can be used to achieve better sensitivity, although this caused A2.2.8.4 Interferences—Glycol will interfere with the quan-
a reduction in the selectivity. titation of water level when present, but the converse is not
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true. Therefore, when glycol is present, water cannot be are reported. The units used for reporting are absorbance per
reliably quantified using the FT-IR measurement. This is not 0.1 mm (abs/0.1 mm), which relates directly to the peak
considered a problem because of the greater significance the intensities observed in the difference spectrum of the in-service
presence of glycol has to engine operation. As with fuel, the oil. The information for these components is most useful in
presence of glycol can be confirmed by gas chromatography or trend analysis.
a colorimetric test, or more commonly, corroborated using A2.2.9.2 The carbon particles that form soot do not cause
elemental analysis results for sodium and boron. localized absorption. Instead, an offset of the spectral baseline
A2.2.8.5 Glycol standards can be prepared over a range due to light scattering and absorption is observed. The magni-
from 0.1 % to 0.5 % by weight glycol using a 50:50 mixture of tude of this offset is determined by the particle size of the soot

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glycol-based antifreeze and water. Calculations should be as well as its concentration. The particle size observed is
made based on the actual amount of glycol-based antifreeze affected by the engine type and lubricant. Absorbance per
added, not on the amount of the 50:50 mixture. Glycol 0.1 mm (abs/0.1 mm) values are reported.
standards should be freshly prepared and analyzed. Adequate A2.2.9.3 Phosphate antiwear additive, typically various
mixing is necessary to obtain valid results. Mixing, sonicating forms of zinc dialkyldithiophosphate in crankcase oils, is
or mechanical shaking for at least 15 min is considered reported in absorbance per 0.1 mm (abs/0.1 mm) the same as
adequate. Do not use plastic containers. the above oxidation components. However, the antiwear addi-
A2.2.9 Reporting of Data—The values determined from the tive is reported as a negative value since in the in-service used
infrared spectrum for the components discussed in the preced- oil difference spectrum the peak is negative due to the
ing sections on spectral subtraction are reported in different depletion of the additive compared to the original reference oil.
ways because of the nature of the materials present. Certain of A2.2.9.4 Fuel, water, glycol, and gasoline are reported in
the components are not calibrated, including oxidation, weight percent values from calibrations with standards. The
nitration, sulfation, soot, and phosphate antiwear additive. calibrations prepared for diesel fuel and gasoline may not
Others are calibrated, including diesel fuel, gasoline, water, accurately reflect the fuels in use in particular regions of the
and glycol. Recommendations for calibration procedures were world. Because of this, these components should be calibrated
included in previous sections of Annex A2. with locally generated weathered fuel standards. Water and
A2.2.9.1 Oxidation, nitration and sulfation components are glycol should not be routinely calibrated locally because of the
not reported as concentration values, because there are many difficulty in making and analyzing standards.
different chemical compounds formed that contribute to the A2.2.9.5 In practice, the approach taken to make use of the
measured absorption. Since no single product is formed, absorbance values for the non-calibrated components is to note
standard materials are not available to generate the calibration their increase over time within an engine. From a plot or table
curves needed to relate absorbance to concentration. Absor- of the change in absorbance with time, judgments about when
bance values related to the thickness of sample exposed to light to change the lubricant can be made.

