ASTM D6443-14(2019)e1
(Test Method)Standard Test Method for Determination of Calcium, Chlorine, Copper, Magnesium, Phosphorus, Sulfur, and Zinc in Unused Lubricating Oils and Additives by Wavelength Dispersive X-ray Fluorescence Spectrometry (Mathematical Correction Procedure)
Standard Test Method for Determination of Calcium, Chlorine, Copper, Magnesium, Phosphorus, Sulfur, and Zinc in Unused Lubricating Oils and Additives by Wavelength Dispersive X-ray Fluorescence Spectrometry (Mathematical Correction Procedure)
SIGNIFICANCE AND USE
4.1 Lubricating oils can be formulated with additives, which can act as detergents, anti-oxidants, anti-wear agents, and so forth. Some additives can contain one or more of calcium, copper, magnesium, phosphorus, sulfur, and zinc. This test method can be used to determine if the oils, additives, and additive packages meet specification with respect to content of these elements.
4.2 Several additive elements and their compounds are added to the lubricating oils to give beneficial performance (Table 3).
4.3 This test method can also be used to determine if lubricating oils, additives, and additive packages meet specification with respect to chlorine concentration. In this context, specification can refer to contamination.
4.4 This test method is not intended for use on samples that contain some component that significantly interferes with the analysis of the elements specified in the scope.
4.5 This test method can complement other test methods for lube oils and additives, including Test Methods D4628, D4927, D4951, and D5185.
SCOPE
1.1 This test method covers the determination of calcium, chlorine, copper, magnesium, phosphorus, sulfur, and zinc in unused lubricating oils, additives, and additive packages by wavelength dispersive X-ray fluorescence spectrometry. Matrix effects are handled with mathematical corrections.
1.2 For each element, the upper limit of the concentration range covered by this test method is defined by the highest concentration listed in Table 1. Samples containing higher concentrations can be analyzed following dilution.
1.3 For each element, the lower limit of the concentration range covered by this test method can be estimated by the limit of detection (LOD)2 (see also 40 CFR 136 Appendix B) or limit of quantification (LOQ),2 both of which can be estimated from Sr, the repeatability standard deviation. LOD and LOQ values, determined from results obtained in the interlaboratory study on precision, are listed in Table 2.
1.3.1 LOD and LOQ are not intrinsic constants of this test method. LOD and LOQ depend upon the precision attainable by a laboratory when using this test method.
1.4 This test method uses regression software to determine calibration parameters, which can include influence coefficients (that is, interelement effect coefficients) (Guide E1361), herein referenced as alphas. Alphas can also be determined from theory using relevant software.
1.5 Setup of this test method is intended for persons trained in the practice of X-ray spectrometry. Following setup, this test method can be used routinely.
1.6 The values stated in either SI units or angstrom (Å) units are to be regarded separately as standard.
1.7 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of regulatory limitations prior to use.
1.8 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.
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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.
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Designation: D6443 − 14 (Reapproved 2019)
Standard Test Method for
Determination of Calcium, Chlorine, Copper, Magnesium,
Phosphorus, Sulfur, and Zinc in Unused Lubricating Oils
and Additives by Wavelength Dispersive X-ray Fluorescence
Spectrometry (Mathematical Correction Procedure)
This standard is issued under the fixed designation D6443; 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.
ε NOTE—Subsection 7.5.2 was editorially corrected in July 2019.
1. Scope 1.6 ThevaluesstatedineitherSIunitsorangstrom(Å)units
are to be regarded separately as standard.
1.1 This test method covers the determination of calcium,
1.7 This standard does not purport to address all of the
chlorine, copper, magnesium, phosphorus, sulfur, and zinc in
safety concerns, if any, associated with its use. It is the
unused lubricating oils, additives, and additive packages by
responsibility of the user of this standard to establish appro-
wavelength dispersive X-ray fluorescence spectrometry. Ma-
priate safety, health, and environmental practices and deter-
trix effects are handled with mathematical corrections.
mine the applicability of regulatory limitations prior to use.
1.2 For each element, the upper limit of the concentration
1.8 This international standard was developed in accor-
range covered by this test method is defined by the highest
dance with internationally recognized principles on standard-
concentration listed in Table 1. Samples containing higher
ization established in the Decision on Principles for the
concentrations can be analyzed following dilution.
