Professional Documents
Culture Documents
Field Determination of In-Service Fluid Properties Using IR Spectros
Field Determination of In-Service Fluid Properties Using IR Spectros
Field Determination of In-Service Fluid Properties Using IR Spectros
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
1
D7889 − 13
definition of terms related to infrared-based in-service fluid Group I-IV) fluids include those established for Oxidation
condition monitoring, refer to Practice D7418. (Test Method D7414, Procedure A), Antiwear Additive (Test
3.2 Definitions of Terms Specific to This Standard: Method D7412, Procedure A), Sulfation (Test Method D7415,
3.2.1 absorbance units (AU), n—units of measurement of Procedure A), Nitration (Test Method D7624, Procedure A),
the raw absorbance spectrum which is obtained using the and Soot (Test Method D7844, Procedure A). These test
definition described in Section 8 (Theory for a Single Com- methods have served to establish the signature infrared spec-
pound Analysis) of Practice E168, which is not normalized for troscopic behavior associated with key in-service monitoring
pathlength. properties. This test method provides property values based on
the examination of each property’s signature infrared spectro-
3.2.2 cell background, n—a single-beam spectrum that is scopic behavior. The essence of this test method is to capture
obtained on a clean, empty wipe-clean transmission cell. the underlying chemical trends associated with each property
3.2.3 mid-infrared grating spectrometer, n—a spectrometer for in-service fluid analysis using a self-contained field appa-
which operates in the mid-infrared spectral range, between at ratus and coupled wipe-clean transmission cell.
least 960 cm-1 and 3040 cm-1 and creates an infrared spectrum 4.1.2 From the infrared absorbance spectrum obtained with
by means of a reflective diffraction grating. the self-contained field apparatus, properties of the in-service
3.2.3.1 Discussion—Such a grating spectrometer may be of fluid are calculated. In particular, those properties in Table 1
any of a variety of designs and optical configurations. Example are calculated by the device and presented to the user on the
designs include monochrometer-type systems wherein the display. Additional properties using infrared calibration meth-
grating is rotated to a single point infrared detector, or ods may be calculated and displayed depending on the particu-
array-type systems which utilize an infrared detector array at lar fluid being analyzed and availability of calibrations for that
the output and a fixed grating. Example optical configurations fluid.
include Rowland-Circle and Czerny-Turner systems. Typical 4.1.2.1 Infrared spectra generated by the described instru-
infrared detectors are uncooled thermal detectors such as ment type can be used to provide a further set of properties of
thermopile or pyroelectric-based sensors. interest to in-service fluid analysis of hydrocarbon type (API
3.2.4 reporting units, n—specifies the reporting units of the Group I-IV) fluids. Such properties must be calibrated to the
fluid analysis property. particular fluid blend, and may be generated using ASTM
3.2.5 self-contained field apparatus, n—a mid-infrared grat- guidelines which govern the creation of such calibrations. Such
ing spectrometer which is of the form factor to allow it to calibrations may be built from either standard regression
operate as an independent device suitable for field use. methods as described in Practice E168 or as described in
Practice E2412. Further, they may also be multivariate
3.2.6 wipe-clean transmission cell, n—an infrared transmis- calibrations, described in Practice E1655 and Practice E2617.
sion cell which is specifically tailored for field use. Example properties include Acid Number (AN), Base Number
3.2.6.1 Discussion—In particular, the cell may be utilized (BN), water contamination, ethylene glycol, fluid mixture
and cleaned with a towel or rag and without the use of reagents content, and antioxidant depletion. It should be noted that, due
or chemicals of any sort, making it convenient for use as a field to the fact that these calibrations are sample-specific, this test
device. Such transmission cells may accomplish this using method does not provide a prescription for calculating such
mechanisms for quick open/close of the cell such as by means properties.
of a mechanical lever, demountable screw or press fit, or
magnetic coupling. To correct for any cell fringing effects, the 4.2 The results of the test method can be compared against
cell utilizes a wedged design both on the interior faces and pre-defined or user-defined limits so as to judge the condition
exterior faces of the cell windows: The cell windows them- of the in-service lubricant. Warning and alarm limits ex-
selves are wedged at an angle of less than 0.5 degrees. The ceedences which may be pre-defined or set by the user are
spacing between the two windows is wedged at an angle of indicated by the property and associated value being high-
approximately 0.013 degrees. The cell is designed to be lighted using coding established in Guide D7720, with either
nominally 100 µm in pathlength, with ZnSe windows. green (favorable alarm level designation showing acceptable
condition), yellow (intermediate level alarm designation warn-
4. Summary of Test Method ing a fault condition is present and will likely need attention in
the future), or red (high level alarm designation showing
4.1 This test method utilizes a self-contained field apparatus
significant deterioration) indicated by the self-contained field
to provide detailed information concerning the condition status
apparatus.