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 E2412 − 23a
TABLE A2.1 Petroleum Crankcase Lubricant Condition Monitoring Parameters—Spectral Subtraction
Component Measurement (cm-1) Baseline (cm-1) Reporting Units Footnotes
Water - A Height at 3428 1 point at 3700 wt% (calibrated method) 9
Water - B Maximum near 3400 2 point: 3120, 3740 A/cm or wt%, vol% calibrated method 1, 2, 3, 9
Soot - A Height at 1950 No baseline Abs/0.1 mm 4
Soot - B Absorbance at 2000, 1950 or 1900 No baseline A/cm or wt% (calibrated method) 5, 9
Oxidation - A Max. Height 1800 to 1660 1 point: 1950 Abs/0.1 mm 6
Oxidation - B Peak closet to 1709 in range of 1685-1725 1 point: 1900 A/cm
Nitration Max. Height 1650 to 1610 1 point at 1950 Abs/0.1 mm 7
Phosphate Antiwear Min. Height 1020 to 930 2 point 1020 and 930 Abs/0.1 mm 8
(Negative peak height)
Gasoline Area 734 to 721 2 point 734 and 721 wt% (calibrated method) 9, 10
Diesel Area 817 to 804 2 point 817 and 804 wt% (calibrated method) 9, 10
Verification peak: Verification peak:
Area 883 to 864 883 to 864
Sulfation Height at 1150 1 point at 1950 Abs/0.1 mm
Ethylene Glycol Height at 883 1 point at 901 wt% (calibrated method) 1, 9, 11, 12
Verification peaks: Verification peaks:
Max ht 1098 to 1069 Min 1110 to 1098
Max ht 1050 to 1030 Min 1063 to 1051
Min 1029 to 1023
As noted in 9.4.2, for all components except soot, spectral subtraction is done followed by tilt correction over the range from 4000 cm–1 to 650 cm–1. For soot, follow
the specific recommendations in Table A2.1. After soot calculation, subtraction is done and a spectral tilt correction is applied from 4000 to 650.
NOTE 1—Calibrated methods for water and ethylene glycol are developed using standard preparations of water or ethylene glycol in appropriate
used oil matrices.
NOTE 2—Peak maxima may be easily identified using second derivative spectra.
NOTE 3—Water measurements can be adjusted for glycol content.
NOTE 4—Soot calculated from unsubtracted sample spectrum.
NOTE 5—Soot calculated from subtracted spectrum, before tilt correction.
NOTE 6—Oxidation region for lubricant blends with diesters base oil can be adjusted to 1710 to 1660.
NOTE 7—Alternate method for nitration has been suggested to eliminate metal soap contribution using peak at 1630 with baseline minima in range
1655 to 1640 and 1620 to 1595.
NOTE 8—Phosphate antiwear is a negative peak height since it represents additive depletion compared to the new oil.
NOTE 9—Calibrated methods are based on standard linear regression models.
NOTE 10—Fuel calibrations are based on weathered fuel and need to be adjusted for local variation in fuels.
NOTE 11—Ethylene glycol calibrations based on 50:50 glycol:water mixtures.
NOTE 12—Glycol verification peak locations can best be derived from the second derivative spectrum.

FIG. A2.1 Water Analysis Region for Petroleum Crankcase Lubricants

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FIG. A2.2 Soot Analysis Region for Petroleum Crankcase Lubricants

FIG. A2.3 Oxidation, Nitration, Sulfation, and Phosphate Antiwear Additive Analysis Regions
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FIG. A2.4 Diesel Fuel Analysis Regions for Petroleum Crankcase Lubricants