Development of International Standards, Guides and Recom-
mendations issued by the World Trade Organization Technical
1.3 For each element, the lower limit of the concentration
range covered by this test method can be estimated by the limit Barriers to Trade (TBT) Committee.
of detection (LOD) (see also 40 CFR 136 Appendix B) or
2. Referenced Documents
limit of quantification (LOQ), both of which can be estimated
from S , the repeatability standard deviation. LOD and LOQ
2.1 ASTM Standards:
r
values, determined from results obtained in the interlaboratory
D1552 Test Method for Sulfur in Petroleum Products by
study on precision, are listed in Table 2.
High Temperature Combustion and Infrared (IR) Detec-
1.3.1 LOD and LOQ are not intrinsic constants of this test tion or Thermal Conductivity Detection (TCD)
method. LOD and LOQ depend upon the precision attainable D4057 Practice for Manual Sampling of Petroleum and
by a laboratory when using this test method. Petroleum Products
D4177 Practice for Automatic Sampling of Petroleum and
1.4 This test method uses regression software to determine
Petroleum Products
calibration parameters, which can include influence coeffi-
D4307 Practice for Preparation of Liquid Blends for Use as
cients (that is, interelement effect coefficients) (Guide E1361),
Analytical Standards
herein referenced as alphas. Alphas can also be determined
D4628 Test Method for Analysis of Barium, Calcium,
from theory using relevant software.
Magnesium, and Zinc in Unused Lubricating Oils by
1.5 Setup of this test method is intended for persons trained
Atomic Absorption Spectrometry
inthepracticeofX-rayspectrometry.Followingsetup,thistest
D4927 Test Methods for Elemental Analysis of Lubricant
method can be used routinely.
and Additive Components—Barium, Calcium,
Phosphorus, Sulfur, and Zinc by Wavelength-Dispersive
X-Ray Fluorescence Spectroscopy
D4951 Test Method for Determination ofAdditive Elements
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
Subcommittee D02.03 on Elemental Analysis.
CurrenteditionapprovedMay1,2019.PublishedJuly2019.Originallyapproved For referenced ASTM standards, visit the ASTM website, www.astm.org, or
in 1999. Last previous edition approved in 2014 as D6443 – 14. DOI: 10.1520/ contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
D6443-14R19E01. Standards volume information, refer to the standard’s Document Summary page on
Analytical Chemistry, Vol 55, pp. 2210–2218. the ASTM website.
Copyright ©ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA19428-2959. United States
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D6443 − 14 (2019)
TABLE 1 Calibration Standard Compositions, Concentrations in
which include influence coefficients (that is, alphas) calculated
Mass %
from theory, empirical data, or a combination of theory and
Std. No. Ca Cl Cu Mg P S Zn
empirical data.
1 0.02 0.02 0.01 0.20 0.25 1.00 0.02
2 0.02 0.02 0.05 0.20 0.02 0.02 0.25 4. Significance and Use
3 0.02 0.20 0.01 0.05 0.25 0.02 0.25
4.1 Lubricatingoilscanbeformulatedwithadditives,which
4 0.02 0.20 0.05 0.05 0.02 1.00 0.02
5 0.40 0.02 0.01 0.05 0.02 1.00 0.25
can act as detergents, anti-oxidants, anti-wear agents, and so
6 0.40 0.02 0.05 0.05 0.25 0.02 0.02
forth. Some additives can contain one or more of calcium,
7 0.40 0.20 0.01 0.20 0.02 0.02 0.02
copper, magnesium, phosphorus, sulfur, and zinc. This test
8 0.40 0.20 0.05 0.20 0.25 1.00 0.25
9 0.20 0.10 0.03 0.10 0.10 0.50 0.10
method can be used to determine if the oils, additives, and
10 0 0 0 000 0
additive packages meet specification with respect to content of
these elements.
4.2 Several additive elements and their compounds are
TABLE 2 Estimated LOD and LOQ, Units are Mass %
added to the lubricating oils to give beneficial performance
Ca Cl Cu Mg P Zn
LOD 0.0002 0.0004 0.0002 0.0039 0.0006 0.0002
(Table 3).