of in-service fluids. In particular, it provides readings of
oxidation, antiwear additive, sulfation, nitration and soot levels
in hydrocarbon type (API Group I-IV) fluids. TABLE 1 In-Service Lubricant Properties Reported by the Test
4.1.1 An absorbance spectrum of the sample under test is Method
obtained. For the background spectrum, the cell background is Property Reporting Units
used. Oxidation Abs/0.1 mm
4.1.1.1 Test Methods have been developed for Fourier- Antiwear Additive Abs/0.1 mm
transform infrared (FTIR) devices using absorbance spectra Sulfation Abs/0.1 mm
Nitration Abs/cm
obtained using Practice D7418. Particular Test Methods devel- Soot Abs/cm
oped for in-service monitoring of hydrocarbon type (API
2
D7889 − 13
5. Significance and Use TABLE 2 Specification for Calculation of Each In-Service Fluid
Property
5.1 This test method provides a means for obtaining useful Property Measurement, Baseline(s), Reporting
in-service fluid analysis properties in the field. It is not to be (cm-1) (cm-1) Units
confused with laboratory or portable FTIR devices which Oxidation Average Average Abs/0.1 mm
1800–1670 1815 to 1805
provide measurements per the existing Test Methods listed in
4.1.1.1. Each of these monitored properties has been shown Antiwear Additive Average Average Abs/0.1 mm
over time to indicate either contamination in the fluid system or 1025–960 1060 to 1030 and
1812 to 1803
a particular breakdown modality of the fluid, which is critical
information to assess the health of the fluid as well as the Sulfation Average Average Abs/0.1 mm
1180–1120 1210 to 1200 and
machinery. By utilizing the field device, it is possible for those 1115 to 1105
operating machinery, in locations and situations where it is not
practical to gather a sample for the laboratory, to obtain quality Nitration 100·Single Average Abs/cm
Point at 1630 1607 to 1597 and
in-service fluid analysis. This may be due to the need to have 1847 to 1837
an analysis done in real-time, on-the-spot to maximize the
operational hours of equipment, or to have the analysis Soot 100·Single None Abs/cm
Point at 2000
performed at a location where no laboratory analysis is
available.
3
D7889 − 13
fully loaded. Such a check is performed according to manu- 15.1.1 Properties are obtained from the absorbance spec-
facturer’s recommendations. trum using the measurement and baseline regions listed in
11.1.3.1 If the cell is determined to not be fully loaded, a Table 2. Properties are presented to the user in the reporting
message that the cell is not fully loaded is displayed alongside units specified.
the results of the analysis. It should be noted that due to the 15.1.1.1 Oxidation is obtained from calculating the average
nature of the design for field use, the wipe clean transmission absorbance (Abs/0.1 mm) in the measurement region between
cell has no need for fringe correction. 1800 cm-1 and 1670 cm-1 Abs,av(1800 to 1670) and performing
11.2 Ensure that wipe-clean transmission cell is clean by a weighted subtraction from the average baseline absorbance
visual inspection. (Abs/0.1 mm) in the region between 1815 cm-1 and 1805 cm-1
Abs,av(1815 to 1805). The resulting units of measurement are
11.3 Gather approximately two drops of sample (on the Abs/0.1 mm:
order of 50 µL).
11.3.1 This may be accomplished using a dropper, syringe, Oxidation=130 · Abs,av~ 1800 to 1670!
or simply by using drops from a fluid dipstick, for example. 2 38.5 · Abs,av~ 1815 to 1805! @ Abs/0.1 mm# (2)
12. Calibration and Standardization 15.1.1.2 Antiwear additive is obtained from calculating the
average absorbance (Abs/0.1 mm) in the measurement region
12.1 A check fluid is supplied with the apparatus as a between 1025 cm-1 and 960 cm-1 Abs,av(1025 to 960) and
qualification test. This fluid should be run after each set of 100 performing a weighted subtraction from the average baseline
samples to ensure that the unit remains within calibration. absorbance (Abs/0.1 mm) in the region between 1060 cm-1 and
12.2 If this qualification test fails, the user should follow 1030 cm-1 Abs,av(1060 to 1030) as well as the region between
manufacturer’s recommendations regarding calibration and 1812 cm-1 and 1803 cm-1 Abs,av(1812 to 1803). The resulting
standardization. units of measurement are Abs/0.1 mm:
Antiwear Additive 5 65 · Abs,av~ 1025 to 960!
13. Conditioning
2 8.4 · Abs,av~ 1060 to 1030!
13.1 The field apparatus does not require conditioning nor
does the sample being analyzed. 2 10.8 · Abs,av~ 1812 to 1803! @ Abs/0.1 mm# (3)
15. Calculation or Interpretation of Results 2 0.11 · Abs,av~ 1847 to 1837!! @ Abs/ cm#
(5)
15.1 Calculation of in-service fluid properties proceeds
according to the spectral analysis detailed in Table 2. These 15.1.1.5 Soot is calculated by measuring the absorbance of
analyses proceed using the signature infrared absorption bands the sample at 2000 cm-1 (Abs/0.1 mm) and multiplying the
gleaned from the obtained infrared absorbance spectrum of the result by 100, yielding a result in units of Abs/cm. This allows
fluid. for numerical results in a typical range of 0-100 Abs/cm.