FIG. A2.5 Glycol Analysis Regions for Petroleum Crankcase Lubricants

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A3. DISTRIBUTION PROFILES AND STATISTICAL ANALYSIS

A3.1 Statistical analysis of historic data from a sufficiently overhaul period. The population should include a minimum of
large population of machinery can be used to explore possible several hundred results for meaningful statistical analysis. If
relationships between condition monitoring test data and ma- the population of machines is very large, less than one overhaul
chinery failure modes. Such statistical analyses are a tool used period may be sufficient.
in establishing alarm limits for condition monitoring tests. A A3.3.2 Unless analysis demonstrates otherwise, segregate
thorough discussion of distribution profile analysis and alarm and separately analyze results from different machine types and
limit determination is beyond the scope of this practice. This for machines using different oil formulations. Even machines
annex merely provides a summary of distribution profile with different sump sizes or different metallurgies should
analysis for the interested user. More detailed descriptions can initially be analyzed separately. If the initial analyses yield
be found in Ref (1). similar limits for all test parameters, it may be appropriate to
A3.2 Frequency Distribution Plots—Histograms: pool results.
A3.2.1 Distribution plots are a common tool used in the A3.3.3 Random selection of samples does not necessarily
statistical analysis of condition monitoring data. The abscissa provide for normally distributed results. Sequential samples
of the plot is the test data result, and the ordinate is the over the course of the overhaul period are more likely to yield
frequency at which a specific result occurs in the test popula- normally distributed results.
tion. Fig. A3.1 shows an example distribution plot. In this A3.3.4 The population analyzed must include examples of
example, the data is from a population of 1910 diesel engine all oil-related failure modes, at typical failure rates. If too many
oils. The abscissa represents the integrated nitration result. A examples of failures are included, the distribution may be
vertical bar is used to represent the number of oils for which broad and calculated limits may be too high. Alternatively, if
the test result falls between the two abscissa values. For failure modes are underrepresented, the distribution may be
example, the tallest bar indicates that approximately 410 narrow, and the calculated limits may be too low.
nitration values were between 7 A ⁄cm and 8 A ⁄cm.
A3.4 Tentative Alarm Limit Calculations—The specific cal-
A3.2.2 To develop reliable alarm limits from statistical
culations and limits used in a condition-monitoring program
analysis of condition monitoring test data, the data must be
are established with advice and guidance from the machinery
approximately normally distributed. The histogram should
manufacturer and maintenance group. The following are pro-
have roughly a bell-shaped appearance and be free of multi-
vided only as an example.
modal features. The histogram in Fig. A3.1 shows an approxi-
mate normal distribution. A3.4.1 The user must first establish categories for test levels
and alarms. Typically a warning or alert level will be used as
A3.2.3 When the FT-IR results are limited to non-negative
an early indication of a potential problem, and an alarm level
values, and the median of the distribution is close to zero, the
will be used as an indication of the need for immediate
distribution will not appear normal (see for example Fig. A3.2).
corrective action. More levels may be used, but at the expense
While a mean and standard deviation can still be calculated, the
of increased complexity.
user should verify that alarm limits based on these statistics are
descriptive of the actual distribution. For example, only about A3.4.2 Plot the oil test result data on histograms, marking
5 % of the values should fall above the mean plus two standard data that corresponds to oil-related failures. Verify that the
deviations. frequency distribution is approximately normally distributed.
A3.2.4 Multimodal distributions (Fig. A3.3) and broad, flat A3.4.3 Calculate tentative limits based on the average and
distributions (Fig. A3.4) should not be utilized for statistical standard deviation of the oil test results.
analysis. Both examples are indicative of multiple sources of A3.4.3.1 Calculate a tentative alert (warning) limit as the
the same data, low ratio of normal data to failure data or poor average plus two standard deviations. This assumes a test result
measurement precision. for which the value increases with time. For results where the
value decreases with time, the limits would be the average
A3.3 Sampling Considerations: minus the corresponding number of standard deviations.
A3.3.1 The data used in the statistical analysis should A3.4.3.2 Calculate a tentative alarm limit as the average
include a history of all machines of a like type for at least one plus four standard deviations.

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FIG. A3.1 Distribution of Nitration Measurements from ~1900 Diesel Engine Oils

FIG. A3.2 Distribution of Measurements for Soot from ~1900 Diesel Engines

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FIG. A3.3 Example of Multi-modal Distribution

FIG. A3.4 Example of Broad, Flat Distribution

APPENDIX

(Nonmandatory Information)

X1. FRINGING EFFECTS IN INFRARED LIQUID TRANSMISSION SAMPLE CELLS

X1.1 When light passes from one material into another, its straight through and out the second surface, and some is
velocity changes as a result of the change in refractive index reflected back at each side of the film. In addition, some of the
encountered. In addition, unless the refractive indices are an light reflected from the second surface is again reflected back
exact match, the amount of light transmitted through the from the first surface, and then is traveling in the original
interface is less than 100 %, as some reflection occurs. If the direction. The result of such multiple internal reflections is that
light passes through a thin film of material, such as a thin the pathlength of the radiation inside the film is increased, and
polymer sheet, there are two such interfaces encountered where the resulting light transmitted has suffered a phase delay from
reflections can occur. The result of this is that some light goes the original beam. This results in the two beams interfering