LOQ 0.0008 0.0015 0.0007 0.0130 0.0020 0.0007
4.3 This test method can also be used to determine if
lubricating oils, additives, and additive packages meet specifi-
cation with respect to chlorine concentration. In this context,
in Lubricating Oils by Inductively Coupled Plasma
specification can refer to contamination.
Atomic Emission Spectrometry
4.4 This test method is not intended for use on samples that
D5185 Test Method for Multielement Determination of
contain some component that significantly interferes with the
Used and Unused Lubricating Oils and Base Oils by
analysis of the elements specified in the scope.
Inductively Coupled Plasma Atomic Emission Spectrom-
etry (ICP-AES)
4.5 This test method can complement other test methods for
D6299 Practice for Applying Statistical Quality Assurance
lubeoilsandadditives,includingTestMethodsD4628,D4927,
and Control Charting Techniques to Evaluate Analytical
D4951, and D5185.
Measurement System Performance
5. Interferences
E29 Practice for Using Significant Digits in Test Data to
Determine Conformance with Specifications
5.1 The additive elements can affect the magnitudes of the
E1361 Guide for Correction of Interelement Effects in
measured intensities for each analyte. In general, the
X-Ray Spectrometric Analysis
X-radiation emitted by each analyte can be absorbed by the
2.2 Government Standard:
other elements.Also, the X-radiation emitted by an analyte can
40 CFR, 136 Appendix B, Definition and Procedure for the
be enhanced by some other component. The magnitudes of the
Determination of the Method Detection Limit—Revision
absorption and enhancement effects can be significant.
1.11, pp. 265–267
However, implementation of accurately determined alphas in
the set of calibration parameters can satisfactorily correct for
3. Summary of Test Method
absorption and enhancement effects, thereby making this test
3.1 The X-ray fluorescence spectrometer is initially cali- method quantitative.
brated by the following procedure. For each element, the slope
5.2 Molybdenum lines can spectrally overlap lines of
and intercept of the calibration curve are determined by
magnesium, phosphorus, sulfur, and chlorine. Lead lines can
regressing concentration data and intensities measured on a set
spectrally overlap sulfur. Thus, this test method cannot be
of physical standards. Empirical alphas can also be determined
applied if molybdenum or lead are present at significant
by regression when the appropriate set of physical standards is
concentrations and if accurate overlap corrections cannot be
used for calibration.Theoretical alphas, calculated with special
made.
software, can also be used. In addition, a combination of
5.3 When a large d-spacing diffraction structure containing
theoretical and empirical alphas can be used.
silicon is used as the analyzing crystal, corrections for the
3.2 AsampleisplacedintheX-raybeam,andtheintensities
fluorescence of silicon may be needed. Calcium X rays from
of the appropriate fluorescence lines are measured. A similar
sample specimens cause silicon to fluoresce. This silicon
measurement is made at a wavelength offset from each
radiation contributes to fluctuations in the background for
fluorescence line in order to obtain a background correction.
magnesium measurements. If the effect is significant, this
Enhancement or absorption of the X-ray fluorescence of an
interference may be treated as a line overlap due to calcium.
analyte by an interfering element in the sample can occur, and
6. Apparatus
these effects can be handled in the data reduction by imple-
mentation of alphas. Concentrations of the analytes are deter-
6.1 X-ray Spectrometer,equippedfordetectionofsoftX-ray
mined by comparison of net signals against calibration curves,
radiation in the range from 1 Å to 10 Å. For optimum
sensitivity, the spectrometer is equipped with the following:
6.1.1 X-ray Tube Source, with chromium, rhodium, or
AvailablefromU.S.GovernmentPrintingOfficeSuperintendentofDocuments,
732 N. Capitol St., NW, Mail Stop: SDE, Washington, DC 20401. scandium target. Scandium can be advantageous for sensitivity
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D6443 − 14 (2019)
TABLE 3 Lubricants and Additive Materials
Element Compounds Purpose/Application
Calcium Sulfonates, phenates Detergent inhibitors, dispersants
Chlorine Trace contaminants, chlorinated cleaning solvents Avoid servo-valve erosion, dewaxing compounds
Copper Copper dithiophosphates Anti-wear agent, anti-oxidant
Magnesium Sulfonates, phenates Detergent inhibitors
Phosphorus dithiophosphates, phosphates phosphites anti-rusting agents, extreme pressure additives, anti-wear
Sulfur Base oils, sulfonates, thiophosphates, polysulfides Detergents, extreme pressure additives, anti-wear
and other sulfurized components
Zinc Dialkyldithiophosphates, dithiocarbamates, Anti-oxidant, corrosion inhibitors, antiwear additives, detergents, crankcase
phenolates carboxylates oils, hypoid gear lubricants, aircraft piston engine oils, turbine oils, automatic
transmission fluids, railroad diesel engine oils, brake lubricants
Other satisfactory gases or gas mixtures can be applicable.