4
D7889 − 13
15.1.2 In the following we provide examples for each of the 15.1.2.4 Nitration Example—Fig. 4 presents a schematic
five (5) properties detailed in 15.1.1: illustration of the calculation for the nitration property. In this
15.1.2.1 Oxidation Example—Fig. 1 presents a schematic case, the absorbance at 1630 cm-1 is 0.246 Abs/0.1 mm, and the
illustration of the calculation for the oxidation property. In this baseline averages are 0.22 Abs/0.1 mm and 0.004 Abs/0.1 mm
case, the average value of absorbance in the oxidation mea- for the low and high frequency baselines, respectively. This
surement region is approximately 0.1216 Abs/0.1 mm, and the yields a nitration value of 5 Abs/cm:
baseline average is -0.005 Abs/0.1 mm. This yields an oxida- Nitration 5 100 · ~ 0.246 2 0.89 · ~ 0.22! 2 0.11 · ~ 0.004!!
tion value of 16 Abs/0.1 mm:
5 5 @ Abs/cm# (9)
Oxidation = 130 · ~ 0.1216! 2 38.5 · ~ 2 0.005! 5 16 @ Abs/0.1 mm#
15.1.2.5 Soot Example—Fig. 5 presents a schematic illus-
(6)
tration of the calculation of soot. In this case, the absorbance at
15.1.2.2 Antiwear Additive Example—Fig. 2 presents a 2000 cm-1 is 0.31 Abs/0.1 mm. Multiplying this value by 100
schematic illustration of the calculation for the antiwear we obtain a soot value of 31 Abs/cm:
additive property. In this case, the average value of absorbance Soot 5 100 · ~ 0.31! 5 31 @ Abs/cm# (10)
in the antiwear additive measurement region is approximately
0.385 Abs/0.1 mm, and the baseline averages are 0.298 Abs/0.1 15.1.3 These methods are chosen so as to give the user a
mm and 0.165 Abs/0.1 mm for the low and high frequency reported value which does not rely on any spectral reference.
baselines, respectively. This yields an antiwear additive value This is in keeping with the apparatus being used as a field tool.
of 20.7 Abs/0.1 mm: 15.1.4 Limits for each particular fluid of interest may be
tailored considering the typical range of that particular fluid.
Antiwear Additive 5 65 · ~ 0.385! 2 8.4 · ~ 0.298! 2 10.8 · ~ 0.165!
5 20.7 @ Abs/0.1 mm# (7) 16. Report
15.1.2.3 Sulfation Example—Fig. 3 presents a schematic 16.1 Properties are calculated as described in Section 15 and
illustration of the calculation for the sulfation property. In this reported in units as described in Table 2.
case, the average value of absorbance in the sulfation measure-
16.2 Trending and Alarm Limits—As defined by the user,
ment region is approximately 0.258 Abs/0.1 mm, and the
the apparatus will acquire, report, and log the fluid measured
baseline averages are 0.168 Abs/0.1 mm and 0.285 Abs/0.1 mm
properties on a periodic basis. The user may monitor this
for the low and high frequency baselines, respectively. This
trending behavior and as well set alarm limits in the apparatus
yields a sulfation value of 11.5 Abs/0.1 mm:
for each particular fluid being analyzed. Guidance on perform-
Sulfation 5 60 · ~ 0.258! 2 11 · ~ 0.285! 2 5 · ~ 0.168! ing trending analysis and setting alarm limits on in-service
5 11.5 @ Abs/0.1 mm# (8) lubricants is provided in Guide D7669 and Guide D7720.
5
D7889 − 13
16.3 Effects of Fluid Formulation—For each measured 17. Precision and Bias
property, the reported values as well as the trending tendencies
17.1 A temporary precision statement including repeatabil-
are in general different for each fluid type. The apparatus may
be designed so that each fluid type may be tracked separately ity is reported in Table 3 based on analyzing five samples tested
with trend histories being viewed and alarm limits set on the thirty times each in the same laboratory. Full precision and bias
apparatus per these fluid types.
6
D7889 − 13
7
D7889 − 13
statements based on interlaboratory round robin testing will be vices; infrared spectroscopy; in-service fluid analysis; multi-
determined within five years of adoption of this standard variate analysis; nitration; oxidation; soot; sulfation
method.
18. Keywords
18.1 antiwear additives; condition monitoring; direct trend-
ing; field-based devices; grating spectrometers; handheld de-
ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned
in this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk
of infringement of such rights, are entirely their own responsibility.
This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and
if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards
and should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the
responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should
make your views known to the ASTM Committee on Standards, at the address shown below.
This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,
United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above
address or at 610-832-9585 (phone), 610-832-9555 (fax), or service@astm.org (e-mail); or through the ASTM website
(www.astm.org). Permission rights to photocopy the standard may also be secured from the ASTM website (www.astm.org/
COPYRIGHT/).