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(weakly) with each other. This interference is wavelength a significant fringe pattern is typically still observed because
dependent and the result is that a spectrum plotted in wav- the refractive index of the ZnSe is much greater than that of an
enumber shows a regular sine wave superimposed on the oil sample. If the empty cell is used to create the background
baseline. spectrum, or when a ZnSe cell with exactly parallel windows is
X1.2 This effect is also observed when using a liquid used to collect the sample spectrum, these fringes will appear
transmission cell because the air gap between the two windows to be in the absorbance spectrum of the oil. Fringe reduction
creates the same interference effect as the polymer film techniques can be used to avoid this problem. A common
described above. This optical effect can be used to measure the method is to locate the secondary (phase-delayed) centerburst
thickness of the empty cell, either from the spectral fringes or in the interferrogram recorded for the empty cell and remove it
from the phase delay observed in the interferogram (see by computer manipulation. The transformed single-beam spec-
Practice E168). In the case where salt windows are used, when trum then shows only minimal fringes. Other techniques based
oil is introduced into the cell the fringe pattern is made much on computer fitting and removing the regular sine wave pattern
weaker because the refractive index of the salt window is in the absorbance spectrum, using cell windows with antire-
relatively close to that of an oil sample. Thus, the fringe pattern flective coatings, or slightly "wedging" the cell windows (<0.5°
essentially disappears from the spectrum. In the case where variance) have also been used to reduce fringing effects
ZnSe windows are used, when the oil is introduced into the cell observed in the spectrum.

REFERENCES

(1) Toms, L. A., and Toms, A. M., Machinery Oil Analysis: Methods, 1992 Joint Oil Analysis Program International Condition Monitoring
Automation& Benefits, 3rd edition, STLE, 2008. Conference, JOAP-TSC, 1992, pp. 233–254.
(2) Lukas, M., and Anderson, D., “Laboratory Used Oil Analysis (5) Powell, J., and Compton, D., “Automated FTIR Spectrometry for
Methods,” CRC/STLE Tribology Data Handbook, ed., E. Booser, Monitoring Hydrocarbon-Based Engine Oils,” Lubrication
CRC Press, 1997. Engineering, 49, 3, March 1993, pp. 233 –239.
(3) Coates, J., and Setti, L., “Infrared Spectroscopy as a Tool for (6) Toms, A., and Powell, J., “Molecular Analysis of Lubricants by FT-IR
Monitoring Oil Degradation,” Aspects of Lubricant Oxidation, ASTM Spectrometry,” P/PM Technology, 10, 4, August 1997, pp. 58–64.
Special Technical Publication 916, ASTM, 1986, pp. 57–78. (7) Muster, D., “Condition Monitoring and Diagnostics of Machines: An
(4) Garry, M., “Applied Interpretation of FT-IR Oil Analysis Results for Emerging Transdiscipline Moving Towards Standardization,” Condi-
Improving Predictive Maintenance Programs,” Proceedings of the tion Monitoring‘94 , Jones, M., ed., Pineridge Press, 1994 , pp. 3–17.

SUMMARY OF CHANGES

Subcommittee D02.96 has identified the location of selected changes to this standard since the last issue
(E2412 – 23) that may impact the use of this standard. (Approved Nov. 1, 2023.)

(1) Replaced Practice E1655 with Guide D8321 in Section 2

and Table A1.3.

Subcommittee D02.96 has identified the location of selected changes to this standard since the last issue
(E2412 – 10 (2018)) that may impact the use of this standard. (Approved May 1, 2023.)

(1) Added Terminology D4175 to Sections 2 and 3.

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