enhancement of the low atomic number analytes. Other targets
may also be employed. Avoid spectral interferences from tube
7.4 Dilution Solvent, a hydrocarbon solvent, which does not
lines on the analyte lines.
contain a detectable amount of any analyte. U.S.P. white
6.1.2 Helium, purgeable optical path.
(mineral) oil has been found to be satisfactory.
6.1.3 Interchangeable Analyzer Crystals, germanium,
7.5 Calibration Standard Materials:
lithium fluoride (LiF ), graphite, pentaerythritol (PE), or a
7.5.1 Concentrated Solutions of Oil-soluble Compounds,
50 Å diffraction structure, or a combination thereof. Other
each containing one of the following: calcium, copper,
suitable crystals can be used.
magnesium, phosphorus, or zinc.
6.1.4 Pulse-Height Analyzer.
7.5.1.1 Some commercially available oil-soluble standard
6.1.5 Detector, gas flow proportional, or tandem gas flow
materials are prepared from sulfonates and therefore contain
proportional and scintillation counter.
sulfur. To use these materials for preparation of the calibration
NOTE 1—A gas sealed proportional counter was used in the interlabo-
standard blends, it is necessary to know their sulfur concen-
ratory study on precision and was found to be satisfactory.
trations.TestMethodD1552,orotherappropriatemethods,can
6.2 Mixing Device Such as a Shaker, Ultrasonic Bath, or
be used to determine sulfur content.
Vortex Mixer, capable of handling from 30 mL to 1 L bottles.
7.5.1.2 Secondary standards, such as those prepared from
6.3 X-ray Disposable Plastic Cells, with suitable film win-
petroleum additives, for example, can also be used if their use
dow. Suitable films can include polyester, polypropylene, or
does not affect the analytical results by more than the repeat-
polyimide. A film thickness of 4 µm is preferred. Avoid using
ability of this test method.
film that contains any of the analytes.
7.5.2 Di-n-butyl Sulfide, a high-purity standard with a cer-
tified analysis for total sulfur content. (Warning—Di-n-butyl
7. Reagents and Materials
sulfide is flammable and toxic.)
7.1 Purity of Reagents—Reagent grade chemicals shall be
7.5.3 Oil-soluble Chlorine-containing Compound, a high
used in all tests. Unless otherwise indicated, it is intended that
purity standard with a certified analysis for total chlorine
all reagents conform to the specifications of the Committee on
content.
Analytical Reagents of theAmerican Chemical Society, where
7.5.4 Stabilizers, Stabilizers can be used to ensure unifor-
such specifications are available. Other grades can be used,
mity of the calibration standard blends. Use stabilizers that do
provided it is first ascertained that the reagent is of sufficiently
not contain a detectable amount of any analyte.
high purity to permit its use without lessening the accuracy of
the determination.
8. Sampling and Sample Handling
7.2 Helium, preferably ultrahigh purity (at least 99.95 %),
8.1 Take samples in accordance with the instructions in
for optical path of spectrometer.
Practice D4057 or D4177, when applicable.
7.3 P-10 Ionization Gas, 90 volume % argon and 10 vol-
8.2 Mixwellsamplesandcalibrationstandardblendsbefore
ume % methane for the flow proportional counter.
introduction into the X-ray instrument.
NOTE 2—P-10 gas was used in the interlaboratory study on precision.
9. Preparation of Calibration Standards
9.1 Prepare calibration standard blends by accurate dilution
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
of the oil-soluble standard solutions with the dilution solvent.
listed by the American Chemical Society, see Annual Standards
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